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Editorial
Batteries & Supercaps doi.org/10.1002/batt.202100089

Batteries & Supercaps: Beyond Lithium-Ion Batteries

Ivana Hasa,*[a] Philipp Adelhelm,*[b] Guozhong Cao,*[c] and Liqiang Mai*[d]

It was about thirty years ago, with the first successful D riven by the societal and governmental goals of transition-
commercialization of lithium-ion batteries (LIBs), that a new era ing to a low-carbon economy, the continuously growing global
begun. These new electrochemical energy storage systems battery demand will approach 1,000 GWh in 2025. The main
were about to transform the way society communicates, contributor to the rising demand for LIBs is the electric vehicle
moves, and lives. The journey that led to this success started (EV) market. The stationary storage market is also expected to
back in the early 70s until the mid 1980 paving the way for LIBs experience significant growth in the next decades.[5] The global
commercialization in 1991.[1] LIBs undoubtably represent the demand is growing at a very fast pace and calls for improved
most successful example of secondary battery. Their impor- cell technologies able to satisfy a variety of requirements
tance is reflected in the 2019 Nobel Prize for Chemistry according to the final application. Market diversification and
awarded to Dr. Yoshino, Prof. Whittingham, and Prof. Good- different application requirements accelerate the research
enough for their pioneering work toward the development of toward the next-generation electrochemical energy storage
the LIB technology.[2] systems, including sodium-based batteries and multivalent
chemistries, where safety, cost, sustainability, dependency on
In the years following commercialization, the performance of raw critical materials, and manufacturability are critical param-
LIBs has drastically improved until 1995, when the golden eters to be considered. In such a scenario, beyond LIB
combination was achieved by matching graphite at the anode, technologies, including supercapacitors and hybrid systems,
LiCoO2 at the cathode, and a carbonate-based solution as the may play a crucial role and become the next generation
electrolyte.[3,4] In the last two decades, the Li-ion technology sustainable electrochemical energy storage system of the
based on intercalation chemistry has seen tremendous techno- future.
logical improvements. This success has been achieved through
extensive collaborative teamwork across the world, involving This Special Collection aims to highlight the dynamic research
research and development on a variety of disciplines at the environment surrounding electrochemical energy storage tech-
interface between chemistry, material science, engineering, and nologies bringing together the latest research conducted
physics. Continuous improvement of the cell technology has beyond lithium-ion batteries. Ten reviews and twelve articles
been achieved by combining efforts in material optimization as highlight the vivid research efforts undertaken all over the
well as advanced engineered cell manufacturing processes. world in a variety of different systems including Na-ion, K-ion
Nowadays lithium-ion cells are lighter, smaller, cheaper, and batteries, Mg-, Ca-, Al-, Zn-based systems as well as all solid-
safer while exhibiting improved energy and power density.[5] state, dual-ion batteries, and hybrid batteries and supercapaci-
tors.

A substantial amount of contributions are focused on the

[a] Dr. I. Hasa
investigation of Na-based battery chemistries, highlighting the
WMG, The University of Warwick great interest and research efforts currently ongoing on these
Coventry, CV4 7AL United Kingdom technologies. Indeed, in the last decade, the development of
E-mail: [email protected]
[b] Prof. P. Adelhelm
Na-ion and Na-based chemistries, including solid-state systems,
Humboldt-University Berlin Na sulfur (Na/S) and Na–air (Na/O2), has continuously grown.
Helmholtz-Zentrum Berlin für Materialien und Energie Na-based batteries have the potential to represent the next
12489 Berlin, Germany
E-mail: [email protected]
generation sustainable and low-cost energy storage solution.
[c] Prof. G. Cao Great achievements in terms of materials development have
Department of Materials Science and Engineering, been reported. However, further work is still needed to fully
University of Washington
Seattle, WA 98195-2120, United States
understand a proper structure-function correlation in several
E-mail: [email protected] Na-ion battery materials. In this collection, two review papers
[d] Prof. L. Mai report on the importance of a fundamental understanding of
State Key Laboratory of Advanced Technology for Materials Synthesis and
Processing
the thermodynamic and kinetic processes occurring upon
Wuhan University of Technology sodiation and de-sodiation and their characterization for a
Wuhan 430070, P. R. China rational design of functional and high-performance Na-battery
E-mail: [email protected]
materials. Brennhagen et al. discuss operando X-ray methods
This Editorial is part of a joint Special Collection between ChemElectroChem
and Batteries & Supercaps dedicated to research Beyond Lithium-Ion providing a critical summary of the characterization techniques
Batteries that have been applied to Na-ion, Na/O2, and Na/S batteries,

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Editorial
Batteries & Supercaps doi.org/10.1002/batt.202100089

offering valuable insights on the choice of the cell design, data (NVP) in an all-solid-state battery (ASSB) cell. It is found that the
processing, and future opportunities. Gotoh reports on the use ionic conductivity decreases with increasing electrochemical
of solid state nuclear magnetic resonance (SS-NMR) as a potential, thus limiting high-rate cycling of the ASSB. The
powerful tool to obtain information on the sodiation mecha- authors propose that small particle sizes are required in order
nism of layered cathode and anode materials including carbon to reduce the ohmic polarization and concentration polar-
and inorganic compounds. ization and increase the power density of Na-ASSBs.

Among the Na-ion cathode candidates proposed so far, Electrolyte is certainly a key player in all electrochemical
transition metal layered oxides and polyanionic compounds systems. In this special collection, two review papers on this
have certainly attracted large attention in the Na-ion battery topic for Na batteries are presented. Yu et al. provide
community. In this Special Collection, Peng et al. highlight the information on the transport of Na ions in solid electrolytes
importance of the particle morphology and crystal orientation whereas Hijazi et al. focus on non-aqueous systems.
on a Ni Mn P2-type layered oxide cathode, proposing a one-
pot synthesis method for high energy/high power applications. For the latter ones, one of the main challenges is to ensure
Also, in search for low-cost cathode candidates, Fehse et al. the formation of a stable solid–electrolyte interphase (SEI) at
investigate the Fe4 + /3 + redox couple in NaFeO2 by simulta- the negative electrode. This crucial factor is assessed by Moon
neous operando nuclear resonance and X-ray scattering et al. by studying the differences in the SEI stability in Li and
studies. Lan et al. study the ionic conductivity of Na3V2P3O12 Na cells by using hard carbon electrodes. By tuning the

Ivana Hasa is Assistant Professor of Electro- Guozhong Cao is Boeing-Steiner Professor of

chemical Materials at WMG, The University of Materials Science and Engineering, Professor
Warwick since 2020. After completing her of Chemical Engineering, and Adjunct Profes-
Ph.D. in 2015 on the design and character- sor of Mechanical Engineering at the Univer-
ization of sodium-ion battery materials at sity of Washington. He received his Ph.D. from
Sapienza University of Rome, she moved to Eindhoven University of Technology (the
Helmholtz Institute Ulm (Ulm, Germany) for a Netherlands). His current research is focused
postdoctoral position working on post-lithium mainly on nanomaterials for energy related
chemistries and the investigation of structural applications, such as solar cells, rechargeable
and chemical composition of battery materi- batteries, supercapacitors, and hydrogen stor-
als. In 2016, she joined the Lawrence Berkeley age. Other research includes scintillation ox-
National Laboratory (California, USA) to inves- ides, nanobiosensors, PZT-based microelectro-
tigate the chemistry and evolution of the solid mechanical (MEMS) devices.
electrolyte interphase for silicon anodes mate-
Liqiang Mai is a Chair Professor of Materials
rials. In 2019, she returned back to the
Science and Engineering at Wuhan University
Helmholtz Institute Ulm as a Research Scien-
of Technology (WUT), Dean of School of
tist responsible of the sodium-ion group
Materials Science and Engineering at WUT,
research activities. Currently, her research
Fellow of the Royal Society of Chemistry. He
activities are directed toward a fundamental
received his Ph.D. from WUT in 2004 and
understanding of the processes governing the
carried out his postdoctoral research at Geor-
chemistry of sodium-ion batteries. At the
gia Institute of Technology in 2006–2007. He
Energy Innovation Centre in WMG, she is
worked as an advanced research scholar at
working toward the development and scale
Harvard University in 2008–2011 and Univer-
up of new battery chemistries from concept
sity of California, Berkeley in 2017. His current
to full proven cell prototypes.
research interests focus on new nanomaterials
Philipp Adelhelm is a professor at Humboldt- for electrochemical energy storage and micro/
University Berlin and is leading a research nano energy devices.
group on operando battery analysis at the
Helmholtz-Zentrum Berlin (HZB). He received
his education at the University of Stuttgart
and was a Ph.D. student at the Max-Planck-
Institute of Colloids and Interfaces in Potsdam
(Germany). He worked as postdoc at the
Debye Institute of Nanomaterials Science in
Utrecht (The Netherlands), and was a group
leader at the Justus-Liebig-University Giessen
(Germany). From 2015–2019 he was professor
at the Friedrich-Schiller-University Jena (Ger-
many). His main interests are on fundamental
aspects of rechargeable batteries (Li-ion, Na-
ion, sulfur) as well as new cell concepts (solid-
state).

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Editorial
Batteries & Supercaps doi.org/10.1002/batt.202100089

electrolyte system and designing a composite Sn/graphite study the AlCl3-saturated ionic liquid anolyte with an excess of
anode for Na-ion batteries, a Na hybrid supercapacitor is also AlCl3, while Elia et al. compare chloroaluminate melts.
presented by Palaniselvam et al., providing insightful informa-
tion on this type of high power device. Beside non-Li chemistries, in this special collection two further
contributes on beyond lithium-ion systems are highlighted.
In their work, Garcia-Quintana et al. investigate hybrid electro- Touja et al. discuss the use of metal anodes such as Li, Na, K
lytes in Na O2 batteries, elucidating the role of speciation in and Mg. They propose metal electrode surface engineering
glyme-ionic liquid hybrid systems. Liang and Lu provide strategies with a focus on the use of metal coatings forming
insights into the mechanistic understanding of oxygen electro- alloys and their possible practical transfer to the battery
des in metal O2 batteries, while Chen et al. provide an over- industry.
view of the latest works focused on using in situ Raman and
Fourier transform infrared spectroelectrochemical techniques The possible use of a solid-state system enabling Li metal use
for studying the electrode–electrolyte interface of Li O2 in combination with a sulfur cathode is also discussed by
batteries. Dewal et al. Their work focuses on the analysis of charge carrier
transport in an all-solid-state Li S batteries.
Among the other monovalent systems, K-ion batteries have
also attracted interest. In this special collection, Verma et al. This Special Collection groups together the latest research
summarize the most recent development on electrolyte conducted toward the development of beyond lithium-ion
systems for K-ion batteries while Zhang et al. shift the focus on battery technology. It is clear that the challenges faced by the
carbon based anodes. From an application point of view, these systems are multifaceted. Indeed, the challenges to be tackled
systems might not result very appealing, especially when lie at the interface of chemistry, materials science, surface
considering safety aspects. However, from a scientific point of science, and engineering. A multidisciplinary approach is
view, they offer ideal comparative systems to evaluate the needed to understand the key interfaces, structures, and
performance of Li and Na systems. mechanisms relevant to these systems. No single technique can
simultaneously achieve the chemical, structural, temporal, and
Multivalent-based ions battery (MIB) technologies are inter- spatial sensitivity required to understand all aspects. Multi-
esting post-Li electrochemical energy storage devices. Beside disciplinary, international collaborations combining experimen-
the promising properties, they are still at a very early stage of tal and computational methods are required to unveil key
research. In this special collection, Maroni et al. provide a knowledge and critical insights necessary for the development
comprehensive review on Mg and Ca systems, highlighting also of the future battery technologies.
the difficult experimental conditions related to the electrolyte
systems and the cathode materials required to investigate In conclusion, it has been a privilege to edit this Special
these systems. In addition, Bitenc et al. evaluate the electro- Collection. We would like to particularly thank all the contribu-
chemical performance and mechanism of Ca metal-organic ting authors for their great work and the reviewers for their
batteries while Meister et al. assess the use of Mg-based ionic commitment. A special Virtual Symposium, jointly organized
liquid electrolytes for hybrid dual-ion capacitors. by Batteries & Supercaps and ChemElectroChem, was also
originated based on this project. Finally, we would like to thank
Among the multivalent systems, Zn-based energy storage Greta Heydenrych, Rosalba A. Rincón, and Kate Lawrence for
devices have received extensive attention in view of their low- initiating this Special Collection, handling all the papers, and
cost and high-safety characteristics. Numerous breakthroughs coordinating the virtual symposium.
have been made in this field in recent years. In this special
collection, Li and Hu discuss a comprehensive overview of the
recent progress on Zn metal energy storage devices under
[1] B. Scrosati, J. Solid State Electrochem. 2011, 15, 1623–1630.
extreme conditions of low temperatures including the design [2] ‘www.nobelprize.org/prizes/chemistry/2019/summary/’, 2019.
of anti-freezing electrolytes, low-temperature-resistant cathode [3] Y. Nishi, Chem. Rec. 2001, 1, 406–413.
materials, and Zn anodes. [4] K. Xu, Chem. Rev. 2004, 104, 4303–4418.
[5] M. Li, J. Lu, Z. Chen, K. Amine, Adv. Mater. 2018, 30, 1800561.
[6] Batteries Europe, 2020 https://ec.europa.eu/energy/topics/technology-
Al-graphite dual-ion batteries represent another compelling and-innovation/batteries-europe_en.
battery concept especially for large-scale stationary storage
application in view of their safety, low-cost, long-cycling life,
and high-energy efficiency. Two articles are reported on this Manuscript received: April 23, 2021
topic with a focus on their electrolyte systems. Wang et al. Version of record online: May 31, 2021

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