Battery Energy - 2023 - Wulandari - Lithium Based Batteries History Current Status Challenges and Future Perspectives

Received: 21 July 2023 | Revised: 27 August 2023 | Accepted: 11 September 2023
DOI: 10.1002/bte2.20230030
REVIEW
Lithium‐based batteries, history, current status,

challenges, and future perspectives
Triana Wulandari1 | Derek Fawcett1 | Subhasish B. Majumder2 |

Gerrard E. J. Poinern1
1
Murdoch Applied Nanotechnology
Research Group, School of Engineering Abstract
and Energy, School of Mathematics, Currently, the main drivers for developing Li‐ion batteries for efficient energy
Statistics, Chemistry and Physics,
Murdoch University, Murdoch,
applications include energy density, cost, calendar life, and safety. The high
Western Australia, Australia energy/capacity anodes and cathodes needed for these applications are
2
Materials Science Center, Indian hindered by challenges like: (1) aging and degradation; (2) improved safety; (3)
Institute of Technology, Kharagpur, India
material costs, and (4) recyclability. The present review begins by summarising the
Correspondence progress made from early Li‐metal anode‐based batteries to current commercial
Gerrard E. J. Poinern, Murdoch Applied Li‐ion batteries. Then discusses the recent progress made in studying and
Nanotechnology Research Group, School
developing various types of novel materials for both anode and cathode electrodes,
of Engineering and Energy, School of
Mathematics, Statistics, Chemistry and as well the various types of electrolytes and separator materials developed
Physics, Murdoch University, Murdoch, specifically for Li‐ion battery operation. Battery management, handling, and safety
WA 6150, Australia.
Email: [email protected]
are also discussed at length. Also, as a consequence of the exponential growth in
the production of Li‐ion batteries over the last 10 years, the review identifies the
challenge of dealing with the ever‐increasing quantities of spent batteries. The
review further identifies the economic value of metals like Co and Ni contained
within the batteries and the extremely large numbers of batteries produced to date
and the extremely large volumes that are expected to be manufactured in the next
10 years. Thus, highlighting the need to develop effective recycling strategies to
reduce the levels of mining for raw materials and prevention of harmful products
from entering the environment through landfill disposal.
KEYWORDS
electrode materials, electrolytes, lithium ion batteries, recyclability, separators
1 | INTRODUCTION Accordingly, in recent years there has been a rapid

increase in the development and usage of renewable
An important global objective is to reduce the emission of energy sources to replace traditional fossil fuel‐based
greenhouse gases and remediate the effects of global electrical power generation and transport systems. How-
warming.1 Therefore, there is an imperative need to ever, harvesting renewable energy from sources like solar
develop eco‐friendly and sustainable green energy‐based and wind is fraught with intermittent energy supply.
technologies to replace fossil fuel‐powered technologies. Therefore, developing large‐scale energy storage systems
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided
the original work is properly cited.
© 2023 The Authors. Battery Energy published by Xijing University and John Wiley & Sons Australia, Ltd.
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designed to store energy during high harvesting periods damage resulting from electric vehicle collisions can
and then releasing energy during low harvesting periods is compromise battery integrity and subsequently lead to
paramount. And recent advancements in rechargeable fire, explosion, and ultimate failure.19,20 While aviation
battery‐based energy storage systems has proven to be an safety incidents involving internal short circuits in Li‐ion
effective method for storing harvested energy and subse- battery‐based auxiliary power units on board aircraft have
quently releasing it for electric grid applications.2–5 also resulted in thermal runaway and fire.21,22
Importantly, since Sony commercialised the world's first Safety issues involving Li‐ion batteries have focused
lithium‐ion battery around 30 years ago, it heralded a research into improving the stability and performance of
revolution in the battery market and the rapid development battery materials and components. This review discusses
of portable electronic devices and portable power tools.6–8 the fundamental principles of Li‐ion battery operation,
Prechargeable battery‐based technologies have become technological developments, and challenges hindering
an important part of building a sustainable energy source their further deployment. The review not only discusses
that does not contribute to greenhouse gas emissions. traditional Li‐ion battery materials but also examines
Among rechargeable batteries, Lithium‐ion (Li‐ion) batte- recent research involved in developing new high‐capacity
ries have become the most commonly used energy supply anodes, cathodes, electrolytes, and separators. Aging
for portable electronic devices such as mobile phones and mechanisms, active material degradation processes safety
laptop computers and portable handheld power tools like concerns, and strategies to overcome these challenges
drills, grinders, and saws.9,10 Crucially, Li‐ion batteries are discussed. The review is divided into eight major
have high energy and power densities and long‐life cycles, sections. After the introduction, the second section
which also makes them ideal for electrical vehicles.11 presents a brief history of electrical storage devices and
From an environmental perspective, if gasoline and diesel‐ early Li‐ion batteries. In the third section, the review
powered vehicles were replaced by electric vehicles, the discusses the operational principles of rechargeable
subsequent reduction in greenhouse gas emissions would Li‐ion batteries. While the current state of research into
significantly reduce the current global warming trend.12,13 major Li‐ion battery components (anodes, cathodes,
Therefore, to support this transition, the manufacture of electrolytes, and separators) is discussed in Section 4.
Li‐ion batteries is predicted to increase exponentially Section 5 discusses the major challenges facing Li‐ion
during this decade. Significantly, in 2019, the Nobel Prize batteries: (1) temperature‐induced aging and thermal
in Chemistry was awarded to John Goodenough, Stanley management; (2) operational hazards (overcharging,
Whittingham, and Akira Yoshino for developing Li‐ion swelling, thermal runaway, and dendrite formation); (3)
batteries. handling and safety; (4) economics, and (5) recycling
However, despite their advantages and wide‐ranging battery materials. And in the final Section 6, the
applications, Li‐ion batteries suffer from aging mecha- conclusion and future perspectives are discussed.
nisms, active material degradation processes, and safety
concerns.14 Operationally, battery longevity is affected by
factors like operating temperature, depth of discharge, 2 | BRIEF HISTORY ELECTRICAL
charge/discharge current rates, and periods between full‐ S T O R A G E DE V IC E S A N D E A R L Y
charge cycles. Each of these factors, including the design LI ‐ IO N BA T TER I ES
and manufacturing of the Li‐ion battery itself, need to be
fully understood and addressed so that aging mechanisms The evolution of electrical storage devices started with
and degradation processes are kept to a minimum.15,16 the discovery of electrostatic effects and electrostatic
Nonetheless, the majority of currently available Li‐ion storage devices. But the first practical method used for
batteries do not meet all these factors. Crucially, safety generating a steady electrical current was the electro-
concerns are still the most important issue facing the chemical battery that was first invented by Italian
large‐scale adoption of Li‐ion batteries in some portable physicist Alessandro Volta in 1800.23 His studies revealed
electronic devices and in the transport sector. For the action of seawater on a number of metals tended to
instance, in terms of portable electronic devices, around produce an excess or deficiency of electrons on metals.
195 fires and explosions were reported between 2009 and The discovery of this phenomena led Volta to build the
2016 for Li‐ion batteries used in electronic cigarettes.17 voltaic pile, a battery that consisted of a series of
Similarly, a battery manufacturing defect present in electrical cells, with each cell containing a copper disk
innumerable Samsung Galaxy 7 mobile phones during and a zinc disk separated by a pasteboard moistened
2017 resulted in thermal runaway, fire, and ultimate with a conducting fluid. Since Volta's time significant
failure.18 Moreover in the transport sector, factors such as advancements and progress has been made towards
careless over charging/over discharging and mechanical developing a wide range of electrochemical batteries.
WULANDARI ET AL. | 3 of 53
Over this period two different types of batteries were vehicles have the potential to transform the transportation
developed and are classified as either primary (disposable) sector by replacing conventional fossil fuel‐powered
or secondary (nondisposable). During the operation of vehicles and contribute to a significant reduction of
primary batteries, the active materials are consumed by greenhouse gas emissions.34 Moreover, environmental
the chemical reactions that generate the electrical current. concerns are also promoting the use of high energy
Thus, the chemical reactions are irreversible and when efficiency Li‐ion battery‐based storage systems for use in
electrically energy can no longer be generated, the active various eco‐friendly electric grid applications that harvest
materials need to be replenished. But in reality these energy from renewable sources like geothermal, hydro‐
batteries are used only once, cannot be recharged and electrical, solar, and wind.35 Thus, replacing conventional
are discarded. A typical example of a primary battery is fossil fuel‐based electrical power generation systems and
the zinc–carbon battery that is used in torches and in the process adopting a more energy‐sustainable global
portable electronic devices.24 Secondary batteries, which economy.
are also known as rechargeable batteries, can be cyclically Historically, lithium was independently discovered
operated by discharging and recharging. The recyclable during the analysis of petalite ore (LiAlSi4O10) samples in
function is derived from the reversible electrochemical 1817 by Arfwedson and Berzelius.36,37 However, it was not
reactions that restore the active materials of these until 1821 that Brande and Davy were able to isolate the
batteries. Restoration is achieved by applying a current element via the electrolysis of a lithium oxide.38 The first
to the battery in the opposite direction to the discharge study of the electrochemical properties of lithium, as an
current. Thus, the advantages of secondary batteries over anode, in a lithium metal battery was reported by Lewis
primary batteries are their higher power densities, higher and Keyes.39 Studies have also shown lithium is the third
discharge rates, and reusability.25,26 lightest element with a low density (0.534 g cm−3) and has
For most of the 19th century batteries were the main one of the smallest ionic radii of any single charged
source of electrical energy before the advent of large‐scale ion.40,41 Lithium also has the lowest reduction potential
mains electricity grids. With the arrival of mains electricity (−3.04 V vs. standard hydrogen electrode) of any element.
in the early 20th century batteries were predominantly Thus, giving lithium‐based batteries the highest possible
used for portable applications and backup electrical power cell potential.4,33 In addition, lithium has the largest
systems. However, the later part of the 20th century saw specific gravimetric capacity (3860 mAh g−1) and one of
the invention and rapid development of a wide range of the largest volumetric capacities (2062 mAh cm−3) of the
portable electrical devices like electronic calculators, elements.42 And during the mid‐1950s Herold discovered
laptop computers, mobile phones, and power tools. These that lithium could be inserted into graphite.43 These
devices have proliferated the world and revolutionized advantageous properties make lithium a very promising
business, science, and society as a whole. At the heart of anode material for high‐performance batteries. With these
these electronic appliances are rechargeable batteries properties in mind Harris, in the late 1950s, studied the
designed to power these devices for extended periods of solubility of lithium in several nonaqueous (aprotic)
time. And as a result, battery performance has become electrolytes. These electrolytes included cyclic esters,
a critical factor for the efficient operation of these molten salts, and lithium salt (LiClO4) dissolved in
devices.27,28 However, these new portable electronic propylene carbonate (PC).44 The study revealed during
devices and power tools require much larger energy and cell operation a thin passivation layer formed over the
power densities than existing rechargeable battery tech- anode surface and blocked direct chemical reactions
nologies could deliver. Thus, the performance deficiencies occurring between the underlying lithium surface and
of earlier rechargeable battery systems resulted in a search the electrolyte. However, the passivation layer did permit
for new types of rechargeable batteries capable of the flow of ions across it. In addition, in 1965 Juza and
delivering higher energy and power densities. The search Wehle were able to synthesize LiC6 using nonelectro-
resulted in the rapid development of new battery types chemical processes.45 The results of these studies kindled
like metal hydride batteries,29 nickel–cadmium batteries,30 interest in developing both primary Li‐metal batteries and
lithium‐ion batteries,31 and sodium‐ion batteries.32 rechargeable Li‐ion batteries.46,47
Among rechargeable batteries, Li‐ion batteries have a Crucially during the early 1970s, there was also a
number of advantageous electrochemical properties over renewed interest in intercalation chemistry. Intercalation‐
other chemistries, which has contributed to their higher based chemistry studies carried out during this period had
energy and power densities compared to other recharge- shown the inclusion of ions or molecules into a host
able batteries.33 Hence, their current dominance in the material, without damaging the host materials structure,
portable electronics, power tools, and a limited range of could change its electronic and optical properties.48,49
electric vehicles. Importantly, Li‐ion powered electrical Importantly, studies during this period also revealed the
intercalation of lithium into different materials had the first commercialized and delivered to the market.
potential to produce rechargeable (secondary) Li‐ion Typical examples include lithium–copper oxide (Li‐CuO),
batteries.50 Also during this period Armand formulated lithium‐sulfur dioxide (Li‐SO2), lithium–manganese oxide
the rocking chair model, which described the motion of (Li‐MnO2) and lithium poly‐carbon mono‐fluoride (Li‐CFx)
lithium ions shuttling to and from the electrodes.51 The batteries.63–65 And since their inception these primary
model was also experimentally verified using titanium batteries have occupied the major part of the commercial
disulphide and lithiated tungsten dioxide as electrodes by battery market. However, there are several challenges
several researchers.52–54 associated with the use of primary batteries. These include
The first rechargeable lithium battery was designed single use, costly materials, and environmental concerns.
by Whittingham (Exxon) and consisted of a lithium‐ For instance, single use primary batteries generate large
metal anode, a titanium disulphide (TiS2) cathode (used quantities of unrecyclable waste materials and toxic
to store Li‐ions), and an electrolyte composed of a materials. And critically, when disposed of, the toxic
lithium salt dissolved in an organic solvent.55 Studies of materials initially contained within the battery escape into
the Li‐ion storage mechanism (intercalation) revealed the the surrounding environment.66–69 Importantly, because of
process was highly reversible due to minimal changes in the problematic issues associated with the disposal of
the TiS2 crystal structures.55–57 Furthermore, following primary and rechargeable Li‐ion batteries, strategies for
on from the NaxCoO2 studies of Fouassier et al., reducing their environmental impact by recycling has
Goodenough et al., replaced Na+ with Li+ to produce attracted considerable interest in recent years. Methods
the more air‐stable cathode material LiCoO2 in 1979.58,59 currently used to recycle electro‐active materials is
Its advantageous electrochemical properties have made it discussed later in Section 5.4.2.
the most commercialized cathode material for the last
four decades.60 And further intercalation chemistry/
battery material studies in this field also investigated 3 | O P E RA T I O N A L PRI N CI P LES
and promoted the development of several new solid‐ O F R E C H A R G EA B L E L I ‐I O N
solution materials.61 For instance, during the early 1980s, BATTERIES
Yazami and Touzain effectively used a graphite−based
anode for use in rechargeable Li‐ion batteries.62 The The operational principle of rechargeable Li‐ion batteries
major breakthroughs since the discovery of lithium‐ is to convert electrical energy into chemical energy
based rechargeable Li‐ion batteries and beyond is during the charging cycle and then transform chemical
presented in Figure 1. energy into electrical energy during the discharge cycle.
But it was several nonaqueous 3 V lithium‐ion primary An important feature of these batteries is the charging
batteries, each with different cathode materials that were and discharging cycle can be carried out many times.
F I G U R E 1 Overview of major events leading to the development of Li‐ion batteries, their current configurations, and possible future
directions based on Manthiram and colleagues.3,27,61,63,64
A Li‐ion battery consists of a intercalated lithium Overall reaction: x LiC6 + Li1− x CoO2  x C6
(3)
compound cathode (typically lithium cobalt oxide, + LiCoO2 .
LiCoO2) and a carbon‐based anode (typically graphite),
as seen in Figure 2A. Usually the active electrode The resulting voltage difference between the two
materials are coated on one side of a current collecting redox reactions generates the output voltage of the
foil. Typically, the cathode material is deposited onto battery. Importantly redox reactions in primary batteries
aluminium foil and the anode material is deposited onto are not reversible. While the redox reactions in recharge-
a copper foil, as seen in Figure 2B. Both electrodes are able batteries are fully reversible and many charging and
submerged in a liquid electrolyte and spatially separated discharging cycles are possible.70 Apart from the four
by a porous polymer separator (typically polypropylene major components mentioned above, many batteries
[PP] or polyethylene [PE]) to prevent shorting between have additional components like safety devices (vents),
the two electrodes. However, the electrodes are linked isolator surrounds, top covers, tabs, and battery manage-
ionically through the electrolyte and electrically con- ment systems.
nected via an external circuit for electron flow.
The operational principle of the rechargeable battery is
centered on a reversible redox reaction taking place 4 | M A J O R CO M P O N E N T S
between the cathode (positive material, the oxidant) and ANODE, CATHODE,
the anode (negative electrode, the reductant). During EL ECTR OL YT ES , AN D
operation lithium ions undergo intercalation and de‐ SEPARATORS
intercalation cycling, and as a result shuttle (back and
forth motions) through the electrolyte between the electro- As previously mentioned, Li‐ion batteries contain four
des (rocking chair model). The resulting redox reactions major components: an anode, a cathode, an electrolyte,
occurring at the electrodes generate electrons that travel and a separator. The selection of appropriate materials
through the external electrical circuit to produce a current. for each of these components is critical for producing a
While lithium ions acting as charge carrier's travel through Li‐ion battery with optimal lithium diffusion rates
the internal circuit (electrolyte). The reactions that occur between the electrodes. In addition, the Li‐ion battery
during the discharge cycle for a LiCoO2 cathode and also needs excellent cycle reversibility, ion transfer
graphite anode battery are described by Equations (1–3): rates, conductivity, electrical output, and a long‐life
span.71,72 This section summarizes the types of electrode
Cathode: x Li+ + x e− + Li1− x CoO2  LiCoO2 , (1) materials, electrolytes, and separators that have been
developed and optimized to produce high‐performance
Anode: LiC6  C6 + Li+ + e−, (2) Li‐ion batteries.
F I G U R E 2 (A) Principle of intercalation and de‐intercalation in the electrode materials and (B) major components in a typical Li‐ion
battery based on Nagaura and Tozawa and colleagues.6,9,23,41,51,61
4.1 | Anode materials presents a selection of anode materials and summarises

the section.
Early Li‐ion batteries consisted of either Li‐metal or Li‐alloy
anode (negative) electrodes.73,74 However, these batteries
suffered from significant capacity loss resulting from the 4.1.1 | Graphite and hard carbon‐based
reaction between the Li‐metal and the liquid organic solvent anode materials
electrolyte, poor cycle life, and dendritic growth.40,75
Dendritic structures emanating from the anode would Carbonaceous materials, each with different formations
grow, penetrate the separator, and continue growing until and structures, were investigated because of their thermal,
they made contact with the cathode (positive) electrode. The mechanical, and electrochemical stabilities. In particular, a
resulting electrically conductive pathway produced a short study by Guerard and Herold confirmed the intercalation
circuit.76 The short circuit would then initiate a thermal and the reversible de‐intercalation of lithium occurred in
run‐away reaction on the cathode surface that would result graphite and a number of other carbonaceous materials.101
in the battery catching fire.77,78 Because of the problems The replacement of Li‐metal anodes by a graphite‐based
encountered with early Li‐ion batteries, subsequent studies carbon material occurred in the early 1980s. The electro-
focused on replacing Li‐metal anodes with alternative chemical activity of graphite‐based materials came from
lithium‐intercalation compounds to enhanced both cell the intercalation and de‐intercalation of Li atoms within
cycle life and safety.61 The following sections present a the graphite structure. The graphite structure consists of
selection of anode materials that have attracted considerable stacked single layered honeycomb‐like sheets (graphene)
research interest. Section 4.1 concludes with Table 1 which that form a regular a two‐dimensional structure, as seen in
TABLE 1 A selection of anode materials developed for Li‐ion batteries.

Theoretical capacity
Material (m Ah g−1) Comments References
Carbonaceous
Hard carbons 200–600 Good working potentials, Less columbic efficiency [79–81]
Carbon nanotubes (CNT) 1115 Relatively low‐cost High voltage hysteresis [82–85]
Graphene 780/1115 Safe to operate & high capacity [86]
Graphene nano‐flakes 165 Good charging for 80 cycles. [87]
Graphene‐like graphite 673 Good stable discharge capacity [88]
Titanium oxides
LiTi4O5 176 Low cost & safe, but low capacity [89]
TiO2 320 High power capacity, low energy density & good service [89]
life cycle.
Alloy/de‐alloy
Germanium 1623 High energy density, but large fading, low life cycle [90]
Silicon oxide 1562 High capacity & density, safe, but suffers from fading [91]
SiO2/CNT/graphene 260–723 Good initial discharge but drops [92]
Tin (Sn) 992 Good charging but suffers fading [93]
SnO2 510 Good charging for 50 cycles [94]
Metal oxides
CoO, Co3O4, CuO, Cu2O, Cr2O3, 500–1200 High capacity, energy, low cost & Ecofriendly, but poor [95–97]
Fe2O3, Fe3O4, MoO2, MoO3, NiO, cycle life, unstable SEI formation, poor columbic
RuO2, etc. efficiency & increased hysteresis issues
Metal phosphides/nitrides and sulfides
MXy M = Fe, Mn, Ni, Cu, Co, etc. 500–1800 Large capacities, but suffer from short life cycles & [98–100]
X = P, S, N higher manufacturing costs.
Figure 3A. The two‐dimensional structure not only materials tend to shield Li+ from dendrite formation
provides a mechanically stable framework, but it can also during battery recharging. Importantly, a graphite‐based
accommodate 1 Li atom for every 6 C atoms. During carbon anode combined with a LiCoO2 cathode enabled
intercalation the Li and C atoms combine to form LiC6.50 the Li‐ion battery to become commercially viable around
The storage pattern of Li atoms within the graphene sheet‐ 30 years ago and is still the most widely used anode
based two‐dimensional structure is shown in Figure 3A.102 material today.23,110
The intercalation and de‐intercalation reaction can be Hard carbons, unlike graphite, are composed of small
expressed by Equation (4)103: disordered graphitic grains with nano to micro‐scale
voids between them. The presence of these voids results
LiC6  C6 + Li+ + e− (4) in a small isotropic volume expansions and also permits
the accommodation of Li+ ions. In addition, the structure
The reaction results in small volume changes (~10%) also permits the accommodation of Li+ ions in the inter‐
in the two‐dimensional structure and offers good Li layers of the grains and it can supplement intercalation
transport and cycle stability.106 Subsequent studies have and deintercalation of Li+ ions in electrode materials
also confirmed several other carbonaceous materials can during charging.111 Studies have also found a propor-
also promote Li intercalation and de‐intercalation pro- tional relationship between the level graphitization and
cesses within batteries.107–109 In addition, carbon‐based lithium capacity. And in general, less graphitized carbon
F I G U R E 3 (A) Lithium intercalation in graphene sheets. Reproduced from open access article in the supplementary information from
Ji et al.,102 Springer Nature Copyright 2019; (B) lithiated Li4Ti5O12 structure reproduced with permission104 American Chemical Society
Copyright 2011; (C) Layered LiCoO2 structure reproduced from ICSD‐155284; (D) Spinel LiMn2O4 structure, reproduced from ICSD‐89985,
and (E) Olivine LiFePO4 structure reproduced from ICSD‐92198.105
materials have higher life cycles due to the many lattice inferior performance at high current densities, poor
defects pinning the graphite grains and layers together. Coulomb efficiency, and a lower life cycles.123 Current
Thus, making it tougher for less graphitized carbon research is investigating the addition of dopants like
materials to be exfoliated.112,113 However, this pinning metal oxides to graphene to produce hybrid anode
and the exposure of large numbers of edge planes also materials as a method of overcoming the abovemen-
increases the density of the electrically resistive solid tioned problematic issues.126,127
electrolyte interphase (SEI), reduces ionic conductivity,
and leads to poor performance.111,114 In recent years
research has focused on modifying the morphology 4.1.3 | Carbon nanotube (CNT)‐based anode
(nanostructured materials) or introducing nanomaterials materials
into the structure to increase Li+ intercalation and
de‐intercalation reaction rates, improve charging and CNTs are composed of graphene sheets rolled into
discharging cycles, and enhance overall battery cylindrical tubes with diameters typically around a few
performance.79,80,115,116 nanometers and lengths of several micrometers. The tube
consists of a framework of strong C–C covalent bonds
which gives the tube graphite‐like properties. The
4.1.2 | Graphene anode materials orientation patterns of the carbon atoms can be classified
as armchair, zig–zag, and chiral. CNTs are further
Graphene is a carbonaceous material consisting of a classified based on their degree of graphitization,
honeycomb framework of sp2 carbon atoms arranged and configuration, and structure. And depending on their
bonded into a two‐dimensional sheet with a single‐atom degree of graphitization, they can be further identified as
thickness. Since its discovery in 1987, it has attracted either amorphous or graphitic.128 Furthermore, CNTs are
considerable interest due to its impressive physical and also categorized as either single‐walled carbon nanotubes
chemical properties.117 Properties like large surface area, (SWCNTs) or multiwalled (MWCNTs) nanotubes. In the
superior mechanical strength, high electrical conductiv- case of multiwalled nanotubes, the graphene sheets are
ity, good charge mobility, and ionic transport make rolled into closed concentric tubes along the central
graphene a good anode material for Li‐ion battery longitude axis of the tube. CNTs have high electrical and
applications.118,119 In particular, graphenes promising thermal conductivities, superior mechanical properties,
chemical stability and its mechanical strength combined and desirable chemical properties that have made them
with high flexibility allows it to be used in a variety forms attractive materials for chemical engineering, energy
for various applications.120 However, studies of the conversion, and storage applications.129 Studies have also
intercalation and storage of Li+ ions within the graphene shown CNTs have good Li adsorption rates, ion diffusion
sheet is debateable. Since the amounts of Li+ ions taken rates, and intercalation/de‐intercalation rates, but these
up by the graphene sheet (equating to storage capacity) is properties are dependent on both morphology and
low compared to the theoretical storage capacity of structure.130,131
graphite (372 mA h g−1).121 On the other hand, when Several studies investigating CNTs as potential
several exfoliated sheets of graphene are combined their anodes materials have shown they have high storage
theoretical storage capacity significantly increases to capacities.132 Importantly, both the intercalation of
between 744 mA h g−1 and 1448 mA h g−1.122 The varia- Li+ on tube surface sites and within the central tube are
tion in storage capacity is due to the morphology of directly influenced by CNT synthesis, process treatments,
graphene and the interaction between Li+ ions and and surface modifications.82,133,134 For instance, SWCNTs
graphene.123 The lower storage value of 744 mA h g−1 produced by laser evaporation were found to have storage
assumes Li+ ions are absorbed on both face surfaces of capacities around 1050 mA h g−1.135 Studies have also
the graphene sheet via the electrochemical reaction of shown that hybrid anode materials composed of CNTs
Li + 3 C ⇄ LiC3 (Li2C6 stoichiometry). doped with nanostructured materials (like Ge, Sb, Sn,
On the other hand, the higher storage value of Si, etc.) or metal oxides (Cr, Cu, Fe, Mn, Mo, Ni, etc.) can
1448 mA h g−1 assumes the Li+ ions are captured by improve electrical conductivity and reduce anode
benzene rings and form covalent bonds to create a volumetric changes during charging and discharging
lithium‐carbon compound (LiC2 stoichiometry).124,125 cycles.128,136 For instance, micro‐coating CNTs with
However, in spite of the advantages of higher Li storage Fe3O4 not only increased Li storage capacity but also
capacity, a number of issue have been identified in improved battery performance.137 However, further
graphene anodes operating in Li‐ion batteries. These research in this field is needed to elucidate the challenges
issues include low Li loading, high operating voltages, facing large‐scale manufacturing and production costs
associated with producing CNTs and CNT/hybrid‐based Lithium titanium oxide, Spinel Li4Ti5O12 (LTO)
anode materials specifically designed for Li‐ion battery The lithium titanium oxide (Spinel) Li4Ti5O12 (LTO) has
applications. advantageous properties suitable for lithium storage,
despite having the theoretically low capacity of around
175 mA h g−1.150 These properties include high thermal
4.1.4 | Titanium‐oxide‐based anode stability, excellent Li‐ion reversibility, and long life
materials cycles.151 The high stability results from a “zero strain”
lithium intercalation and de‐intercalation process oper-
Titanium oxides combine the advantages of low ating in combination with a high lithiation potential.
cost, minimum safety issues, low toxicity, and increased And during the intercalation and de‐intercalation cycles
life cycles.138 In addition, titanium oxides only experi- the volumetric changes have been found to be negligible
ence small volume changes (2%–3%) during lithium‐ (~0.2%).152 The subsequent intercalation and de‐
intercalation and de‐intercalation.139,140 Importantly, the intercalation mechanism is unique, because it is depen-
intercalation and de‐intercalation of Li depends directly dent on two lithiation reactions, as presented in
on the size, morphology, and structure of the titanium Equations (5) and (6) below and seen in Figure 3B
oxide. And studies have also shown nanostructured showing the lithiation of Li4Ti5O12.153
titanium oxides display superior storage capacity and
longer life spans compared to their equivalent bulk Li 4 Ti5O12 + 3Li+ + 3e−  Li7 Ti5O12 , (5)
scale.141,142 Due to these advantages significant progress
has been made in developing anodes containing titanium Li7 Ti5O12 + 2Li+ + 2e−  Li9 Ti5O12 . (6)
oxides nanostructures. To date, titanium dioxide is
being investigated for potential use in anodic materials During this process, the resulting solid electrolyte
and spinel Li4Ti5O12 (LTO) has been successfully interface (SEI) formation prevents the formation of
commercialized.143,144 lithium dendrites, which is a serious problem for
carbon‐based anodes.143 Thus, the avoidance of dendrites
Titanium dioxide materials dramatically improves Li‐ion cells performance and
In recent years titanium dioxide (Titania) has attracted increases its lifespan to tens of thousands of cycles.154
considerable interest as a prospective anode material in But, LTO suffers from higher costs associated with
Li‐ion batteries due to its attractive properties. These titanium, lower electronic conductivity (10–13 S cm−1)
properties include chemical stability, low cost & availabil- and gassing resulting from a reaction between LTO
ity, advantageous electro‐activity and good oxidizing surfaces and organic electrolytes. However, two methods
capacity.145,146 Studies have also shown lithium intercala- can be used to mediate low electronic conductivity
tion and de‐intercalation in titanium dioxide is dependent and surface reactions. The first involves applying
on particle size, morphology, and crystalline structure.147 surface treatments like coating with carbon or lithium
Titanium dioxide has several allotropic forms that have titanate.155,156 However, carbon coatings can also pro-
attracted the interest of researchers. The most studied mote electrolyte decomposition that is subsequently
allotropic forms that have been investigated for anode deposited into the forming SEI at higher temperatures.157
applications include anatase (tetragonal, I41/mnm), brook- While the second method involves developing nanos-
ite (Orthorhombic, Pbca), and rutile (tetragonal, P42/ tructured forms of LTO that are designed to increase Li‐
mnm).148 An anodic material generated from 1 M lithium ion diffusion rates.158 Even so, LTO anodes have distinct
and 1 M of TiO2 is expected to have a maximum capacity of advantages over most other anode materials and as a
around 330 mA h g−1 and stoichiometry of LiTiO2. How- result they have been successfully commercialized.
ever, studies have also shown obtaining this optimum
storage capacity is challenging.146 For instance, titanium
dioxide (anatase) with a mean particle size of 6 nm was 4.1.5 | Alloying materials for anodes
found to have a capacity of around 125 mA h g−1 with a
current density of 10 A g−1. However, when mean particle A challenge facing Li‐ion battery development is to
sizes were increased to 15 nm and 30 nm, the respective increase their energy capacity to meet the requirements
capacities were reduced to 80 and 71 mA h g−1.149 Thus, of electrical vehicles and the demand for large‐scale
smaller particle size was found to promote easier lithium storage of renewable energy generated from solar and
intercalation and de‐intercalation and improve Li+ ion wind installations. Therefore, one method for increasing
diffusion. Thus, titanium dioxide‐based anode materials capacity is to develop new alloyed‐based anodic materials
are actively being researched. that incorporate dopants that can significantly improve
performance. In this case, dopants need to electroche- 2 A g−1, 1600 mA h g−1 at 4 A g−1 and 1100 mA h g−1 at
mically alloy and form compounds with Li. Importantly, 8 A g−1.169 Importantly, recent studies have also shown
these new alloy materials need to have large volumetric SiOx is an attractive alternative to pure Si due to its
and gravimetric capacities. Alloying dopants that can minimal volume changes resulting from the coordination
deliver higher capacities include germanium (Ge), of oxygen with lithium.170,171 Interestingly, SiO has a
silicon, and silicon monoxide.159 In general, the fully large energy capacity (>1600 mA h g−1) and a low
reversible reaction for alloy‐based materials is presented activation of energy.172,173 Typically, during the dis-
in Equation (7) below.160–162 charge cycle, SiO changes to Si and the forming lithium
oxides can subsequently interact with Si to form a
A + x Li+ + xe−  Lix A. (7) lithium silicate alloy (Li‐Si), as seen in Equations (8–10)
below.174
However, these alloy‐based materials suffer from
SiO + x Li  Si + Lix O, (8)
extremely large volume expansions and contractions
during lithium intercalation and de‐intercalation cycles.
xLi + Si  Lix Si, (9)
As consequence of large volumetric variations the anodes
SEI protective layer is seriously damaged. This results in
accelerated electrolyte decomposition, loss of active or
materials, and increasing cell impedance. Another
consequence of these large volumetric changes is much xLi + SiO  Lix − y Siz + Lix SiOz . (10)
shorter life cycles.163 However, in recent years several
approaches have been investigated as possible methods
for overcoming large volumetric variations. These Ge
approaches have focused on two strategies. The first Ge is also an attractive alloy material for anodes (Li22Ge5)
involves the reduction in size of bulk materials down to due to its high lithium capacity of 1623 mA h g−1 and its
the nanometer scale level. Since nanoparticles have high high electronic conductivity which is 104 times greater
surface area‐to‐volume ratios, they tend to promote than silicon.175 However, despite being an important
increased SEI formation rates, which in turn helps anode alloying material for high‐density applications like
stabilize the SEI. The resulting stabilized SEI also electric vehicles, it is hampered by very higher cost and
promotes longer cycle lifespans.164 And the second large volumetric changes (~300%) during lithium inser-
involves developing composite materials composed of tion and de‐insertion.176 But recent studies indicate
active lithium and inert materials that form a conductive nanometer scale structures of Ge such as nanoparticles,
buffer between the lithium source and the alloying nanotubes, and nanowires could handle volumetric
materials.163 Critically, alloy materials display a variety of changes more easily than bulk structures.177,178 For
nanometer scale morphologies like nanotubes and instance, crystalline Ge nanoparticles formed on
nanowires that promote higher capacities longer life SWCNTs by chemical vapor deposition (CVD) increased
cycles.165,166 conductivity between the Ge nanoparticles and the
current collector. Importantly, during battery cycling
Silicon (Si) and silicon oxides (SiOx) higher lithium diffusion rates were detected and the
Notably, Si has attracted considerable interest in recent SWCNT matrix permitted Ge volumetric changes during
years due to its advantageous properties that make it an lithium insertion and de‐insertion cycles.179
attractive alloy material for anodes. These properties
include: (1) An extremely high gravimetric capacity
(4200 mA h g−1 for Li22Si5); (2) large volumetric capacity 4.1.6 | Conversion materials—Transition
(9786 mA h cm−3); (3) its discharge potential is close to metal compounds
graphite (0.4 V vs. Li/Li+); (4) chemical stability; (5) low
cost due to its abundance (25.7% of earth's crust); and (6) In recent years transition metal compounds like oxides
its eco‐friendly nature due to its nontoxicity. Because of (O), nitrides (N), phosphides (P), and sulfides (S) have
these properties, the lithiation of silicon to form Li‐Si also been investigated for potential use as an alloying
intermetallic binary compounds like Li12Si7, Li13Si4, and materials in the manufacture of Li‐ion battery anodes.
Li22Si5 have been extensively studied.167,168 For instance, The main metallic elements that have been studied
Si nanowire structures were reported to be electroche- include tin (Sn), iron (Fe), and cobalt (Co), while others
mically stable and after 250 cycles the reverse capacities that have attracted scientific interest include nickel (Ni),
and current densities were found to be 2000 mA h g−1 at copper (Cu), and manganese (Mn). Significantly, studies
have shown anodes composed of transition metal developed strategies for producing iron oxide nanostruc-
compounds have large reversible capacities ranging from tures of suitable size, shape, and porous structures
500 to 1000 mA h g−1.180,181 During lithiation processes, designed to improve electrochemical kinetic processes
electrochemical reactions (oxidation/reduction) of the and overcome the abovementioned shortcomings.196,197
transition metal results in its participation in reversible Studies have revealed improved kinetics, capacity reten-
lithium conversion reactions. For instance, metal oxides tion, and structural stability of both hematite and
have been used to produce lithium compounds like Li2O. magnetite can be achieved through carbon coating.181
Typically, metal oxides will undergo an electrochemical Similarly, tin oxide (SnO2) has also attracted considerable
conversion reaction according to Equation (11)182: interest due to its theoretical capacity of 1491 mA h g−1.
However, due to the conversion process, the actual
Ma Ob + (b. n)Li  a M + bLin O, (11) capacity is reduced to 783 mA h g−1.198 In addition,
anode degradation rates are high due to the large
where M is the transition metal element and n is the volumetric changes (~200%) occurring during charging
oxidation state of oxygen. As mentioned above, Li2O is one and discharging cycles. Thus, there is a need to improve
such lithium compound that can be produced. It has the SnO2 cycling stability and reduce its volumetric changes.
advantages of acting as an amalgam to hold the alloying Studies have also shown that porous SnO2 nanostruc-
material together and reduce overall volumetric changes.180 tures and composites can mediate the effects of
Conversely, Li2O suffers from low electrical conductivity volumetric changes caused by lithium intercalation and
that results in voltage hysteresis and irreversible capacity.183 de‐intercalation.199
Thus, conversion reactions are often limited by their Other electrochemically active materials that have
irreversibility94,184,185 and careful consideration must be been studied for anode applications include metal
taken into account when alloying186 or intercalation95 phosphides, sulfides, and nitrides. Studies have shown
processes are involved. For instance, several transition phosphorus reacts with lithium in both the conversion
metal oxides like molybdenum oxide,187 vanadium oxide188 reaction and in the intercalation/de‐intercalation
and niobium oxide189 have been found to undergo reaction.200,201 In the first case, a converting mechanism
conversion/intercalation reactions. A general conversion results in electrochemical reactions breaking the metal
mechanism is presented in equation 12, where M is a and phosphorus bonds to produce lithium phosphides
suitable transition metal like Co, Cu, Fe, Mn, Ni, and so and nanometer scale metal particles. In the second case,
forth and N is either O, S, N, or P.98,188 the intercalation/de‐intercalation of lithium takes place
without breaking the metal and phosphorus bonds.99
Mx Ny + z Li+ + z e−  Liz Ny + x M. (12) However, current research is evaluating metal phos-
phides, since they suffer from low conductivities and
In particular, metal oxides like cobalt oxides (Co3O4 and large volumetric changing during charging. Alterna-
CoO), iron oxides (hematite [α‐Fe2O3] and magnetite tively, both metal sulfides and nitrides have also been
[Fe3O4]) and tin oxide (SnO2) have been extensively studied considered as potential anode materials. In particular,
for potential use in composite anode materials. Like other sulfides and nitrides of metals like cobalt, iron, nickel,
electrochemically active materials, cobalt oxides have manganese, and tin have attracted considerable interest
attracted significant interest due to their high capacities. due to their large lithium capacities and structures which
For instance, Co3O4 has a capacity of 890 mA h g−1, while promote the intercalation/de‐intercalation of lith-
CoO has a capacity of 715 mA h g−1.190,191 Several studies ium.202,203 Many of these metal sulfides and nitrides
have also investigated a variety of fabrication techniques have good energy capacities and are promising anode
like wet chemical, hydrothermal, and microwave‐based materials for Li‐ion batteries, but further research is
chemical synthesis to produce a variety of nanostructures needed to fully elucidate their electrochemical properties
like nanocubes, nanotubes and nanowires.192,193 and activity.
Likewise, iron oxides have also been extensively
investigated due to their high capacities, availability, low
material cost, and low toxicities. Importantly, the 4.2 | Cathode materials
theoretical capacities for iron oxides are 1007 mA g h−1
for hematite (α‐Fe2O3) and 926 mA g h−1 for magnetite Research into developing new battery technologies in the
(Fe3O4).194 Unfortunately, iron oxides suffer from poor last century identified alkali metals as potential electrode
Li+ ion diffusion, poor conductivity, iron agglomeration, materials due to their low standard potentials and
and large volumetric variations during charging and densities. In particular, lithium is the lightest metal in
discharging cycles.195 However, a number of studies have the periodic table and has the lowest standard potential
of all the elements. Importantly, Li+ ions are very small and capacity fading at high currents, and degradation of the
rapidly diffuse into and out of solids, therefore capable of LiCoO2 structure with time. In addition, during charging
promoting fast intercalation/de‐intercalation. Thus, an ideal and discharging cycles several phase transitions take
cathode in a Li‐ion battery should be composed of a solid place at different stages of Li intercalation and de‐
host material containing a network structure that promotes intercalation process. With the charging and discharging
the intercalation/de‐intercalation of Li+ ions. However, characteristics of LixCoO2 being a function of the amount
major problem with early lithium metal‐based batteries was of Li (x) and voltage. For instance, between lithium
the deposition and build‐up of surface lithium on the anode concentrations of x = 0.75 and x = 0.93 there is a phase
to form dendrites. In addition, early Li‐ion batteries also change that results in the material changing from a
tended to have low voltage outputs and capacities between semiconductor to a conducting metal phase.211 Further-
100 and 200 mA h g−1.55,204 Consequently, there has been more, charging and discharging cycle voltages in the
extensive research into finding new materials suitable for range from 3 to 4.5 V indicates material volumetric
developing novel cathodes for more efficient Li‐ion changes or irreversible structural changes resulting in
batteries. Since the development and commercialisation of rapid capacity decreases or fading.212 Studies have also
lithium cobalt oxide (LiCoO2) cathodes in the early 1990s, shown that low Li contents in LixCoO2 can result in
other categories like spinel LiM2O4 (where M = Mn, Ni, thermal instability at higher voltages.213,214 While inter-
etc.), olivine LiMPO4 (where M = Fe, Mn, etc.) and layered facial degradation resulting from the electrochemical
ternary metal oxides have been studied and evaluated for interaction between the electrolyte interface layer and
their operating voltages, energy densities, and discharge surface causes the failure of the cathode.215 One method
capacities.205–207 There is also other essential cathode that has been shown to reduce interfacial degradation
material, like air‐cathode and sulfur‐cathode,208 but it is and improve surface stability at high voltages (>4.2 V) is
out of the scope of this review. the use of surface coatings.216,217
Following on from the development of the LiCoO2
cathode, a number of other layered LiMO2 oxides like
4.2.1 | Layered transition metal oxide lithium nickel oxide (LiNiO2) and lithium manganese
cathodes oxide (LiMnO2) were studied and evaluated over the
years. The initial studies into alkali metal‐nickel oxides
The earliest layered transition metal oxide structure was carried out by Dyer et al. but it was not until the
studied and subsequently commercialised by Goodenough early 1990s that Daln et al. identified LiNiO2 (LNO) as an
was LiCoO2.60,209 Transition metal oxides LiMO2 (where alternative to LCO.218,219 LiNiO2 is considerably less
M = Co, Mn, Ni) continue to be researched for potential expensive due to the much larger quantities of nickel
use as cathode materials because of their high Li+ ion naturally occurring in the earth's crust compared to
mobility. The crystallographic structure of layered LiMO2 cobalt. Other advantages include higher attainable
(O3 type structure) is equivalent to a α‐NaFeO2 like reversible capacity (240 mA h g−1) and higher electrical
lattice, where the Li and M ions occupy the 3a and 3b conductivity compared to LCO.220 However, LNO is
sites respectively and the oxygen atoms form cubic close‐ difficult to synthesize due to the instability of Ni3+ at
packed arrays that occupy the 6c sites.210 The difference higher temperatures (700–800°C) that results in its
in size and charge between the Li and M ions leads to reduction to Ni2+ and to form Li1–yNi1+yO2.221 The
cation ordering on alternative (111) planes. Because of surplus Ni ions end up substituting for Li+ ions in sites
this layered structure it forms a two‐dimensional Li during synthesis and restricting the motion of Li ions
plane that promotes high Li ion diffusion and electrical during charging and discharging cycling. Thus, blocking
conductivity, as seen in Figure 3C. Because of high Li ion Li diffusion pathways and resulting in lower battery
diffusion and electrical conductivity, combined with performance.222 In addition to temperature instability,
structural stability, metal oxide cathodes were found to other factors that were found to influence the synthesis
provide effective reversibility and fast charging and of LNO was the quality of the precursors and atmo-
discharging behavior. spheric conditions.219 And even under ambient condi-
It was these advantageous features that enabled Sony tions LNO is susceptible to the formation of inactive
to combine a LiCoO2 (LCO) cathode with a carbon anode materials like LiOH and Li2CO3.223 A further detrimental
to produce the first commercially successful rechargeable feature that also results in capacity loss is the structural
Li‐ion battery. Even today LiCoO2 remains one of changes occurring in LNO during both the charging and
the most successful high operating voltage (~4 V) cathode discharging cycles.224 During the delithiation process,
materials. But its performance is influenced by material LixNiO2 undergo a series of phase transformations that
stability at high voltages and high temperatures, rapid includes hexagonal H1, monoclinic, hexagonal H2, and
hexagonal H3.225 For instance, during delithiation the changes from the layered structure to the spinel LiMn2O4
Li content range between 0.4 and 0.75 a monoclinic that was identified as the cause for the rapid capacity
phase is produced. And when the Li content is less fade.241 Also, occurring during the charging and dischar-
than 0.4, a hexagonal phase forms.226 During these ging cycles is the dissolution of Mn from the LMO
phase changes, the atomic rearrangements generate cathode. Once released from the cathode, soluble Mn2+
large stresses that can compromise the structural accumulates in both the electrolyte and the SEI layer of
integrity of the material. the anode. The subsequent accumulation in the SEI de‐
To alleviate thermal, structural, and electrochemical stabilizes the layer and increases anode impedance.242
instability issues with LNO, several studies have investi- However, studies have shown the LMO layered structure
gated using doping techniques and surface coating as a can be stabilized by partially substituting Mn with
possible method for resolving these issues. Dopants like cations like aluminium, chrome, and cobalt.239,243 For
aluminium (Al), magnesium (Mg), gallium (Ga), and cobalt instance, Co doping (~10%) achieved a capacity of around
(Co) have been found to be beneficial in improving the 200 mAh g−1 for a LMO cathode material, but subse-
properties of LNO.227–230 For instance, Mg doping was quent cycling revealed a gradual loss in capacity and a
found to improve thermal stability under high charging gradual phase transformation to spinel.244,245 However,
conditions.231 While the addition of small amounts of Al LMOs capacity fade with increasing numbers of charging
was found to improve electrochemical activity and thermal and discharging cycles has hindered its widespread
stability.232 Because of the success of the LCO cathode, Co commercialization. Another interesting material is lith-
was investigated as a possible dopant for LNO cathodes. ium manganese‐rich (LMR) cathode, which has gained
Studies have found small amounts of Co substituted for Ni significant attention as a promising cathode material due
tend to reduce cationic disorder and improved thermal to its high energy density, good safety profile, good
stability. For instance, the LiNi0.7Co0.3O2 composite was cycling stability, and cost‐effectiveness.246–248
found to be a suitable and thermally stable cathode The search for less expensive cathode materials has
material.233 Moreover, surface coating LNO with materials lead researchers to investigate the properties of mixed
like ZrO2, SiO2, Co, and Mn have also been found to transition metal oxides. The search also investigated
improve electrochemical performance. For instance, coat- mixtures that would overcome the limitations of
ing LNO with ZrO2 was found to retain 98% of its original individual metal oxides like capacity, low stability and
capacity even after 70 charge/discharge cycles over the safety. This research lead to the developments of a family
voltage range from 4.3 to 2.75 V.234 Similarly, a SiO2‐coated of layered ternary metal oxides with the general formula
LiNiO2 cathode was able to retain 92% of its original of Li (Ni1−x−yCoxMny) O2.249 The family of ternary metal
capacity after 60 charge/discharge cycles.235 oxides are designated as NMC or NCM and the
Another interesting material that has attracted associated numbers indicate the decimals of each
considerable interest is manganese oxide. Using manga- respective element. For instance, NCM523 indicates
nese (Mn) oxide to form LiMnO2 (LMO) offers a LiNi0.5Co0.2Mn0.3O2. As mentioned above, doping was
promising cathode material, since Mn is less toxic and found to improve the properties and stability of layered
cheaper than both Co and Ni. Thus, making LMO a more metals oxides. And for ternary metal oxides this is also
eco‐friendly alternative to either LCO or LNO. In the case. For example, the addition of Co improves the
particular, the high initial charge capacity of around rate capacity and the addition of nickel increases the
220 mAh g−1 generated a lot of scientific interest, but energy capacity. While Mn acts as a structure stabilizer
LMOs capacity rapidly fades with cycling and its layered and also enhancing safety.250 Generally, NCMs have
structure changes to manganese spinel LiMn2O4.236 LMO similar or higher capacities compared to LCO for similar
exists as two polymorphs, namely the orthorhombic operating voltages. They also tend to be more easily
(o‐LiMnO2) and monoclinic (m‐LiMnO2) phases. High‐ synthesized and are less expensive since the Co content is
temperature synthesis yields the electrochemically much lower.251 NCM333 has been commercialized and is
active o‐LiMnO2 phase, but the capacity rapidly fades the most common and widely used NMC material in the
and the structure transforms to the manganese spinel battery market. The summary of cathode materials
LiMn2O4.237 While low‐temperature hydrothermal described in this section is presented in Table 2.
approaches can produce a layered m‐LiMnO2 phase that
is electrochemically active.238
During the intercalation/deintercalation process, 4.2.2 | Spinel cathode materials
the m‐LiMnO2 phase is thermodynamically less stable
than the o‐LiMnO2 phase and the manganese spinel Spinel LiMn2O4 is another well studied cathode material
LiMn2O4.239,240 Importantly, it is the resulting phase that attracted considerable interest due to its low cost,
TABLE 2 A selection of cathode materials for Li‐ion batteries.

Theoretical
capacity
Material structure (m Ah g−1) Comments References
Layered
LiCoO2 274 High operating voltage (~4 V) but suffers [211]
from fading at high temperatures and
voltages.
LiNiO2 275 High operating voltage (~3.8 V), less [220]
expensive than Co, has higher reversible
capacity and higher electrical conductivity
compared to LCO.
LiMnO2 285 Operating voltage (~3.3), Mn is less toxic and [236]
cheaper that both Co and Ni, but capacity
rapidly fades with cycling and its layered
structures changes to manganese spinel.
LiNi0.33Mn0.33Co0.33O2LiNi0.7Co0.3O2 ~280 Composites doped with Ni or Mn or Al with [232–234]
LiNi0.8Co0.15Al0.05O2Li (Ni1−x−yCoxMny) O2 surface coatings have improved thermal
stability, performance & life cycles.
Spinel
LiMn2O4 148 Low cost, reversibility, high lithium‐ion and [252]
electrical conductivity and eco‐friendly
nature of Mn, suffers from capacity
fading.
LiMn2O4 + dopants ~142 Doping with Al, Co, and Cr improved cycle [253, 254]
capacity retention.
LiAlxMn2−xO4 Improved cycle capacity retention of around [255]
94% after 400 charge/discharge cycles
showing electrochemical performance
enhancement.
Olivine
LiFePO4 170 Good stability performance, but suffers from [256, 257]
low electrical conductivity and low ionic
conductivity and low energy density.
LiCoPO4 167 Lower electrical conductivity than LiFePO4, [258]
but nano‐composites have displayed high
rate capabilities and improved
performance compared to LiFePO4
reversibility, high lithium‐ion diffusion, electrical con- octahedral provides an effective three‐dimensional path-
ductivity, and the eco‐friendly nature of Mn.252 However, way for rapid Li+ ion diffusion as seen in Figure 3D.260
spinel cathodes do suffer from lower capacities and Interestingly, when the operating voltage is around
energy densities comparable to other cathode materials. 4 V the Li+ ions reside in the 8a sites (LixMn2O4
They also suffer from capacity fading, especially at (0 < x ≤ 1). But when the voltage drops to 3 V, the Li+
elevated temperatures. The LiMn2O4 spinel structure ions in the 8a sites relocate to empty 16a sites, causing a
has a space group Fd3m configuration, with the Li+ ions phase transition to Li2Mn2O4 and the resulting chemical
occupying the 8a tetrahedral sites of the spinel frame- instability results in the dissolution Mn3+ ions into the
work and the Mn3+/4+ ions occupying the 16d octahedral electrolyte.261 Thus, operating spinel LiMn2O4 at 3 V is
sites in an array of cubic close‐packed oxide ions.259 The not recommended, yet surface Li2Mn2O4 can still be
resulting [Mn2]16dO4 framework with edge‐shared detected on spinel LiMn2O4 cathodes operating at 4 V
after discharging.262 Besides the capacity fading due to structure of LiMn2O4.274 Importantly, studies have
phase transitions and the formation of surface Li2Mn2O4, reported that doping with Al, Co, and Cr can improve
long‐term fading is thought to be the result of oxygen loss the overall cycle capacity retention, but with some
from the de‐lithiation of LiMn2O4, irreversible side reduction of initial capacity.253,254 For instance, a study
reactions with electrolyte and Mn dissolution.263,264 The by Zhenfei et al. reported that an Al‐doped LiAlxMn2−xO4
presence of small amounts of H+ ions (ppm) in the (produces by a combustion method) with x values of 0,
electrolyte promote the disproportionation of Mn3+, 0.05, 0.1, and 0.16 tended to improve cycle capacity
with Mn4+ being retained in the lattice structure and retention. Their study revealed the x = 0.16 fraction
Mn2+ being leached out by the electrolyte as seen in produced the best electrochemical performance, with
Equation (13). cycle capacity retention being 93.9% after 400 charge/
discharge cycles.255
(solid)  Mn (solid) + Mn (solution) .
2Mn3+ 4+ 2+ (13)
In addition to losing Mn (an active material) to the 4.2.3 | Olivine cathode materials
electrolyte, there is also a degradation in the performance
of the cathode. While at the same time the migration of LiFePO4 belongs to the olivine‐structured lithium ortho‐
Mn2+ ions to the anode relentlessly pollutes the graphite phosphate family (LiMPO4, where M = Fe, Co, Mn)275
anode. Ultimately, anode poisoning and the loss of Mn and was first identified as a suitable cathode material by
from the cathode significantly reduces the operational Padhi et al.276 As a cathode material it offers a number of
performance and lifecycle of the Li‐ion battery.265,266 advantageous properties like being environmentally
To mitigate those effects, a number of strategies have benign, safe, abundant, low cost, low volume expansion,
been investigated for suppressing Mn dissolution and and a relatively high specific capacity with low capacity
reducing capacity fading. Strategies investigated include fading characteristics.41 The structure of LiFePO4
producing a protective metal oxide coatings on cathode belongs to space group Pnma configuration. The Li, Fe,
surfaces to reduce the direct contact with the electrolyte, and P atoms occupy octahedral 4a, octahedral 4c, and
coating with different electrochemically active materials, tetrahedral 4c positions, respectively. The oxygen atoms
oxygen stoichiometry and doping with different ele- are in a hexagonal close‐packed configuration. The
ments. For instance, a study by Li et al. revealed that a structure consists of [PO4] tetrahedra, [FeO6] octahedra,
Mn4+ rich surface coating produced by hydrothermal and [LiO6] octahedra. Each [FeO6] octahedron shares
synthesis and subsequent calcination under different common corners in the bc plane and shares edges with
atmospheres showed different capacity retention capabil- two [LiO6] octahedrons. While each [PO4] tetrahedron
ities for treated LiMn2O4 samples. Atmospheres investi- shares one edge with one [FeO6] octahedron and two
gated were air designated LMO‐A and oxygen designated edges with [LiO6] octahedrons, thus forming the three‐
LMO‐O and both were compared to commercially dimensional framework, as seen in Figure 3E.277
available LiMn2O4 designated LMO‐C. After 500 cycles The three‐dimensional framework also creates one‐
(charge/discharge rate of 1 C), capacity retention for dimensional (1‐D) channels (along the b‐axis) for the
LMO‐O, LMO‐A, and LMO‐C was found to be 94%, 86%, easy diffusion of Li+ ions during the lithiation/delithia-
and 75%, respectively.267 tion processes.278 During the delithiation process, the
Alternative studies have investigated the use of orthorhombic structure of LiFePO4 transforms into
electrochemically active material‐based coatings like FePO4, which has a trigonal quartz‐like structure.41,277
LiCoO2, LiNi0.5Mn1.5O2 and Li4Ti5O12 as a way of The structural change occurs by the creation of a two‐
improving cathode stability and performance.268–270 phase transition region (LiFePO4 and FePO4) that
While other studies have investigated the use of metal displays a voltage plateau of around 3.4 V in the
oxide coatings such as Al2O3, B2O3, TiO2, ZnO, and V2O5 discharge profile. Thus, during the lithiation/delithiation
to prevents the dissolution of Mn ions from the cathode processes the two phases coexist and both have the same
into the liquid electrolyte and thereby improve cycle space group (Pnma) configuration. And due to the small
capacity retention and improve the overall electrochemi- variations in crystal structure distortion during the phase
cal performance of the system.271–273 Another strategy for change, there is much better charging/discharging cycle
improving the electrochemical performance of LiMn2O4 stability. In addition, LiFePO4 has a theoretical capacity
is doping with different metal elements. A variety of of 170 mAh g−1 and a discharge voltage of around
dopants like Al, Cr, Co, Cu, Fe, Mg, Ti, and Zn have been 3.4 V.256 However, LiFePO4 suffers from low electrical
studied and found to suppress the formation of conductivity (10−8–10−10 S cm−1) and low ionic conduc-
Jahn–Teller active Mn3+ ions and stabilize the crystal tivity (~1.8 × 10−14 cm2 s−1).
Three strategies have been investigated to improve instance, a recent study by Li and Taniguchi reported
both electrical conductivity and ionic conductivity. The the synthesis of spherical nanostructured LiCoPO4 (SN‐
first, is particle size reduction and studies have shown LiCoPO4) particles, with diameters of several hundred
LiFePO4 composed of small particles with a narrow size nanometers, and their electrochemical characterization
distribution can reduce both electrical and ionic diffusion for Li‐ion battery applications. Their study used the
lengths and improve overall material conductivity.257,279 lithium half‐cell test and a cathode material composed of
The second is using conductive surface coating like the synthesised SN‐LiCoPO4 nanoparticles. The cathode
carbon to improve electrical conductivity between parti- exhibited a wide voltage plateau at around 4.75 V with an
cles and the electrode.280,281 And third, LiFePO4 elec- initial discharge capacity of 135 mAh g−1. The high rate
trical conductivity can be improved by doping with capability of the cell was attributed to particle size
metallic elements.282,283 Generally, a combination of reduction that reduced Li+ ion pathways during the
these strategies is used to improve the overall electrical charging and discharging cycles.258
conductivity and ionic conductivity of LiFePO4.
Despite the advantages of LiFePO4, its low energy
density has restricted its use in the electrical vehicle 4.3 | Electrolytes
industry. However, encouraged by its advantages, research
has focused on other olivine‐structured cathode materials The electrolyte, as previously mentioned, is one of the
with higher discharge voltages and energy densities. Studies four main components of a Li‐ion battery and acts as
have revealed LiMnPO4 displays a higher voltage potential the medium for Li+ ion transport (via migration and
(~4.1 V) and a higher energy density (~700 W h kg−1) when diffusion) between the cathode and anode during
compared to LiFePO4.284,285 Importantly, the higher voltage charging and discharging cycles. Therefore, the conduc-
and higher energy density of LiMnPO4 makes it attractive tivity of the electrolyte determines resistance, heat
for both electric vehicles and power back‐up systems. generation, current density, and consequently maximum
Conversely, LiMnPO4 suffers from low electrical conductiv- power output of the cell. The electrolyte is also in close
ity, slow Li+ ion diffusion rates and the presence of Mn3+ contact with all battery components including the anode,
ions located in unstable lattice positions can directly impact cathode, and separator.290 However, a critical factor that
on rate capacity and cyclic stability.275,286 needs to be considered when using lithium is its violent
But as previously mentioned, the performance of reaction with water and the subsequent generation of
LiMnPO4 cathodes, like LiFePO4 cathodes can be lithium hydroxide and hydrogen gas. With this in mind
improved by: (1) particle size reduction with a narrow the electrochemistry of Li‐ion batteries is based on using
size distribution to reduce Li+ ion pathways; (2) using nonaqueous electrolytes.
conductive surface coatings (carbon) to increase elec- In addition, the electrolyte also needs to have the
trical conductivity, and (3) doping with metallic ele- following parameters: (1) It must provide a high Li+ ion
ments.287 For instance, Wang and Li reported the results conduction pathway between the electrodes (closes the
of synthesizing LiMnPO4 (LMP) nanoparticles with cell circuit during operation) and conversely reduces
different morphologies using a solvothermal method. the internal resistance of the cell during operation; (2) It
Four morphologies were produced and included rectan- must provide electronic insulation and spatial separation
gular, pellet, rod and porous spindle shaped LMP between both electrodes to prevent short‐circuits; (3) It
nanoparticles. The subsequent electrochemical testing must have good electrochemical stability range to prevent
revealed the porous spindle shape nanoparticles had the decomposition at higher operating voltages; (4) Its
highest specific capacity and after 100 cycles the capacity electrochemical stability should also avoid parasitic side
retention was found to be 80.55%.285 reactions occurring on electrode surfaces and not degrade
In comparison with LiFePO4, both LiCoPO4 and within the range of anode and cathode working potentials;
LiNiPO4 display much higher working potentials of 4.8 V (5) It must be both mechanically and thermally stable,
and around 5.2–5.4 V, respectively.288 Moreover, both with both boiling and melting points for liquid electrolytes
LiCoPO4 and LiNiPO4 have much lower electrical occurring well outside the cells operational temperature
conductivities than LiFePO4 and LiMnPO4. However, range; (6) It also needs to be chemically inert towards
because LiCoPO4 has a theoretical capacity of 167 mAh other battery components like electrodes, current collec-
g−1, it has attracted more interest from researchers in tors and separator; (7) It must be economically viable
recent years. With research focusing on particle size to produce and have a long service life, and (8) it must
reduction (with a narrow size distribution) and control- have low toxicity, be recyclable and have minimal
lable particle morphology as a method for improving environmental impact.291,292 To successfully address each
the electrochemical performance of LiCoPO4.289 For of these parameters research and development has
focused on four types of electrolytes and these include: (1) complex anionic salts, usually lithium hexafluoropho-
liquid electrolytes (Li salt in solvents); (2) ionic sphate (LiPF6) which has good solubility in organic
liquids (ILs); (3) solid/gel systems, and (4) solid‐state solvents.295 A selection of Li‐based salts that have been
electrolytes.293 In the following sections, the thermal, used in organic solvent‐based electrolytes is presented in
physical, and chemical properties of each electrolyte type Table 3. However, a serious concern with organic
is discussed. solvents, both linear and cyclic, is their flammability
and the tendency of their vapors to ignite when exposed
to an ignition source. Linear carbonates like diethyl
4.3.1 | Liquid electrolytes carbonate (DEC) and dimethyl carbonate (DMC) will
ignite at much lower temperatures (low flash point) than
Currently, most commercially available Li‐ion batteries those of cyclic organic carbonates like ethylene carbon-
use nonaqueous liquid electrolyte solvents containing ates (EC), and PC.298 Other advances of using cyclic
lithium salts. The range of solvents suitable for electro- organic carbonates include higher dielectric constants
lytes is limited since they must be mechanically, and their ability to form low‐energy complexes with
thermally, and electrochemically stable at both the anode lithium cations. Thus, several types of lithium salts can
(low potential) and the cathode (high potential).294 And dissolve in either EC or PC, or mixtures of both to form
as previously mentioned, the electrolyte should not suitable electrolytes. Typical organic solvents used in
degrade and should be stable over a wide temperature Li‐ion battery electrolytes are presented in Table 4.
range, with both boiling and melting points outside the On the other hand these solvents also have high
cells operational temperature range.295 Thus, the ideal melting points and high viscosities. For instance, EC are
electrolyte solvent must be able to meet the following solid at room temperature and additives must be used to
parameters: (1) It must be able to dissolve sufficient lower its melting point and viscosity. In many cases, the
concentrations of lithium salts and promote optimal Li+ salt is LiPF6 and the solvent is EC and both are the main
ion conductivity; (2) It must have a low viscosity to components in current liquid electrolytes. However, in
promote optimal Li+ ion transfer through the electrolyte spite of the advantages of this salt/solvent combination,
and also allow fast filling of cells during manufacture; (3) both materials are sensitive to the operating temperature.
It must be chemical stable and remain in the liquid phase At low temperatures, EC is unstable due to its lower
over a wide range of operating temperatures; (4) It must conductivity and higher melting point. While at higher
have good wettability towards battery components like temperatures LiPF6 tends to react with EC and other
the electrodes and the separator; and (5) It must be inert organic solvents in general.295 Furthermore, the electro-
to all cell components and not promotes side reactions on lyte components (lithium salt and solvent) are important
the electrodes.296 factors in the performance of the cell, since they directly
Since the early 1990s, commercial rechargeable Li‐ion influence the properties of the respective electrolyte‐
batteries have used electrolytes typically composed of electrode interfaces. But due to the absence of suitable
organic carbonates, at least one lithium salt, and a alternatives, current commercial cells use various mix-
number of additives.297 However, because of the smaller tures of organic carbonates and property‐enhancing
ionic radius of the Li+ ion and structure of simpler additives as electrolytes. Typically, acyclic alkyl carbon-
molecular salts like LiCl and LiF they cannot be used in ates are added to commercial cells due to their low
electrolytes due to their poor solubility in organic melting points and lower viscosities to improve the
solvents. Therefore, current electrolytes consist of properties of organic carbonate‐based electrolytes.302
TABLE 3 A selection of Li salts used in liquid organic‐based electrolytes.299,300

Ionic conduct.
Li salt Mol. Wt. Salt anion Tmelt (°C) Tdecomposition (°C) (m S cm−1)
LiBF4 93.9 BF4− 293 >100 4.9
−
LiClO4 106.4 ClO4 236 ~80 8.4
−
LiPF6 151.9 PF6 200 >100 10.7
Li Triflate 155.9 Triflate 300 >100 3.1
LiAsF6 195.9 AsF6− 340 >100 11.1
Li Imide 286.9 Imide 234 >100 9.0
TABLE 4 Property characteristics of organic solvents used to dissolve Li salts to form organic electrolytes for Li‐ion batteries.192,301
Electrolyte Solvent Mol. Density Tmelt Tboil Tflash
component Abrev. formula (25°C) g cm−3 (°C) (°C) η (25°C) cP (°C) ε(25°C)
Diethyl carbonate DEC C5H10O3 0.969 −43 126 0.75 25 2.805
Di‐methyl carbonate DMC C3H6O3 1.063 2 91 0.59 (20°C) 18 3.107
Ethyl methyl EMC C4H8O3 1.006 −14 107 0.65 25 2.958
carbonate
Ethylene carbonate EC C3H4O3 1.321 36 248 1.90 (40°C) 145 89.78
Propylene carbonate PC C4H6O3 1.200 −49 242 2.53 135 64.92
Note: η is viscosity and ε is emissivity.
Similarly, the addition of esters like methyl acetate to EC electrolytes stems from their high oxidation potentials
also reduces solvent viscosity and improves low‐ resulting from the strong electron‐extracting effect of the
temperature performance, with only a minimal effect fluorine atom.304 A study by Zhang et al. found that
on electrolyte conductivity.303 fluorinated electrolytes have superior electrochemical
Moreover, in recent years there has been an increas- stability compared to nonfluorinated electrolytes.309 In
ing demand for Li‐ion batteries with larger energy addition, fluoro‐carbonate and fluoro‐ether‐based elec-
capacities and power densities for various applications. trolytes also produce rapid SEI formation on graphite
The simplest way to achieve this was by increasing the upon reduction during charging and discharging experi-
energy capacity and voltage of the cells, which equated to ments. They have also been shown to improve the
finding new electrochemically stable organic solvent‐ thermal and electrochemical oxidation stabilities of
based high‐voltage electrolytes.304 Studies have shown electrolytes, which also makes them good candidates
these electrolytes can be incompatible with electrode for low‐flammability electrolytes.310
materials and unstable at higher charging voltages. For
instance, Li et al. studied the performance of a
LiNi0.5Mn1.5O4 (LNMO) cathode in a conventional 4.3.2 | Ionic electrolytes
electrolyte composed of a lithium salt (1 M LiPF6) and
an organic solvent mixture (DEC/DMC/EC in the weight In recent years room‐temperature ILs have attracted
ratio of 1:1:1) over the voltage range between 4.0 and considerable scientific interest due to their high ionic
5.3 V versus Li/Li+. Their study found at charging conductivity, noncombustibility, nonvolatility, stable
voltages above 4.5 V the electrolyte became unstable.305 thermal and chemical properties, and stability over a
Likewise, a study by Hu et al. also investigated the wide potential range.311 In particular, studies have
voltage charging performance of another conventional shown that ionic liquid electrolytes display much higher
electrolyte composed of 1.2 M LiPF6 salt dissolved in an thermal stabilities than organic solvent‐based electrolytes
organic solvent mixture consisting of three parts EC and and also display high electrochemical stability at high
seven parts EMC. Their study found the electrolyte temperatures and developed potentials.312,313 Impor-
readily decomposed when charging voltages exceeded tantly, the main attraction for Li‐ion battery researchers
4.9 V.306 Interestingly, studies have shown the stable is their nonflammability and their resistance to oxidation
upper operating temperature for LiPF6 salt is 70°C, while which makes them a promising alternative to conven-
for organic solvent‐based electrolytes temperatures tional organic solvent electrolytes. Conversely, the
can vary. For instance, DEC is 120°C, DMC is 90°C disadvantages associated with ILs is their high produc-
and ethyl methyl carbonate (EMC) is 110°C. At the tion cost and their much higher viscosities compared to
other extreme, organic solvent‐based electrolytes also organic solvents. Importantly, a high ionic fluid viscosity
display low‐temperature instability. For instance, the leads to lower mobility and reduced conductivity.314
low‐temperature operating limit for an electrolyte However, recent studies have shown mixing ionic fluids
composed of EC/DMC (3:7 by wt.) is −25°C.307,308 with traditional organic carbonate solvents leads to
Alternatively, charging and discharging experiments electrolytes with the high conductivity of the organic
have also shown organic fluoro‐compounds like fluoro‐ carbonate solvent and the safety properties of the ionic
carbonates and fluoro‐ethers are promising candidate fluid.315 For instance, the addition of an ionic fluid
electrolyte solvents for high‐voltage operation. The (40% wt.) to an organic solvent was found to enhance its
suitability of fluorinated molecules for high‐voltage thermal stability greatly.316 Ionic fluid electrolytes are
currently being both experimentally and theoretically the addition of small quantities of lithium salts to solid
studied for possible future use in Li‐ion batteries. PEs can enhance ionic conductivity effectively. However,
studies have also shown increasing lithium salt concen-
trations in the host polymer can decrease ionic conduc-
4.3.3 | Solid/gel polymer electrolytes (GPEs) tivity due to the formation of ion pairs that reduce
polymer chain motion.322 Also, PEOs performance can
Polymer electrolytes (PEs) consist of a polymer host and be influenced by anion migration within the electrolyte
a lithium salt that forms a membrane with good ionic resulting in a decrease of the lithium transference
transport properties between the battery electrodes. PEs number. While the use of large organic anions complexes
are believed to be an attractive alternative to conven- like lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)
tional organic solvent‐based electrolytes. The advantages leads to lower crystallinity, higher ion conductivity, and a
of PEs over organic solvent‐based electrolytes include: lower anion transference number.322 What is more, solid
(1) no electrolyte leakage; (2) nonvolatility; (3) Non‐ PEs have the potential to suppress lithium dendrite
flammability; (4) reduced decomposition rates at the nucleation and growth, which makes them an interesting
electrode surfaces; (5) Hinders dendrite growth so no‐ field of research and development for future solid Li‐ion
internal shorting, and (6) improved safety.317,318 There batteries.
are two categories of PEs which are based on their
material state. Solid PEs have superior mechanical GPEs
properties compared to gel polymers, and both are Compared with solid PEs, GPEs are different since the
thermally and electrochemically stable over a wide range majority of the ion charge is carried through the plasticizer
of temperatures and electrode voltages. Importantly, they phase that contains the dissolved salt. While the polymer
also need to be nonreactive at the electrolyte‐electrode framework creates a flexible supporting matrix that may
interfaces.319 The following sections discuss solid/gel PEs contribute to ionic transportation. However, the interac-
in more detail. tions between the polymer matrix, the plasticizer, and the
lithium salt is complicated and is not fully understood at
Solid PEs present.323,324 Host polymers include poly(ethylene oxide)
The materials used in solid PEs must be electrochemi- (PEO), poly(vinylidene fluoride) (PVDF), poly(vinylidene
cally stable at high and low voltage potentials, be fluoride‐hexafluropropylene) (PVDF‐HFP), poly(methyl
chemically stable at the electrolyte‐electrode interfaces methacrylate) (PMMA), and polyacrylonitrile (PAN).
and have high dimensional stability. In addition, PEs While PC, EC, ethyl‐methyl carbonate (EMC), DMC, and
need to have a low glass transition temperature because DEC are commonly used as plasticizers.325 The GPE
highly crystalline polymer structures result in lower consists of the host polymer matrix containing a lithium
ionic conductivities. For Li‐ion batteries lithium ionic salt, which is then plasticized.326 The ionic conductivities
conductivity should be between 10−3 and 10−4 S cm−1.320 of such systems are slightly lower than those obtained with
Polymeric materials like poly(aza alkanes), poly(oxa liquid electrolytes, especially when the viscous solvent is
alkanes), poly(thia alkanes), and poly(ethylene oxide) used as a plasticizer.
have been extensively studied for use in Li‐ion battery The plasticization process increases the amorphous
applications. However, low ionic conductivities have phase present in the matrix which promotes higher
limited their application to date. Generally, ionic lithium salt dissociation and the cation mobility.327 Some
transport occurs in highly viscoelastic (amorphous) studies have reported increasing ionic conductivity with
polymers, but there are crystalline polymers that are increasing concentrations of lithium salt being added to
ion conductive like poly(ethylene oxide). Poly(ethylene the plasticizer.328 However, most studies highlight the
oxide), or PEO, has a high molecular weight, a importance of lithium salt to plasticizer ratio. Increasing
crystallinity of around 80%, and becomes conductive lithium salt to plasticizer ratio is accompanied by
when complexed with an alkali metal ion. And due to increasing ionic conductivity to a critical point and from
PEOs ion conductivity it has been used as an electrolyte this point the ionic conductivity remains fairly constant.
in batteries since 1979.321 Importantly, because of PEOs The highest conductivities are achieved when the
polymer framework and the strong coordination of the plasticizers have low viscosities and high dielectric
oxygen atoms with Li+ cations it makes a good salt constants.329 On the other hand, poor contact and
solvation medium.322 wetting of PEs on electrodes produce poor electrode/
In addition, PEO forms stable complexes with Li+ GPE interphase properties. In particular, highly polar
ions which promotes good ionic conductivity compared organic solvents are generally electrochemically unstable
to other solvating polymers. Some studies have shown when in contact with alkali metal electrodes. The
resulting electrochemical reactions at the electrode/GPE higher than 45°C the composite PE displayed an
interface produces passive layers that significantly amorphous nature with ionic conductivities around
increase resistance of the electrolyte. However, the 0.1 mS.cm−1.336 However, further study is needed to
addition of mediators like poly(trimethylene carbonate) establish a stable phase with a fairly stable ionic
oligomer could improve the electrode/GPE interphase conductivity over a wide temperature range.
properties.330 It is also known that GPEs suffer from poor Contrary to inert ceramic fillers, active fillers take
mechanical and thermal stability, and it has hindered part in promoting ionic conductivity. Both metal oxides
their applications. However, the use of crosslinking and metal sulfides are promising candidates for promot-
agents like isocyanates can improve both mechanical ing lithium‐ion conductivity.337 However, lithium‐ion
and thermal stability.331 Unfortunately, the possible transport within PEs with active fillers is problematic,
formation of lithium dendrites that ultimately lead to since the active fillers not only influences the polymer
cell short‐circuiting cannot be ruled out when chain structure, but they can also produce additional Li+
using GPEs. ion pathways. The three pathways include the polymer,
the active filler, and the interface between the polymer
Solid polymer/inorganic composite electrolytes and active filler. Inorganic materials evaluated for
One method for modifying the properties of polymer‐based possible active fillers for Li‐ion battery electrolytes
electrolytes is to incorporate filler particles and form a include: (1) Perovskites (i.e., Li3xLa2/3−xTiO3, LLTO);
polymer composite composed of organic and inorganic (2) Garnet types (i.e., Li7La3Zr2O12, LLZO); (3) sodium
materials. In these types of composites the polymer forms superionic conductors (NASICON); (4) amorphous
the organic part and the filler particles form the inorganic oxides, and (5) sulfide materials.338
part. Two types of filler particles have been investigated. The Several studies have shown these active fillers create
first are the inert ceramic particles, while the second are the new Li+ ion pathways and together with Li+ ion
active metal oxides or sulfides particles. As mentioned concentration and ion mobility collectively contribute
above, several studies have shown that polymers with high to PEs ionic conductivity. For instance, a study by Choi
crystallinity have poor ionic conductivity. Thus, the concept et al. found the addition (52.5% wt.) of a garnet‐based
of introducing ceramic oxide nanoparticles like Al2O3, TiO2, active filler (Li7La3Zr2O12, LLZO) into PEO‐based elec-
and SiO2 into a polymer to improve its ionic conductivity trolyte produced an ionic conductivity of 10−4 S.cm−1 at
was investigated. Despite ceramic oxide particles not 55°C.339 While Li‐ion conducting superionic conductors
directing participating in ion conduction, they inhibited Li1−xAlxTi2‐x (PO4)3 (LATP) and Li1+xAlxGe2−x (PO4)3
the crystallization kinetics of the polymer segments, thus (LAGP) can be used to enhance ionic conductivity.
promoting ion mobility.332 For instance, the inclusion of Studies have also shown that when Ti and Ge elements
SiO2 spherical nanoparticles (12 nm Dia.) into PEO during are partially substituted with Al, significant improve-
synthesis was able to significantly reduce PEO crystallinity, ments in ionic conductivity can be achieved. When
increased ionic conductivity (4.4 × 10−5 S.cm−1 at 30°C and Al substitution was carried out in LATP, its ionic
1.2 × 10−3 S.cm−1 at 60°C) and increased its electrochemical conductivity increased from 10−4 to 10−3 S.cm−1 at room
stability window up to 5.5 V.333 temperature.340 Similarly, when Al substitution was
Studies have also investigated the role of filler particle carried out for LAGP, its ionic conductivity increased
size, surface functionalities, and amounts of fillers from 10−4 to 10−2 S.cm−1 at room temperature.341 Like-
included, and their subsequent influence on electroche- wise, when a 66% wt. loading of LATP was added to PEO,
mical and mechanical properties. For instance, the its ionic conductivity increased from 10−6 to 10−4 S.cm−1
tensile strength improved from 1.42 to 2.12 MPa at at 40°C.342
80°C when BaTiO3 nanoparticles (10% wt.) were added to
a cross‐linked poly(ethylene oxide‐co‐propylene oxide)
amorphous polymer.334 Similarly, a study by Ramesh 4.3.4 | Inorganic solid‐state electrolytes
et al. found that Young's modulus increased from 500 to
2300 Pa when SiO2 particles (10% wt.) were added to Solid‐state electrolytes are composed of inorganic mate-
polyvinyl chloride–polyethylene oxide (PVC–PEO) based rials that are nonflammable, have high thermal stability
PEs.335 Likewise, a recent study by Marangon et al found with much higher melting points compared to either
the addition of SiO2 filler particles to a polyethylene‐ liquid or polymer‐based electrolytes.293,343 Both crystal-
glycol dimethyl‐ether (PEGDME) PE found two line (glass‐based) or amorphous inorganic materials with
temperature‐dependent ionic conductivity ranges. From fast interfacial charge transport properties and high
room temperature to 45°C the composite PE displayed a room‐temperature ionic conductivity have been investi-
crystalline nature with low conductivity. At temperatures gated for potential use as solid‐state electrolytes in Li‐ion
batteries.344 A wide range of materials have been studied the electrodes and the electrolyte is challenging during
and include amorphous oxides, perovskites, garnet‐type, charging and discharging cycles. Furthermore, there are
sodium superionic conductors (NASICON)‐type, and also issues with the brittle nature and the effects of large
sulfides. Both perovskites‐type and garnet‐types display volumetric changes experience during charging and
high conductivities greater than 10−3 S.cm−1 at room discharging cycles which can result in mechanical
temperature and stability towards lithium metal.345,346 failure.365 Thus, further research is needed to resolve
The perovskite‐type materials have a general formula of the issues associated with solid‐state electrolytes.
ABO3, where A is a cation element in the groups I, II,
and III of periodic table and B is a cation of the d‐block
element in the periodic table.347 The garnet‐type 4.4 | Separators
materials have a general formula of A3B2C3O12, where
A, B, and C can adapt to different combinations of Many current Li‐ion batteries have a porous separator
cations.348 made from a polyolefin polymer like PE or PP or a
The NASICON‐type materials are phosphate‐based combination of both. The separator is an important safety
ion‐conducting glass‐ceramics with the general formula of feature designed to prevent electrical short‐circuiting and
AM2 (PO4)3, where A = Li, Na or K and M = Ge, Zr, or Ti. is located between the anode and cathode. The porous
These materials have both good chemical stability and structure of the separator also acts as a Li+ ion reservoir
mechanical stability.349 In particular, these materials have that assists in the unrestricted flow of Li+ ions. The
the potential to prevent dendrite growth, which is a major functions and related properties of a separator are: (1) to
problem with some traditional liquid electrolyte‐based Li‐ reduce the risk of short circuits by providing a physical
ion batteries. Also, the properties of glass ceramics makes barrier that prevents direct contact between the anode
their boundary resistance low, which help promote and the cathode. To achieve this goal, the separator must
diffusion channels and ion mobility.350 In addition, the be chemically stable, resist shrinkage, and have sufficient
ionic conductivity of these phosphate‐based ceramics can mechanical strength to avoid rupturing during charging
be improved by replacing metals (Ge, Ti, or Zr) with and discharging cycles over the range of operational
hafnium (Hf) or tin (Sn).351 Studies have also shown the temperatures; (2) to have a porous structure that permits
ionic conductivity is influence by different microstructures the migration of Li+ ions while at the same time prevents
resulting from different synthesis processes.352,353 the flow of electrons through the electrolyte. Therefore,
Whereas, sulfides are another material that has the separator surface must have high wettability propert-
attracted considerable interest due to their high ionic ies towards the electrolyte, thus promoting optimal Li+
conductivities, low grain boundary resistances, and inter- ion flow at the lowest possible resistance, and (3) to be as
facial resistances.354 These properties make them potential thin as possible to promote the shortest Li+ ion migration
candidates for all‐solid‐state Li‐ion batteries.355–358 The pathways.366,367 Thus, the properties of a separator are
initial low ionic conductivity at ambient temperature of very important for it to achieve a high overall perform-
sulfides can be overcome by doping with Ge or phosphorus ance in a Li‐ion battery. The following sections discuss
or both.359 For instance, sulfide‐based materials doped the required physical properties of a separator, materials
with Ge and phosphorus like Li10GeP2S12 (LGPS) can have used to manufacture separators, shortcoming of current
an ionic conductivities as high as 25 × 10−3 S/cm, which separators, and methods for improving the performance
betters current liquid electrolytes.360 However, a major of separators.
problem associated with sulfide‐based solid electrolytes is
their chemical instability with air, moisture, and cathode
materials.361 A recent study shows that argyrodite and 4.4.1 | Separator properties
halide solid‐state electrolytes are more promising materials
for industrialisation compared with LGPS.362,363 The property parameters needed for an efficient and safe
Another inorganic material type studied for use as a separator can be broadly categorized by: (1) Structural
solid electrolyte are lithium cations like LiX, where X is properties; (2) Intrinsic material properties, and (3) The
an element such as nitrogen. For instance, the ionic properties needed to withstand external influences. The
conductivity of Li3N is 1 × 10−3 S.cm−1 and Li3N‐based following three sections discuss each of the parameters
electrolytes can be used in lithium‐metal batteries.364 On that make up each of these categories.
the other hand, the main issue of both amorphous and
crystalline inorganic materials is their brittleness which Separator structural properties
makes manufacturing problematic. In addition, their lack The three structural property parameters that a separator
of flexibility means maintaining good contact between must have include: (1) a uniformly thin cross‐section; (2)
a well‐developed pore structure, and (3) be highly strength; (4) thermal dimensional stability; (5) effective
porous. The separator must be uniformly thin to promote melt temperature, and (6) shut down temperature at an
uniform Li+ ion flow. However, if the separator is too elevated temperature. The separator must have sufficient
thin dendrites can puncture and cause short‐circuiting. mechanical properties to overcome dimensional instability
On the other hand, if the separator is too thick it can and withstand physical stresses produced within the cell
generate high resistances that reduce energy and power during its operation. In terms of dimensional stability the
densities. The thickness of current separators used in separator must not curl up and should remain a flat
commercial Li‐ion batteries ranges between 20 and surface. Hence, the higher the tensile strength, the more
25 µm.368 Pores should be uniformly distributed over rigid the separator. Also the higher the tensile strength,
the separator surface to facilitate Li+ ion diffusion and the greater the resistance to dendrites puncturing the
large enough to absorb the electrolyte and assist in the separator, thus preventing dendrite growth.368
passage of Li+ ions through the separator. Studies have Moreover, the separator material should also have
shown that sub‐micrometer pore sizes have proven to thermal‐dimensional stability over the operational tem-
be suitable for blocking penetrating Li‐dendrites, with perature range of the cell. In current commercial‐grade
commercial separator pore sizes being around 1 µm or separators the thermal‐dimensional instability is less
smaller.369 The porosity needs to be as large as possible to than 5% in all direction after 60 min at 90°C. The overall
maximize surface area without compromising mechani- thermal stability of the separator is defined by the melt
cal strength. Low porosities have lower levels of temperature and the shutdown temperature. Under
electrolyte wettability and higher internal resistances. abnormally high temperatures, the separator will begins
Typically, commercial separators have porosities ranging to melt, this point is the melt temperature and is typically
from 40% to 60% and have been found to provide effective between 130°C to 200°C or higher, depending on the
wettability and good ionic conductivity.370 material used to make the separator.374 At the melting
temperature, the separator pores will close and block.
Intrinsic material properties This event prevents ionic flow between the electrodes
The three intrinsic material property parameters that a and terminates all electrochemical processes within the
separator must have include: (1) effective electrochemi- cell. This event occurs at the shutdown temperature
cal stability; (2) beneficial wettability, and (3) superior (around the melt temperature) and is called the separator
ion conductivity. Two importantly requirements of a shutdown function. For polymer‐based separators the
separator include being an electronic insulator and being shutdown temperatures are typically around 140°C for
completely electrochemically stable under redox reaction PE and 160°C for PP.375 Importantly, even after separator
potentials. In addition, the separator also needs to be shutdown, the separator should still prevent any damag-
completely chemically stable with the electrolyte and ing contact between the electrodes.
other cell components.371,372 Another intrinsic property
of the separator is its wettability. This is important
because the separator must take up and retain enough 4.4.2 | Separator types and materials
electrolyte to promote optimal ionic conductivity.368 For
instance, when the wettability of the separator is high Lithium‐ion batteries employ three different types of
(low contact angles indicate larger affinity between the separators that include: (1) microporous membranes; (2)
electrolyte and separator), ionic resistance is low and Li+ composite membranes, and (3) polymer blends. Separa-
ion flow rates are high. Thus, wettability is important for tors can come in single‐layer or multilayer configura-
both cell performance and longevity, since poor wetta- tions. Multilayered configurations are mechanically and
bility results in low Li+ ion flows and poor Li+ ion thermally more robust and stable than single‐layered
distribution resulting in dendritic growth.373 Crucially, configurations. A wide range of materials have been
the ionic conductivity of the separator must be optimal investigated and numerous composites, polymer blends,
for cell performance and safety. Ideally, ionic conductiv- and solid have been developed for use in Li‐ion
ities for separators are expected to be in the range from batteries.376 The following three sections discuss the
10−3 to 10−1 S.cm−1.372 configurations and materials used to make each of these
types of separators.
Material properties needed to withstand external
influences Microporous separators
The six material property parameters needed by a Separators have been fabricated from a variety of
separator for successful operation include: (1) dimensional inorganic and organic materials (both natural and
stability; (2) high tensile strength; (3) high puncture synthetic), that generally have some sort of pore
structure. The most commonly use separator type is the separators.381 Ceramic compounds like silica (SiO2) and
microporous and is composed from a polyolefin polymer alumina (Al2O3) have been studied for potential use as
like PE or PP or a combination of both.377 There are two fillers due to their attractive properties. For instance,
microporous separator categories and these are either silica apart from being abundant and low cost, it has high
single‐layer or multilayer configurations. However, thermal stability which can be used to improve the
multilayered separator are more robust and stable over thermal stability of the host materials.382 Similarly, the
a wider range of temperatures and mechanical stresses. addition of alumina to conventional separator materials
Many kinds of microporous polymer‐based single‐layered improves their thermal stability.382 While silica or
and multilayered materials have been investigated and alumina coatings have been found to improve wettability
commercialized for use in Li‐ion batteries. This is and reduce thermal shrinkage.383,384
because, despite the advantages, polyolefin materials like Critically, the quality of the coating is extremely
PE and PP suffer from poor wettability and low thermal important, since coating defects can result in cell failure.
stability. In the case of acyclic alkyl carbonate‐based For instance, the recent failure of the Samsung Galaxy 7
electrolytes, the wettability is poor due to the lack of in 2017 was in part due to defects in the alumina coating
polar groups in the separator. While at high tempera- on the monolayer separator.18 In addition, the addition of
tures, the low thermal instability of polyolefin materials varying quantities of zeolite (5%, 10%, and 15% wt.) to
results in shrinkages that can lead to short‐circuiting polyimide (PI) matrixes revealed the 10% wt. based
issues.378 composition produced the optimal ionic conductivity
Other materials investigated to overcome these compared to the untreated sample.385 In addition, PI
drawbacks include poly(ethylene oxide) (PEO), poly- nano‐fiber‐based separators were found to be thermally
acrylonitrile (PAN), poly(methyl methacrylate) (PMMA), stable up 500°C, unlike traditional polyolefin‐based
poly(vinylidene fluoride) (PVDF), and poly(vinylidene separators which start shrinking around 150°C. More-
fluoride‐co‐hexafluoropropylene) (PVDF‐HFP).376 PAN‐ over, a recently developed hybrid PI‐based separator
base separators have good mechanical strength and combined with nanostructured core‐shell silica fillers
stability which can suppress dendritic growth. They also was found to have extremely good wettability, high
have high electrolyte uptake, Li+ ion conductivity, and tensile strength, and good thermal stability accompanied
good thermal stability. But can suffer from electrolyte with fire resistant properties.386
leakage. While PMMA‐based separators have good Carbonaceous materials have also been investigated
compatibility and wettability with electrolytes, their because porous carbons are lightweight compared to
amorphous structure has poor mechanical properties. other materials, have high accommodation due to their
Similarly, PVDF‐based separators have high Li+ ion porous structure, extremely large surface areas, and high
conductivity and good wettability, but they also suffer conductivities.387 For instance, graphene with a large
from poor thermal stability and low mechanical electrochemically active surface area and huge meso‐pore
strength.379,380 Because of these shortcomings new volume, was used by Zhou et al. to produce a coating on
approaches were investigated to improve the mechanical the one side of a separator and on a sulfur electrode in
and thermal properties of these separator materials. The a lithium‐sulfur battery. The coatings were found to
new approaches include introducing different inorganic promote both ion conduction and electron transport,
filler materials into a polymer hosts to produce compos- while the pore volume of the graphene coating was able to
ite materials with superior properties. These composite accommodate the volume expansion of sulfur.388 Other
materials are discussed in the following section. studies have shown that graphene can be combined with a
variety of polymers or metal oxides to improve the
Composite separators electrochemical performance of the composite separators
Commercial separators are predominantly composed of compared to graphene‐free separators.389,390 While a
organic polyolefin materials like PE and PP. However, recent study found that by adding graphene to a polymer
despite their good performance, they still have some matrix provides antipiercing properties to the separator
inherent property limitations. Therefore, recent research which significantly reduced the risk of dendrite penetra-
has focused on introducing reinforcing additives or tion in lithium metal batteries.391 Furthermore, the
coating to conventional materials to form composite mechanically strong two‐dimensional structure of gra-
separators with enhanced intrinsic, structural, and phene oxide (GO) provides diffusion channels to promote
material properties. Several materials like ceramics, fast Li+ ion transportation. Both GO and reduced
carbonaceous materials, metal oxides, nitrides, and graphene oxide (rGO) have functional groups that can
phosphorus have been investigated as potential fillers promote the accommodation sulfur species in lithium‐
or coatings for incorporation into advanced composite sulfur batteries. While the GO structure is mechanically
flexible and readily handle volumetric changes occurring responsible for promoting high ionic conductivity and the
during charging and discharging cycles.392,393 secondary polymeric material improves the mechanical
Several studies have attempted to use metal particles or and thermal properties.370,372 For instance, a recent study
metal oxide particles to produce composite separators. by Chen et al. found a separator blended from poly
Studies have shown lithiophilic metal particles can (oxyphenylene benzimidazole) (PBI) and ethyl cellulose
suppress the growth of Li‐dendrites. Since metals like (EC) could withstand elevated temperatures of around
Ag, Au, and Mg can lower the Gibbs free energy needed 350°C. Their study used thermo‐gravimetric analysis
for Li electro‐deposition.394 While the presence of oxygen (TGA) to investigate thermal stability of the PBI/EC blend.
atoms in metal oxides can assist in the absorption of LiPS The study revealed: (1) all moisture was extracted from the
and reduce the effects of shuttling in lithium‐sulfur blend at temperatures below 200°C; (2) decomposition of
batteries. Also, because of their polar affinity, metal oxides EC occurs between 200 and 350°C, and (3) At 500°C, the
promote the catalytic conversion of LiPS during the remaining weight of the PBI/EC blend was typically
recharging cycle.395 Alternatively, other studies have between 53.5 and 60.2 wt.%. This study revealed the high
investigated the use of nitrides like aluminium nitride thermal stability of the PBI/EC blend and the ultimate
(AN), boron nitride (BN), and niobium nitride (NbN) for decomposition temperature of PBI occurred at 540°C.399
separator applications. In particular, BN is an electrical Similarly, a study by Wu et al. examined the mechanical
insulator, thermally stable, and displays good thermal and thermal stability of a separator produced by electro‐
conductivity. Due to these properties BN‐coated separators spinning. The separator was composed of PI and PVDF
have uniform thermal surface distributions that promotes and consisted of a sandwich structure (PI/PVDF/PI). The
the development of a stable SEI which assists in Li separator had both high mechanical and thermal stability
stripping and plating during charging and discharging because even at 500°C the PI displayed low shrinkage.
cycles.396 While a recent study by Moraes et al. found that However, the inner PVDF layer melted after 10 min at
a separator composed of a PVDF matrix containing 170°C (shutdown temperature), thus demonstrating the
hexagonal boron nitride (hBN) nanosheets (filler) dis- separators shutdown function. The PI/PVDF blend
played good stability and performance in a Li‐ion battery separator also displayed good porosity, excellent electrolyte
operating at 120°C. Furthermore, when the temperature uptake, and high ionic conductivity.400
was increased up to 130°C, the hBN nanosheet composite
remained thermally stable, unlike conventional PE sepa-
rators which are thermally unstable at this temperature 5 | C U R R E N T CH A L L E N G E S
and underwent irreversible structural changes.397 FA CI N G LI ‐ ION B ATTERIES
While separators composed of a poly(vinylidene
fluoride‐co‐hexafluoropropylene) (PVDF‐HFP) matrix Today, rechargeable lithium‐ion batteries dominate the
and BN nanosheets manufactured by 3D printing were battery market because of their high energy density,
found to inhibit Li‐dendritic growth.379 Studies have also power density, and low self‐discharge rate. They are
examined the impact of black‐phosphorus (BP) and red‐ currently transforming the transportation sector with
phosphorus (RP) as filler materials to improve the electric vehicles. And in the near future, in combination
properties of conventional separator materials. Interest- with renewable energy sources like wind and solar, they
ingly, BP has similar properties to graphite and can form are expected to fully replace fossil‐fuel‐based power‐
chemical P‐S bonds with LiPS in lithium‐sulfur batteries. generating facilities and change the face of the global
Also, the phosphorene monolayer (zigzag direction) has economy. However, despite their many advantages and
an ionic diffusion rate around 104 times greater than applications they suffer from a number of challenges
graphene at room temperature.398 Besides being chemi- such as safety, high cost, degradation rates, and the
cally stable and easily prepared, it has a high specific recyclability of battery materials. These challenges are
capacity and is highly stable under charging and dischar- discussed in the following sections.
ging cycles.
Polymer blend separators 5.1 | Temperature‐induced aging and

Another method of improving the performance of a single battery thermal management
polymer‐based separator is to combine it with another
polymeric material to produce a blend. If the right 5.1.1 | Temperature‐induced aging
combination of polymers are used, then the blend will
have superior properties compared to either of the Importantly, there is an expectation that rechargeable Li‐
constituent polymers. In many cases one polymer is ion battery packs be: (1) defect‐free; (2) have high energy
densities (~235 Wh kg−1); (3) be dischargeable within 3 h; Globally, the environmental temperature is the prod-
(4) have charge/discharges cycles greater than 1000 uct of geographical location, climatic weather conditions,
cycles, and (5) have a calendar life of up to 15 years.401 and season. Thus, at lower latitudes, the temperatures are
Calendar life is directly influenced by factors like depth higher than those in higher latitudes. For instance, in the
of discharge, charge/discharge current rates, frequency of northern hemisphere, outdoor temperatures in winter are
charging cycles, and temperature.402–405 The most well below 0°C in countries like Canada, Greenland, and
important factor that impacts on battery performance Russia. Several studies have shown at these low tempera-
and calendar life is temperature.14,406 Moreover, both tures both the performance and battery calendar life are
high and low temperatures conditions result in different detrimentally affected418,437,438 and there is a significant
adverse effects that lead to accelerated Li‐ion battery overall degradation in the battery state of health.439 For
degradation.407 In particular, battery temperatures con- example, Nagasubramanian reported the reduction of
tinue to rise during long driving times and periods of electrical characteristics with decreasing temperature for
acceleration in electrical vehicles due to space constraints Panasonic type 18650 Li‐ion cells. The study revealed as
of the battery pack compartment, battery ventilation, and the environmental temperature was dropped from 25°C
heat accumulation resulting from charging and dischar- down to −40°C, both the power and energy densities fell
ging cycles.408–412 by 98.7% and 95%, respectively.440 While a study of the
And when temperatures exceed the upper safety operational range at different environmental temperatures
temperature of 60°C there is a possibility of thermal for an electric vehicle found its range decreased from 120
runaway reactions occurring and a resulting fire or miles at 20°C down to 60 miles at −20°C.441 And in recent
explosion taking place.413,414 Generally, the operational years, prospective space exploration mission studies have
temperature range for Li‐ion batteries is between −20°C identified an extremely low cold surface temperature on
and 60°C.415 However, for most commercial Li‐ion Mars, which can be as low as −120°C. Consequently,
batteries the recommended optimal working temperature making the design of any Li‐ion battery‐based power
range is between 15°C and 35°C.416,417 And since all main system for space exploration applications extremely
chemical reactions and side reactions within the battery challenging.442,443 Thus, highlighting the importance and
are all influenced by temperature, operating outside this impact of environmental temperatures on battery per-
optimal temperature range will have a detrimental effect formance, life cycle, and its state of health.436
on battery performance.418,419 The adverse effects resulting During normal operational temperatures, the electro-
from temperature can be divided into two categories. The chemical processes involved in converting electrical
first being low temperature (environment) effects, and energy into chemical energy during charging and
second is high temperature effects.420,421 converting chemical energy into electrical energy during
At low operating temperatures, chemical‐reaction discharging all produce heat. However, at high operating
activity and charge‐transfer rates are much slower in temperatures the effects produced are more complicated
Li‐ion batteries and results in lower electrolyte ionic than those generated at lower temperatures. At higher
conductivity and reduced ion diffusivity within the temperatures the active materials in the electrodes and
electrodes.422,423 Also under low temperatures Li‐ion the electrolyte undergo physiochemical changes. For
batteries will experience higher internal charge transfer instance, there are surface changes in the SEI, increasing
resistances resulting in greater levels of polarization of the side reactions, and electrolyte decomposition all contrib-
graphite anode and higher levels of lithium deposi- ute to declining battery performance.419,444 Thus, under-
tion.424–427 Under these conditions material embrittlement standing how heat is generated and methods of reducing
and battery degradation shortens battery life and leads to high temperatures is critical for improving battery
safety issues.428,429 Studies have shown the operational performance and prolonging the life span of the
performance of Li‐ion batteries will significantly degrade at battery.445 Typically, high temperatures result from the
temperatures below 0°C.374,430 In particular, lower temper- heat generated during high current operations such as
atures result in reduced charging/discharging cycle per- fast charging rates and fast discharging rates.446,447
formance and battery capacity.431–433 Importantly, studies Higher temperatures lead to a decline in battery
have shown the surrounding environmental temperature capacity due to higher chemical‐reaction activity, loss of
has a major influence on battery calendar life and its state reversible lithium due to electrode passivation processes,
of health (SOH).434,435 In the case of electrical vehicles structural degradation of the cathode, and electrolyte
(EV), the majority of the time the vehicle is in the degradation resulting from electrochemical side reactions
powered‐off state (parking state or storage state) and occurring at the electrodes.448 Furthermore, as the
battery temperature is the ambient environmental internal temperature increases the interfacial impedance
temperature.436 at the electrodes also increases due to increased
passivation processes. While increasing temperature also resistance, and lithium plating on carbon‐based anode.
results in increasing electrical resistance of other battery While high temperatures speed up thermal aging and
components like connectors and busbars, which also shorten the calendar life of the Li‐ion battery. In
contribute to the overall increasing internal resistance of addition, high temperatures can also trigger exothermic
the battery.449 reactions that generate even larger amounts of heat and
In recent years, several researchers have investigated result in thermal runaway. Furthermore, high charging
the causes of degradation on various Li‐ion battery rates also lead to high battery temperatures that can
components operating at high temperature (around influence calendar life. Therefore, Li‐ion batteries require
80°C) and the resulting impact on battery performance a battery thermal management system (BTMS) that can
and lifetime.450,451 Their studies have shown there are monitor and estimate the batteries state of health (SOH)
significant morphological and structural changes occur- during its lifespan.439,464 The well‐known BTMS is using:
ring on both electrodes at elevated temperatures during (1) air for cooling/heating ventilation; (2) liquid for
cycling.452–454 The studies have also shown higher cooling/heating; (3) phase change material (PCM); (4)
temperatures accelerate the degradation of the cathode heat pipe for cooling/heating. Examples of air BTMS are
via structural/phase changes taking place.407,455 While presented in Figure 4.
elevated temperatures also accelerate the formation of From the temperature perspective, the BTMS must
the SEI on the anode.453,456 Importantly, the SEI has supply heating at low temperatures and supply cooling
been shown to be a major contributor to increasing at high temperatures to ensure the battery operates in
internal battery resistance.457 the optimal temperature range. For large‐scale energy
In addition, studies have shown higher temperatures storage stations, battery temperature can be maintained
cause the electrode binder to migrate to the surface of the by in‐situ air conditioning systems. However, for other
positive electrode and form a binder layer which then battery systems alternative temperature control measures
reduces lithium re‐intercalation.450,458,459 Studies have
also shown electrolyte degradation and the products
generated from battery housing degradation at elevated
temperatures can also significantly contribute to battery
aging processes.378,460 Furthermore, uneven temperature
distributions between cells within a battery pack produce
electrical imbalances that result in localized aging,
capacity and power fading, and in general poor battery
performance.
Moreover, high temperatures and excessive tem-
perature variations result in self‐heating and thermal
runaway, and ultimately leads to self‐ignition and
possible catastrophic failure.461,462 Consequently,
proper thermal management is critical for the safe
operation, optimising performance and promoting
longer battery life spans.461–463 The following sections
discuss thermal management and hazards such as
overcharging, swelling and thermal runaway.
5.1.2 | Battery thermal management
The thermal challenges facing Li‐ion batteries arises

from their temperature‐dependent performance. As
previously mentioned, the optimal temperature range is
between 15°C and 35°C. Operating outside this range
will directly influence their overall performance and can
result in irreversible changes to the Li‐ion battery. Both
low and high temperatures can have detrimental effects,
with low‐temperature degradation resulting from F I G U R E 4 (A) Insight pack, (B) Prius pack, (C) Highlander
reduced of ionic conductivity, increased charge‐transfer pack. Reproduced with permission,417 Copyright 2016 Elsevier.
must be implemented. At low temperatures the BTMS equate to Li+ ion intercalation and de‐intercalation
is required to supply heating and this is supplied by either occurring at the anode and cathode. Once the battery is
internal or external heating systems. Several external charged, a high state of charge (SOC) will indicate a high
heating systems including heating films, heating plates, terminal voltage and signifies a lower anode potential
and Peltier heating systems have been used, but tempera- and higher cathode potential. When a carbon‐based
ture uniformity is poor and the energy losses are high.465 (graphite) anode has a low potential, the side reactions
Whereas, internal heating methods that use methods like taking place at the anode like SEI thickening will be
alternating current heating and built‐in nickel chip above normal levels indicating a higher degradation
systems have good heat distribution, lower heat losses, rates.481 For abnormal charging scenarios like over-
and are more efficient that external heating.466,467 charging (usually accompanied by rapid temperature
At high temperatures, the BTMS is required to supply rises) or low‐temperature charging (suffers from low Li+
cooling and this can be supplied by air cooling, liquid ion transportation rates), the resulting very low anode
cooling, refrigerant cooling, and phase change materials. potentials will cause lithium deposition and accelerate
The simplest method of cooling is by air and using battery degradation.482,483 Alternatively, when high
natural convection to dissipate heat from the battery cells cathode potentials occur there is significant cathode
into the surrounding environment.468 In many cases decomposition and electrolyte oxidation.484,485 Other
forced air‐cooling with different ducting structures is consequences of overcharging include battery swelling
used to direct air into the battery‐pack enclosures.469,470 (large volume expansions) and thermal runaway (dis-
However, sudden temperature rises in the battery pack cussed in the next section).
resulting from large charging or discharging cycles Battery swelling during overcharging is a symptom of
requires very large volumes of air.471 Consequently, the rapid increase of stresses within the battery structure
other studies have investigated liquid cooling to reduce resulting from large internal volumetric increases. For
temperatures more efficiently. Various configurations instance, a study by Spingler et al.486 investigated the
like cooling plates between batteries, cooling flow volume expansion of lithium‐ion pouch cells during a fast
channels, and tubes have been studied.472–474 In addition, charging mode. Their study used commercially available
even the more complicated refrigerant‐based cooling 3.3 Ah pouch cells with a nickel‐manganese‐cobalt‐
systems have been studied by some researchers.475,476 lithium oxide (NMC) cathode and graphite anode,
Research has revealed that refrigerant‐based cooling commonly known as a (NMC/G) Li‐ion battery. The
systems use more power, but are capable of maintaining dimensions of the pouch cell used were 95 mm in length,
battery systems below 40°C. Current research has 64 mm in width and 5.2 mm in thickness. Laser‐based
focused on developing and optimizing refrigerant cooling techniques were used to detect localized regions of
for the next generation of electrical vehicles.477 Alterna- expansion over the upper surface of the pouch cell.
tively, other researchers have focused their attention to During charging (constant current‐constant voltage
less complicated systems using phase change materials (CC‐CV) operation), several test pouch cells were charged
like paraffin enhanced with materials like nanoparticles from 0% to 100% (SOC) at four Coulombic rates (0.5, 1,
and carbon fiber to provide cooling.478,479 1.5, and 2 C). Representative results are presented in
Figure 5A, and reveal the largest expansion measured was
around 50 µm or 0.96% of the pouch cell thickness. Their
5.2 | Operational hazards of Li‐ion study revealed pouch cell expansion occurred during
batteries normal fast charge mode and the deformation was
tolerated by the casing.486
5.2.1 | Battery overcharging and swelling A similar study by Tomaszewska et al.487 explored the
phenomenon of battery swelling caused by overcharging.
Battery calendar life and degradation rates are influenced Their study was able to identify four distinct stages of the
by a number of critical factors that include: (1) operating overcharging process. In stage (1) for 100% to 120% of
temperature of battery; (2) current rates during charging SOC, is the beginning of overcharging and the anode can
and discharging cycles; (3) depth of discharge (DOD), handle lithium overload in spite of the battery voltage
and (4) time between full charging cycles.480 The battery exceeding the cut‐off voltage. Also in this stage both
charging process is generally controlled by a battery battery temperature and internal resistance are starting
management (BMS) and a specifically designed charger to rise, while some side reactions are beginning to occur
that regulates the charging current supply. Thus, the in the battery. Next is stage (2) for 120% to 140% SOC, the
charging process can be optimized. From the battery's cathode begins to decompose and depending on its
perspective, the charging and discharging processes composition will release transition metal ions (e.g.,
F I G U R E 5 (A) Localized regions of expansion of a commercial NMC pouch cell operating at various Coulombic rates. Reproduced with
permission,486 Copyright 2018 Elsevier and (B) The four stages of the overcharging process Reproduced with permission487 Copyright 2019
Elsevier.
Mn2+) due to the excessive de‐intercalation of lithium. 5.2.2 | Thermal runaway

Meanwhile at the anode, increasing lithium intercalation
results in the deposition of Li+ ions on its surface. And Because of the influence of temperature on battery
because the battery potential now exceeds its stable performance and calendar life, commercial Li‐ion batte-
operating potential window, the surface Li+ ions reacts ries are recommended to operate between 15°C and
with the electrolyte to generate a thicker SEI layer, which 35°C.416 Critically, the rate of all reactions (main and
in turn increases internal battery resistance. Also, during side) occurring within the battery are related to
this stage the electrolyte starts to oxidize; Following is temperature. The higher the temperature, the higher
stage (3) for 140% to 160% SOC, during this stage Li+ ions the reaction rate. So when the battery's temperature
continue to move from the cathode to the anode and Li+ reaches a critical value, it can trigger heat‐generating
ion activity with the electrolyte at the anode surface exothermic reactions that result in thermal runaway.488
increases. Meanwhile, oxidative decomposition of the Once this chain reaction gets underway, the heat being
electrolyte continues and large amounts of heat and gases generated by the various reactions exceeds the batteries
are generated, which also leads to the volumetric capacity to dissipate heat. Hence the temperature rapidly
expansion of battery. As the battery SOC approaches increases and causes irreversible damage to the electro-
160%, the battery voltage begins to drop with increasing des (chemical breakdown), the separator (melt tempera-
structural changes occurring in the cathode. In the final ture then shutdown), and the electrolyte via oxidation
stage (4) for above 160% SOC, oxidative decomposition of and breakdown. Which ultimately leads to battery
the electrolyte continues to generate large amounts of gas failure, fire, or even explosion.413,489
until the battery casing ruptures. During this stage, the The causes of thermal runaway come from three main
separator is also ruptured and as a result electrical sources: (1) temperature; (2) cell chemistry, and (3) abuse
contact is made between the anode and cathode that of the battery. In the case of temperature, thermal
leads to a short circuit and thermal runaway, as seen in runaway has been reported to start from around 130°C
Figure 5B.487 At this stage it is also too late to avert cell and go as high as 250°C.19 However, the temperature
component breakdown and destruction. varies between battery types (size, electrode materials,
electrolytes, and design & fabrication of battery structure rapidly.497 The outward growth of lithium dendrites from
and materials) and configurations (battery packs, applica- the surface of the anode travels through the electrolyte.
tions, cooling system, etc.). Cell chemistry and component The growing dendrites then penetrate through the
design have a significant influence on the cell's electro- polymer separator towards the cathode. The dendrites
chemical performance and safety. Significantly, the redox reach the cathode and make electrical contact. The
reactions between the cathode (i.e., Li(NixCoyMnz)O2) and ensuing short‐circuit is one of the major processes in a
the anode generate significant amounts of heat.19 Li‐ion cell that results in its failure.498 The resultant short‐
Current research is investigating alternative materials circuit further exacerbates the exothermic reactions taking
for the development of new and efficient cathode and place between the organic electrolyte and the electrodes,
anode materials that use chemistries that reduce the thus triggering thermal runaway.414 Consequently, signifi-
potential high exothermic reactions and hence improve cant research has concentrated on methods for suppress-
safety.490 And as mentioned above, at high temperatures, ing dendrite growth. Research has shown there four
cathode degradation (oxidation) and oxidative decompo- effective methods for suppressing dendritic growth.
sition of the electrolyte generate large amounts of heat The first method utilises surface modifications and
and gases. To reduce oxygen levels being liberated from coatings to suppress dendritic growth and has been
cathode degradation, recent research has focused on studied by several researchers.499,500 Carbon‐based ma-
increasing the spacing between layers in the cathode terials, polymers, and lithium compounds like lithium
structure to reduce activation energies and promote nitride and lithium fluoride have been used to modify the
faster Li+ ion diffusion pathways or to use dopants to SEI formation and its wettability to inhibit dendritic
improve the structurally stability of the cathode.491,492 growth.501,502 A number of coatings techniques, using a
Furthermore, a Li‐ion battery can also experience variety of materials have proven to be effective strategies
thermal runaway reaction caused by abuse. Physical abuse for reducing lithium nucleation and preventing dendritic
can result from poor handling or damage. For instance, an growth. For instance, lithiophilic coatings composed of
electrical vehicle battery pack could become penetrated by nickel foam containing graphitic carbon nitride g‐C3N4
fragments or experience mechanical deformation during a have been shown to suppress dendritic growth.503
collision. Alternatively, thermal runaway in a battery pack Whereas a lithiophilic–lithiophobic gradient‐based coat-
could also be triggered by electrical abuse as a result of ing composed of zinc oxide and carbon nanotubes (CNT)
charging or discharging above or below the manufacturer's produced by Zhang et al. suppressed dendritic growth
high/low voltage rate specification. In terms of charging/ while at the same time allowing lithium stripping. Their
discharging abuse, commercially available Li‐ion batteries study found the underlying zinc oxide (lithiophilic) layer
come equipped with safety devices like charge interrupt stabilized the SEI and the upper CNT (lithiophobic) layer
devices (CID), pressure relief vents, positive temperature suppressed dendritic growth.504
coefficient (PTC) systems, and fuses usually located in the The second method has focused on including organic
cell cap. While separators composed of phase transition and inorganic additives in the electrolyte that strongly
materials are designed to melt at elevated temperatures, attach to the facets of growing lithium crystals, suppress
seal the separators pore structure, and prevent Li+ ion their growth, and prevent dendritic formations. For
transport and current flow from the cell.493 Critically, Li‐ instance, Li et al. have investigated the influence of
ion battery system needs an efficient battery management varying concentrations of lithium polysulfide and lithium
system to monitor and control its voltage range, SOC, nitrate and found it to be an effective method for
current flows, release gases when over pressured, regulate preventing dendritic growth and achieving a Coulombic
and prevent excessive internal heat build‐up.464 efficiency of around 99% for over 300 cycles.505 Alterna-
tively, the addition of non‐Li cations to the electrolyte
produces positively charged electrostatic regions (cation
5.2.3 | Lithium dendrite formation shield) on the anode surface, which effectively suppresses
the formation of dendrites.506 However, the disadvantage
Lithium dendrites growth has become a big challenge for of this strategy is the possibility of the additive interfering
lithium batteries since it was discovered in 1972.40 In 1973, and reducing the Li+ ion conductivity of the electrolyte.
Fenton et al studied the correlation between the ionic A third method of suppressing dendritic growth is by
conductivity and the lithium dendrite growth.494 Later, in confinement, which involves controlling the direction of
1978, Armand discovered PEs that have been considered lithium growth pathways. Current research is focused on
to suppress lithium dendrites growth.40,495,496 The latest developing mixed ionic and electronic conductor (MIEC)
study by He et al. in 2019 revealed that Li ions are less composite scaffolds as a method for directing the flow of
prone to deposit as dendrites if the SEI layer conducts ions Li+ ions from the anode and controlling the direction of
dendritic growth.507,508 For instance, Zhang et al. manufac- setting off thermal runaway is possible. In any event, if
tured a composite MIEC scaffold that consisted of thermal runaway is triggered, the ensuing chain reaction
Li6.4La3Zr2Al0.2O12 (LLZO) nanoparticles included in the and rapid increase in temperature results in the organic
carbon nano‐fiber (CNF) structure. Their study found the electrolyte vaporizing. The rapid build‐up of pressure
Li+ ions would selectively settle on the LLZO‐decorated within the battery is either released by pressure relief
nano‐fibers and dendritic growth would be in a non‐vertical vents or casing failure, but in any event there is the release
direction. Then the Li+ ions would dissolve from the of flammable and toxic gases. The scale of the resulting
nano‐fibers during lithium stripping.509 However, further incident is dependent on the battery size, casing
research is needed to further develop this technique. construction, chemistry, SOC, and battery safety features.
The fourth method for suppressing dendritic growth In terms of chemical hazards, LiPF6 salt is widely
is by the use of solid‐state electrolytes.510 Monroe and used in current Li‐ion batteries and easily reacts with
Newman, in 2005, have shown dendritic growth can be water due to its poor stability.284,295 Even solid LiPF6 salt
suppressed when the shear modulus of the separator is and dissolved LiPF6 can exist in equilibrium with their
1.8 times higher (approx. 6 GPa) than that of Li metal decomposition products at room temperature as seen in
(4.9 GPa).511 Recent work by Lv et al. shows that Equation (14).513,514 And when LiPF6 comes into contact
inorganic solid‐state electrolytes can suppress dendritic with either atmospheric moisture of small amounts of
growth.512 They suggested combining organic SSEs (for water present in the electrolyte it undergoes hydrolysis to
eliminating pores, voids, cracks, and grain boundaries generate products like hydrogen fluoride (HF) and
between Li and SSE interfaces) and inorganic SSEs (for phosphoryl fluoride (POF3) as seen in Equation (15).514
improving ionic conductivity and reducing electronic Moreover, due to phosphoryl fluorides reactive nature it
conductivity) to achieve the best advantage.512 As a undergoes further hydrolysis to generate addition HF
consequence, a considerable amount of research effort and difluorophosphoric acid as seen in Equation (16).
has been undertaken to develop solid electrolyte/separa-
tors specifically designed to prevent dendritic growth, LiPF6 (solid salt or in solution)
(14)
which was discussed in Section 4.4.2 above. ⇄ LiF(solid) + PF5 (gas or in solution)
LiPF6 + H2 O  LiF + 2HF + POF3 (15)

5.3 | Handling and safety
POF3 + H2 O  HF + POF2 (OH) (16)
Li‐ion batteries have two major inherent risk factors that
contribute to a fire hazard. The first is their inherent high Additionally, difluorophosphoric acid will then
energy density compared to other battery types and the slowly react and generate additional HF as seen in
second is the highly flammable organic solvents that are Equation (17).514,515
used to make the battery's electrolyte. Section 5.2 above
discussed how physical abuse, electrical abuse, and POF2 (OH) + 2H2 O  2HF + H3 PO4 (17)
exposure to high temperatures can initiate thermal
runaway. Because of these issues and the associated fire Thus, the leakage of LiPF6 salt from the cell and
hazard, storing and handling Li‐batteries is certainly subsequent hydrolysis resulting from atmospheric
challenging. Even Li‐ion batteries, battery packs, and moisture or water contamination can result in the
equipment containing Li‐ion batteries stored in ware- generation of dangerous HF. Importantly, HF is a very
houses or being transported are exposed to hazards. For toxic and corrosive compound and its toxicity levels are
example, damage caused by forklift accidents or dropping reached within a few ppm. Similarly, other compounds
incidents or general mishandling can be serious. present in Li‐ion batteries or produced during a burning
Physical abuse resulting from crushing or puncture situation516 also have associated toxicities and hazards.
can lead to the release of electrolyte materal, initiate short‐ For instance, the USA's Protective Action Criteria
circuits, and possibly set off a thermal runaway reaction. (PAC) identify three levels of exposure. Each level
In particular, Li‐ion batteries should be stored in indicates an increasing level and severity of exposure.
well‐ventilated dry storage areas (isolated from other The levels include: PAC‐1, mild, transient health effects;
types of batteries, flammable liquids or explosive materi- PAC‐2 irreversible or other serious health effects and
als) and not exposed to direct sunlight, heat sources, and the in ability to take protective action; and PAC‐3, life‐
water. For example, when lithium‐ion graphitic anodes threatening health effects.517 Table 5 presents hazard
immersed in organic electrolytes are heated between 70 types and PAC exposure levels for several materials
and 90°C, the possibility of initiating self‐heating and currently used Li‐ion batteries.
In the event of battery venting without ignition,
Acute toxicity, skin corrosion, corrosive to the respiratory

flammable and toxic gases are emitted and consist mainly
Eye irritation, skin irritation; specific targeted organ
Eye irritation, skin irritation, specific targeted organ

of carbon monoxide (CO), dioxide (CO2), hydrogen (H2),
and several hydrocarbons (CxHx). In this scenario, a well‐
ventilated storage area is paramount so that the vented
materials can freely disperse into the atmosphere without
risk of ignition. For the burning case situation, Peng et al.
studied the thermal and toxic hazards resulting from
thermal runaway of a Li‐ion battery (LiFePO4 electrolyte/
toxicity‐single exposure.
graphite electrode). The study identified three important
Hazard to personnel
parameters: (1) heat release rate; (2) time taken for

ignition, and (3) fire radiation and gas emissions.516 A
selection of batteries, each having varying amounts of SOC
(0%, 50%, 75%, and 100%), were individually ignited inside
tract a combustion chamber and the resulting gas emissions
were analysed using Fourier‐transform infrared (FTIR)
spectroscopy. During each combustion test, the analysis
revealed the primary products were asphyxiant gases (CO
and CO2), irritant gases (HF, SO2, NO2, NO, and HCl), and
PAC‐1: 30 mg m−3 PAC‐2: 330 mg m−3PAC‐3: 2000 mg m−3
PAC‐1: 3.3 mg m−3 PAC‐2: 37 mg m−3 PAC‐3: 220 mg m−3
water vapor (H2O).

Moreover, several studies have also confirmed the
PAC‐1A: 1 ppmPAC‐2A: 24 ppmPAC‐3A: 44 ppm
liberation of fluorine from lithium salts (typically LiPF6)

PAC‐1: 0.42 ppmPAC‐2: 4.6 ppmPAC‐3: 70 ppm
PAC‐1: 11 ppmPAC‐2: 120 ppmPAC‐3: 700 ppm
dissolved in the electrolyte and from the PVDF electrode

binder (Pyrolysis temp. 380°C to 400°C).519 The liberated
Hazard types and PAC exposure levels for some material used in Li‐ion batteries.514,518
fluorine readily reacts with hydrogen to produce hydrogen

fluoride (HF). Interestingly, the amount of HF produced
has also been found to be proportional to the amount of
energy stored in the battery. Thus, it is possible for
PAC levels not available
dangerous concentrations of HF to be generated during

combustion. Also, the LiPF6‐based electrolytes are
unstable and readily begin to decompose into PF5 when
the battery temperature reaches 60°C.520 Critically, both
PAC Level
PF5 and HF are extremely toxic gases. Furthermore, when

HF comes into contact with water, either water vapor
from the reaction process or water present in the
surrounding environment or water present in the mucus
membranes present in the human body (i.e., eyes, lungs,
Hazard type
nose, and throat), it hydrolyses and forms hydrofluoric

Flammable
Flammable
Flammable
acid.518 One further hazard associated with Li‐ion

Irritant
Irritant
Toxic
batteries is their disposal. Even when they can no longer

hold a useful charge, they still have significant residual
energy that can lead to fire accidents and even explosion
during recycling. Therefore, It is important that Li‐ion
DMC
EMC
DEC
batteries have to be fully discharged before recycling.521

HF
EC
PC
Ethyl methyl carbonate
5.4 | Li‐ion batteries, their economics,

Propylene carbonate
Dimethyl carbonate
Ethylene carbonate
and their recycling

Hydrogen fluoride
Diethyl carbonate
5.4.1 | The economics aspect

Substance
TABLE 5
Today, Li‐ion batteries are extensively used in many

portable electronic devices and are currently the main
electrical power technology for novel electrical vehi- Li, Co, and Ni, graphite in the anode and Al and Cu in
cles.522 For instance, the portable electronic device other battery components. The most commonly used
market has doubled in the period from 2014 to 2019. cathode chemistries at present and their market share are
And in recent years the demand for electric vehicles and lithium cobalt oxide (LCO, 37.2%), lithium nickel manga-
energy storage systems for renewable energy sources has nese cobalt oxide (NMC, 29%), and lithium iron phosphate
rapidly increased.523 In 2012 Yoshino examined the use (LFP, 5.2%).530 Importantly, because of the increasing
of Li‐ion batteries in consumer products and electrical demand for Li‐ion batteries with higher energy densities
vehicles since 1998 and found a rapidly increasing trend and faster charging times, improved and new chemistries
in market share, as seen in Figure 6A.524 A similar study are rapidly being developed and can be expected in the
by Pillot for Avicenne Energy also found increasing near future.531 Especially, since major battery manufac-
trends in the sales of consumer products and electrical turers have committed to investing around US$ 50 billion
vehicles, as seen in Figure 6B. Their study predicted dollars to increase Li‐ion battery production to meet the
Li‐ion battery sales would reach around US$ 10 billion
dollars in 2025.525 While Gao et al. found the Li‐ion
battery pack sales related to electric vehicles increased
from 5 million in 2015 to also most 7 million in 2020,
and predicted sales would reach around 180 million in
2045.526 Further, the total annual growth rates for Li‐ion
batteries between 2015 and 2018 were around 24% and
these rates were propelled by their increasing use of
transport and power applications.527
The demand for Li‐ion batteries pushes lithium
mining production worldwide. According to the British
Petroleum Statistical Review of World Energy 2021,
global lithium production has more than doubled since
2016.528 In 2020, Australia, Chile, and China accounted
for 86% of worldwide lithium production, which are
40,000 tones, 20,600 tones, and 14,000 tones, respectively.
This data is presented in Figure 7.
While electric vehicle production consumed around
43% of the global production of Li‐ion batteries in 2012,
by 2018 it had reached 70% and the trend is expected to
continue. Typical Li‐ion batteries used in electrical F I G U R E 7 Lithium mine production by country from 1995 to
vehicles are currently made from cathode materials like 2020. Adapted from.529
F I G U R E 6 (A) The demand for Li‐ion batteries from 1998 to 2018. Reproduced with permission,524 Copyright 2012, Wiley and
(B) Market value of Li‐ion batteries from 2005 to 2025. Adapted from Yan et al.507
ever‐increasing global demand.527 And as a consequence metals contained within Li‐ion batteries and the extremely
of increasing electrification in the automotive sector and large numbers of batteries being produced that makes
energy storage system sector, the adoption of Li‐ion recycling worthwhile. A recent study by Mossali et al.
battery‐based energy also represents the fastest‐growing examined the economic value of metals currently used in
waste stream.532 In spite of around 500 thousand tons of the manufacture of Li‐ion batteries. Their study found
Li‐ion battery waste being generated in 2020, there is no cobalt and nickel were the most expensive metals used in
established recycling strategies for collecting and proces- the manufacture of cathodes, as seen in Table 6.537
sing waste Li‐ion batteries.533 Currently, only metallic materials (Al, Co, Cu, Ni, and
There are a number drivers for promoting Li‐ion steel) are recycled, while Li, Mn, and graphite are rarely
battery recycling strategies and these include: (1) recycled due to economic considerations.
sustainable circular management of resources and reduce Any plastic components used in the battery structure
mining usage of natural resources, as seen in Figure 8; are usually burnt for energy recovery to off‐set the costs
(2) reduce fossil fuel usage and therefore reduce green- of recycling.538 The jellyroll construction of the 18–650
house gas emissions; (3) minimise environmental con- Li‐ion battery and the major materials used in its cathode
tamination from toxic waste battery products; (4) reduce and anode are presented in Figure 9A. Inspection of
the levels of waste being generated, and (5) create Figure 9A reveals Ni is the largest component found in
financial gain from used batteries.534 In recent years the cathode, followed by Co and then Li and Al. Of these,
there has been considerable interest shown in developing only Ni and Co are of significant economic value and
economically viable and eco‐friendly sustainable strate- recycled.
gies for producing a wide variety of products from However, when large numbers of Li‐ion batteries are
recycled materials. Recycling Li‐ion batteries is one such considered, other metallic elements become significant.
strategy that meets this goal and also mediates the effects For instance, Figure 9B presents a schematic of Li‐ion
of diminishing natural resources. Importantly, recycling battery pack modules in a Tesla Model S electric vehicle.
prevents harmful products entering the environment The 16 modules forming the battery pack contain 7104
through landfill disposal. Li‐ion (18–650) batteries.539 From the recycling perspec-
Unfortunately, the chemistry of Li‐ion batteries is tive, the battery pack equates to 47.2 kg of Ni (US$ 623),
not eco‐friendly. For instance, metallic Li reacts with 7.1 kg of Li (US$ 71), 9 kg of Co (US$ 320), and 1.3 kg of Al
moisture and coupled with the highly flammable electro- (US$ 2.30). This equates to a material value of US$ 943 per
lyte could explode releasing harmful gases. Alternatively, vehicle battery pack for recycling the Co and Ni alone.
the disposed batteries will degrade and ultimately release Therefore, taking into consideration the very large
toxic materials into the environment, as mentioned in numbers of Li‐ion batteries being manufactured, both
Section 5.3.535,536 However, it is the economic value of currently and in the near future, developing a green
circular Li‐ion battery recycling economy is critical for
long‐term viability and sustainability of this technology
Figure 10.
5.4.2 | Recycling techniques for a circular

economy
The recovery of valuable materials from spent Li‐ion

batteries through recycling will help to reduce primary
material production and further promote a circular
economy.541 The recycling process is a multistage process.
It begins with a preparation stage that sorts the various
Li‐ion battery types, discharges the batteries, and then
dismantles the batteries ready for the pretreatment stage.
The subsequent pretreatment stage is designed to separate
high‐value metals from nonrecoverable materials. Impor-
tantly, pretreatment results in higher recovery rates
F I G U R E 8 The sustainable circular management of resources and lower energy usage in subsequent pyrometallurgical
to reduce mining and promote viable eco‐friendly recycling and/or hydrometallurgical processes. Pyrometallurgical
strategies. recycling involves smelting to recover metals, while
T A B L E 6 Typical chemical composition and economic value of materials used to produce Lithium‐ion batteries. Reproduced and
adapted with permission,537 Copyright 2020, Elsevier.
Value (US$ per ton)
Cell
components Chemical element in composition % wt. 2001 2017 2019
Cathode 25−30
Aluminium Al current collector foil 5–8 1250 2000 1800
Metal oxide Li 1.5–7 7500 9000 10000
Co LCO (LiCoO2) 5–20 38000 55000 35500
Ni LNO (LiNiO2) NCA 5–10 8600 10000 13200
(LiNi0.8Co0.15Al0.05O2)
Mn LMO (LiMnO2) NMC (LiNixCoyMnzO2) 5 1100 2000 2000
Anode 15–25
Copper Cu Current collector foil 8–10 1800 5500 5800
Graphite C 15–17 550 1000 800
Ext. Casing
Steel Fe‐Ni typical of cylindrical cells 20–26 ‐ ‐ ‐
Aluminium Al Usually in prismatic cells 10 1250 2000 1800
F I G U R E 9 (A) Material content of a Li‐ion (18–650) battery and (B) Tesla Model S battery pack and its metal content and cost,
Reproduced from.539
F I G U R E 10 Comparison chart of hydrometallurgy and pyrometallurgy. Reproduced from reference.540
hydrometallurgical processing involves acid leaching The goal of pretreatment processes is to reduce scrap
followed by solvent extraction and precipitation to obtain volumes and target valuable metals for accumulation.
metals.542,543 Several chemical and physical processes like chemical
dissolution of collector foils, physical separation by
Waste preparation and pretreatment stages floatation, mechanical methods like crushing and shred-
The main function of the waste preparation stage is ding, and thermal vaporization of organic compo-
battery deactivation. All Li‐ion batteries destined for nents.548,549 After undergoing chemical and physical
disposal have already being used and still have residual processing the metal‐enriched fraction is directed towards
energy. Because of the residual energy, handling pyrometallurgical and/or hydrometallurgical processes. In
and manipulation can lead to accidental fires and the case of hydrometallurgical processing, pre‐treatments
explosions during the ensuing recycling processes.168,544 are important because of the high selectivity of leaching
Deactivation usually involves immersing the battery in agents used in the process. The performance of the
aqueous salt baths, either saturated solutions of NaCl or leaching agents is reduced by the presence of impurities
Na2SO4. During immersion, the battery discharges, and like Al and Cu emanating from the current collector foils.
the Li+ ions move to the cathode reducing the amount of
metallic Li at the anode. However, because of the Pyrometallurgical recycling processes
possibility of battery leakage and the subsequent genera- Pyrometallurgical recycling is an energy‐intense process
tion of HF gases, alternative discharge methods such as that involves high temperatures to smelt metals. There are
covering batteries with stainless steel chips or connecting three stages: (1) the pyrolysis of electrolyte and plastic
the batteries to resistors are being considered as materials; (2) the reduction of metal alloys, and (3)
alternative.544,545 Following deactivation, the Li‐ion pyrolysis and quenching of gases to avoid toxic emissions
batteries are dismantled to reduce the volume of (i.e., dioxins, furans, etc.). In the first stage, pyrolysis
materials to be handled in subsequent pretreatment electrolyte at place around 300°C and this is followed by
methods. Dismantling is usually carried out manually, the pyrolysis of plastic components at around 700°C. The
but because of the time involved and labor costs, heat generated during this stage could be used to offset the
automated dismantling systems are currently being demand for energy in the metal reduction stage. In the
investigated.546,547 After dismantling the waste is ready metal reduction stage, valuable smelt materials containing
for pretreatment. Cu, Co, Ni, and Fe are formed, also produced in the slag is
Al, Ca, Li, and Si.550 Unfortunately, only Co, Cu, Ni, and entities for recovering spent LCO cathode‐based materi-
to a less extent Fe can be economically recovered. als. Studies have shown the metabolites secreted by
Leaching the slag for Al and Li is not economically microorganisms can be used to dissolve spent electrode
feasibility. This type of processing is strongly dependent materials and extract metals.556 Several bacteria and
on the Li‐ion battery chemistry, since the price of Co and fungi have been studied as bio‐leaching agents for
the Co content of the cathode is the main driver. dissolving and processing spent LiCoO2‐based materials.
Currently, Co‐based cathodes are extensively used in However, achieving optimal bio‐leaching is challenging
Li‐ion batteries, but evolving battery chemistries could see because of factors like thermodynamics and leaching
this material being significantly reduced or phased out.551 kinetics which are dependent on biomass density.557
Moreover, the pyrometallurgical process has several Furthermore, both eco‐friendly bio‐hydrometallurgical
disadvantages that include: (1) high capital costs; (2) high and conventional hydrometallurgical processes are heav-
energy consumption; (3) material loss (loss of Li and Al), ily dependent on the pretreatment process used to
and (4) emission of toxic gases. And because of the large separate and produce the cathode material‐based pow-
number of Li‐ion batteries predicted for future applica- ders. Thus, the quality of the pretreatment processes can
tions, it is necessary to find alternative recycling processes have a significant impact on the quality and recovery
with lower energy demands, higher efficiencies, and lower rates in the subsequent leaching and recovery methods.
environmental risks. Furthermore, a major issue with any form of acid‐based
leaching is the selectivity towards other metal ions. The
Hydrometallurgy recycling processes leaching process may dissolve several metal ion species,
Hydrometallurgical processing is an attractive strategy which makes selective separation of the preferred high‐
for recovering metals from spent Li‐ion batteries. value metal more difficult.
Typically, the process involves acid leaching that is
followed by recovery methods like solvent extraction and
precipitation. In particular, acid leaching can achieve 6 | CONCLUSION AND F UTURE
high recovery rates due to the soluble nature of cathode PERSPEC TIVES
materials in acids like hydrochloric acid (HCL). In
addition, hydrometallurgical processing can achieve high The present review has outlined the historical back-
metal purities and high recovery rates due to its ground relating to lithium, the inception of early Li‐ion
adaptability to different battery chemistries.552 Recovery batteries in the early 20th century and the subsequent
of metals is dependent on reductant species, solid/liquid commercialisation of Li‐ion batteries in the 1990s. The
ratios, leaching times, and temperature.553 When fully operational principle of a typical rechargeable Li‐ion
optimised hydrometallurgical processing can recover battery and its reaction mechanisms with lithium was
97% of cobalt and around 98% of copper from waste discussed. The discussion also identified major battery
streams.552 For instance, HCL is an efficient acid for components and their respective functions. Importantly,
leaching Co from LCO cathode‐based materials as seen the review then summarised the current status of
in Equation (18). However, a further posttreatment step advanced intercalation and de‐intercalation anode and
is required to address the emission of toxic Cl2 gases. cathode materials used in the manufacture of recharge-
able Li‐ion batteries. Anode materials like soft & hard
2LiCoO2 + 8HCl  2CoCl2 + Cl2 + 2LiCl carbons, graphene, CNTs, titanium‐oxide/dioxide, lith-
(18)
+ 4H2 O. ium titanium oxide (Spinel, LTO), alloying materials
(silicon, silicon oxides, and Ge), and conversion materials
Alternatively, other strong inorganic acids like sulfu- (metal compounds like oxides, nitrides, phosphides, and
ric acid in combination with hydrogen peroxide avoid the sulfides) were comprehensively discussed. While cathode
production of harmful Cl2 as seen in Equation (19). In materials like transition metal oxide cathodes (i.e., LCO),
addition, some studies have also investigated the use of spinel materials (i.e., LMO), and olivine materials (i.e.,
mild organic acids like oxalic acid for recovering cobalt LMP) were also discussed.
and lithium from LCO cathodes.554,555 The review also summarised the current status of
research into both electrolytes and separators. Electrolyte
2LiCoO2 + 3H2 SO4 + H2 O2 types (liquid, ionic, solid/gel polymers, and solid
(19)
 2CoSO4 + O2 + Li2 SO4 + 4H2 O. polymer/inorganic composites) and properties (high Li+
ion conduction, electronic insulation to prevent short‐
Importantly, recent research has focused on eco‐ circuits, good electrochemical stability to prevent decom-
friendly hydrometallurgical processes that use biological position and parasitic side reactions, good mechanical
and thermally stable, chemically inert, long service life circular economy that fully recycles materials and
and low toxicity) were elucidated. Likewise, separator reduces wastes to a minimum. Current industrial‐scale
types (microporous, polymers, and composites) and metal recovery processes like pyrometallurgical and
properties (intrinsic and structural) were also discussed hydrometallurgical can be used, but further research is
at length. needed to optimise these processes specifically for battery
The review highlighted the high capacity and high metals. In addition, further research is needed to
power characteristics of Li‐ion batteries makes them investigate the use bacteria and fungi as bio‐leaching
highly relevant for use in large‐scale energy storage agents for dissolving and processing spent battery
systems to store intermittent renewable energy harvested materials. Since it offers an eco‐friendly alternative to
from sources like solar and wind and for use in electric conventional industrial processes.
vehicles to replace polluting internal combustion engine The present review has summarised the current
vehicles. The main drivers for developing Li‐ion batteries status of Li‐ion batteries and has identified a number of
for these applications include energy density, cost, challenges that will need to be addressed in the near
calendar life, and safety. Thus, to ensure the long‐term future. The review can also be considered a convenient
sustainability of the Li‐ion battery market, significant reference for researchers and engineers working in the
progress is needed to improve intrinsic properties of field, since it provides key information relevant electrode
current electrode chemistries and operational parameters materials, electrolytes and separators. It also highlights
for promoting longer calendar life and grater safety. important economic aspects and environmental consid-
However, despite the current success of Li‐ion erations that make recycling spent Li‐ion materials an
batteries, the review has identified a number of important part of developing a sustainable circular
challenges that still remain to be addressed before material life cycle.
improved performances and wider applications can be
achieved. These challenges include: (1) aging and A U T H O R C O N TR I B U T I O N S
degradation; (2) improved safety; (3) material costs, All authors contributed equally to this work.
and (4) recyclability. Temperature influences all main
chemical reactions and side reactions within the cell and AC KNOW LEDGM ENTS
operating outside the optimal temperature range Miss Triana Wulandari would like to thank Murdoch
(15°C–35°C) has a detrimental effect on cell perform- University for a scholarship to undertake her PhD studies
ance. At higher temperatures the active materials present at Murdoch University, Australia.
in the electrodes and the electrolyte undergo physio-
chemical changes that result in compositional modifica- C O NF L I C T O F I N T E R E S T S TA T E M E N T
tions of the SEI, increasing side reactions and electrolyte The authors declare no conflict of interest.
decomposition. Moreover, the resulting electrical imbal-
ances accelerate aging, reduce capacity produce power ORC ID
fading, and ultimately shorten cell life. And in the worst‐ Gerrard E. J. Poinern http://orcid.org/0000-0003-
case scenario trigger self‐heating and thermal runaway, 0937-4482
which ultimately leads to catastrophic failure. Thus, for
large‐scale applications that require thousands of cells to
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Triana Wulandari completed her MSc
Banerjee PC. Current challenges and future opportunities
toward recycling of spent lithium‐ion batteries. Renew degree in Nanoscience from the Univer-
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148‐156. She received her BSc in Physics from
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University with the Murdoch Applied Innovation
lithium‐ion batteries: a critical examination of current Nanotechnology Research Group–MAINRG, under
the supervision of Assoc. Prof. Gerrard E.J. Poinern. potential skin tissue engineering applications. He is
Her research interests focuses on the use of sustain- the recipient of a Gates Foundation Global Health
able nanomaterials in the field of Next Energy and Grand Challenge Exploration Award for his work in
Environment. Her current research activity involves the development of biosynthetic materials and their
synthesizing and characterizing novel hematite na- subsequent application in the manufacture of bio-
noparticles for Li‐ion battery anodes. medical devices. To date, the MAINRG has several
PhD completions, Physics Honors completions to its
Associate Professor Gerrard E. J. Poi- credit and it has published more than 90 peer‐reviewed
nern MASC, MAIP, received a double journals and five book chapters in the nanotechnology/
major (BSc) in Chemistry and Physics nanoscience field and several innovation patents with
(Hons‐Physics) from Murdoch Univer- the members of the group. He is also the author of the
sity. He holds a PhD in Physics from 2014 CRC Press experimental textbook “A Laboratory
Murdoch University, Western Australia. Course in Nanoscience and Nanotechnology.” In 2023
He has served on the Editorial board of Springer he edited the CRC book “Harnessing Synthetic
Nature‐Scientific Reports since 2017. He is currently Nanotechnology‐Based Methodologies for Sustainable
the director of Murdoch Applied Innovation and Green Applications together with A/Prof Suraj Tri-
Nanotechnology Research Group‐MAINRG, Murdoch pathy from India and Dr Derek Fawcett from Murdoch
University. Previous to joining Curtin University at University which details the various aspect of nano-
the Nanochemistry Research Institute in Perth, he technology adoption in the community. Currently, his
was the Monbusho Fellow at the High Energy research group has various projects in Green Nano-
Accelerator Research Organization (Photon Factory) materials for Battery technology and Bio‐nanocarbons
in KEK, Tsukuba, Japan A/Prof Poinern has been from biowaste as electrode materials and biomaterials.
dedicated to the advancement of Nanotechnology and
Nanoscience since its inception at Murdoch Univer-
sity and created the Murdoch Applied Nano- How to cite this article: Wulandari T, Fawcett D,
technology Research Group‐MAINRG for the devel- Majumder SB, Poinern GEJ. Lithium‐based
opment of technologies such as nanomembranes for batteries, history, current status, challenges and
wound healing, biomedical nanobone and engineered future perspectives. Battery Energy.
green nanomaterials. In 2003, he discovered and 2023;2:20230030. doi:10.1002/bte2.20230030
pioneered the use of an inorganic nanomembrane for

Battery Energy - 2023 - Wulandari - Lithium Based Batteries History Current Status Challenges and Future Perspectives

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Received: 21 July 2023 | Revised: 27 August 2023 | Accepted: 11 September 2023

Lithium‐based batteries, history, current status,

Triana Wulandari1 | Derek Fawcett1 | Subhasish B. Majumder2 |

1 | INTRODUCTION Accordingly, in recent years there has been a rapid

Battery Energy. 2023;2:20230030. onlinelibrary.wiley.com/r/batteryenergy | 1 of 53

4.1 | Anode materials presents a selection of anode materials and summarises

TABLE 1 A selection of anode materials developed for Li‐ion batteries.

TABLE 2 A selection of cathode materials for Li‐ion batteries.

TABLE 3 A selection of Li salts used in liquid organic‐based electrolytes.299,300

Polymer blend separators 5.1 | Temperature‐induced aging and

5.1.2 | Battery thermal management

The thermal challenges facing Li‐ion batteries arises

Mn2+) due to the excessive de‐intercalation of lithium. 5.2.2 | Thermal runaway

LiPF6 + H2 O  LiF + 2HF + POF3 (15)

In the event of battery venting without ignition,

Acute toxicity, skin corrosion, corrosive to the respiratory

Eye irritation, skin irritation, specific targeted organ

Eye irritation, skin irritation, specific targeted organ

Eye irritation, skin irritation, specific targeted organ

Eye irritation, skin irritation, specific targeted organ

parameters: (1) heat release rate; (2) time taken for

PAC‐1: 3.3 mg m−3 PAC‐2: 37 mg m−3 PAC‐3: 220 mg m−3

water vapor (H2O).

liberation of fluorine from lithium salts (typically LiPF6)

PAC‐1: 11 ppmPAC‐2: 120 ppmPAC‐3: 700 ppm

dissolved in the electrolyte and from the PVDF electrode

fluorine readily reacts with hydrogen to produce hydrogen

dangerous concentrations of HF to be generated during

PF5 and HF are extremely toxic gases. Furthermore, when

nose, and throat), it hydrolyses and forms hydrofluoric

acid.518 One further hazard associated with Li‐ion

batteries is their disposal. Even when they can no longer

batteries have to be fully discharged before recycling.521

5.4 | Li‐ion batteries, their economics,

and their recycling

5.4.1 | The economics aspect

Today, Li‐ion batteries are extensively used in many

5.4.2 | Recycling techniques for a circular

The recovery of valuable materials from spent Li‐ion

F I G U R E 10 Comparison chart of hydrometallurgy and pyrometallurgy. Reproduced from reference.540

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