Inorganic Solid-State Electrolytes For Lithium Batteries - Mechanisms and Properties Governing Ion Conduction

Inorganic Solid-State Electrolytes for Lithium Batteries:
Mechanisms and Properties Governing Ion Conduction
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Citation Bachman, John Christopher, Sokseiha Muy, Alexis Grimaud,

Hao-Hsun Chang, Nir Pour, Simon F. Lux, Odysseas Paschos,
et al. “Inorganic Solid-State Electrolytes for Lithium Batteries:
Mechanisms and Properties Governing Ion Conduction.” Chemical
Reviews 116, no. 1 (January 13, 2016): 140–162.
As Published http://dx.doi.org/10.1021/acs.chemrev.5b00563
Publisher American Chemical Society (ACS)
Version Author's final manuscript
Citable link http://hdl.handle.net/1721.1/109539
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Review
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Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms

and Properties Governing Ion Conduction
John Christopher Bachman,†,‡ Sokseiha Muy,†,§ Alexis Grimaud,†,∥ Hao-Hsun Chang,†,∥ Nir Pour,†,∥
Simon F. Lux,⊥ Odysseas Paschos,# Filippo Maglia,# Saskia Lupart,# Peter Lamp,# Livia Giordano,†,∥,∇
and Yang Shao-Horn*,†,‡,§,∥
†
Electrochemical Energy Laboratory, ‡Department of Mechanical Engineering, §Department of Materials Science and Engineering,
∥
Research Laboratory of Electronics, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States
⊥
BMW Group Technology Office USA, Mountain View, California 94043, United States
#
Research Battery Technology, BMW Group, Munich 80788, Germany
∇
Dipartimento di Scienza dei Materiali, Università di Milano-Bicocca, 20126 Milano, Italy
*
S Supporting Information
ABSTRACT: This Review is focused on ion-transport mechanisms and fundamental

properties of solid-state electrolytes to be used in electrochemical energy-storage
systems. Properties of the migrating species significantly affecting diffusion, including the
valency and ionic radius, are discussed. The natures of the ligand and metal composing
the skeleton of the host framework are analyzed and shown to have large impacts on the
performance of solid-state electrolytes. A comprehensive identification of the candidate
migrating species and structures is carried out. Not only the bulk properties of the
conductors are explored, but the concept of tuning the conductivity through interfacial
effectsspecifically controlling grain boundaries and strain at the interfacesis
introduced. High-frequency dielectric constants and frequencies of low-energy optical
phonons are shown as examples of properties that correlate with activation energy across
many classes of ionic conductors. Experimental studies and theoretical results are
discussed in parallel to give a pathway for further improvement of solid-state electrolytes. Through this discussion, the present
Review aims to provide insight into the physical parameters affecting the diffusion process, to allow for more efficient and target-
oriented research on improving solid-state ion conductors.
CONTENTS 4.2. Lattice Dynamics 152

5. Size-Tailored Ionic Conductivities 153
1. Introduction: Applications of Solid-State Electro- 6. Conclusion and Future Perspectives 154
lytes 140 Associated Content 155
2. Fundamentals of Solid-State Ion Conductors 142 Supporting Information 155
2.1. Known Chemistry of Solid-State Ion Con- Author Information 155
ductors 142 Corresponding Author 155
2.2. Ion-Transport Mechanisms and Properties 143 Present Address 155
3. Enhancing Lithium Conductivity by Structure Author Contributions 155
Tuning 144 Notes 155
3.1. LISICON-like 145 Biographies 155
3.2. Argyrodite 146 Acknowledgments 157
3.3. NASICON-like 146 References 157
3.4. Garnet 147
3.5. Perovskite 147
3.6. Relating Lattice Volume to Lithium-Ion 1. INTRODUCTION: APPLICATIONS OF SOLID-STATE
Conductivity 148 ELECTROLYTES
3.6.1. Tuning Lattice Volume by Substitution 148
3.6.2. Tuning Lattice Volume by Mechanical Solid-state inorganic electrolytes enable a number of emerging
Strain 148 technologies ranging from solid oxide fuel cells,1 smart
3.7. Comparison of Normalized Lithium Ion windows,2 sensors,3,4 memristors,5 microbatteries for on-chip
Conductivity 149
4. Reported Descriptors of Ionic Conductivity 150 Received: September 22, 2015
4.1. Volume of Diffusion Pathway 150 Published: December 29, 2015
© 2015 American Chemical Society 140 DOI: 10.1021/acs.chemrev.5b00563

Chem. Rev. 2016, 116, 140−162
Chemical Reviews Review
power,6 and solid-state batteries for electrical vehicles.7 While it diminished flammability.37,42 The enhanced stability and safety
is well-known that silver-8,9 and sodium-ion10,11 conductors can of solid-state inorganic electrolytes provides opportunities to
have ionic conductivities comparable to that of liquid simplify and redesign safety measures currently used in the
electrolytes,12 recent breakthroughs have led to marked battery cell, for example, overpressure vents or charge-
increases in lithium-ion conductivity. Considerable research interruption devices as well as sophisticated thermal manage-
has focused on a number of crystal structures including ment systems or constraints in the operational strategy in the
LISICON-like (lithium superionic conductor),13 argyrodites,14 battery pack.
garnets,15 NASICON-like (sodium superionic conductor),16 Although many solid-state electrolytes are found to have a
lithium nitrides,17,18 lithium hydrides,19 perovskites,20,21 and wide electrochemical stability window, there are still numerous
lithium halides,22 where increasing conductivities can be fast ion conductors reported to date that are unstable at low
achieved by structural and compositional tuning within a potentials against negative electrodes such as graphite and
given family of structures. Lithium-ion conductivities in the metallic lithium,43 requiring the use of electrode materials such
argyrodites,14 thio-LISICON,23 and the Li10MP2S12 (LMPS) as titanates.44 Fast ion conductors can also react with positive
(M = Si, Ge, Sn)24−26 structures are approaching that of liquid electrode materials, resulting in low interfacial charge-transfer
electrolytes such as ethylene carbonate/dimethyl carbonate kinetics.36,37 Although structural tuning by substitution within a
with 1 M LiPF6 ≈ 10−2 S/cm, shown in Figure 1.27 These given structural family can enhance lithium-ion conductivity,
there is a lack of fundamental understanding to establish a
universal guide for fast ion conductors among different
structural families. Thus, it is not straightforward to predict
the most conducting structure/composition, which limits the
design of new or multilayer lithium-ion conductors with
enhanced conductivity and stability in order to meet all the
requirements of solid-state lithium-ion batteries. Therefore,
further studies in the lithium-ion conductivity trends and
mechanisms among different classes of ion conductors are
needed to provide insights into universal descriptors of lithium-
ion conductivity and to aid the design of advanced lithium-ion
conductors.
In this Review, we survey previous research to search for key
physical parameters that have been found to have a large
influence on the ionic conductivities of crystalline solids, with
emphasis on solid-state inorganic lithium conductors. While
previous reviews report detailed structures and conductivities
for each class of solid electrolyte45 or focus on a specific family
such as lanthanide oxides,12 perovskites,20,21 and garnets,15 for
instance, we aim to provide researchers new insights into
correlating lithium-ion conductivity with lattice volume or
diffusion bottleneck sizes across several well-known structural
families, as well as opportunities in developing universal
descriptors governing ionic conductivity and using interfaces/
sizes to design next-generation solid-state electrolytes for
Figure 1. Reported total lithium-ion conductivity (unless otherwise lithium batteries.
mentioned) as a function of temperature adapted from Kamaya et al.,24 We first survey ions that are reported to be mobile in solid-
which includes liquid (blue) ethylene carbonate/dimethyl carbonate state conductors, as well as cations and ligands that are used in
(EC/DMC) 1 M LiPF627 and ionic liquid LiBF4/EMIBF4;46 polymer the structure of solid-state ion conductors. We show that
(dashed black) PEO-LiClO4;47 and inorganic solids (black) consisting
of amorphous LiPON 48 and crystalline solids: perovskite
monovalent ions have the highest diffusion coefficients and
Li 0 . 3 4 La 0 . 5 1 TiO 2 . 9 4 (bulk conductivity shown), 4 9 garnet lowest migration energies by comparing diffusion coefficients of
Li6.55La3Zr2Ga0.15O12,50 and Li10GeP2S12.24 Top right and top left M+ (Li+, Na+, K+, etc.), M2+ (Mg2+, Ca2+, Zn2+, Cd2+, etc.), and
show the potential energy of migration in liquid electrolytes of a M3+ (Tm3+ and Al3+) in Li2SO4 at 550 °C. In addition, by
charged species in red with a solvation shell of electrolyte molecules examining the trends found in the diffusion coefficients and
(highlighted in blue) and an interstitial mobile ion in a crystalline activation energies of monovalent cations in β-alumina at 440
solid, respectively. °C, we discuss that the highest diffusion coefficient and lowest
activation energies can be obtained for monovalent ions whose
lithium-ion conductors provide exciting opportunities in the sizes are not too small nor too large for a given structure.
development of solid-state lithium-ion and lithium−air batteries Moreover, even though higher ionic conductivity can be
for vehicle applications. Replacing the aprotic electrolytes used obtained by increasing the concentration of mobile ions and/or
in current lithium-ion batteries7,28−30 by these solid-state lowering the energy of migration, these two parameters cannot
electrolytes can lead to transformative advances in electrode be decoupled, which limits the maximum ionic conductivity and
concentration polarization due to the high lithium transference highlights current challenges in lithium-ion conductor research.
number of solid-state electrolytes (∼1) compared to aprotic Second, we show that there are a number of structural
electrolytes (0.2−0.5),31,32 increased lithium-ion battery life- families that exhibit high lithium-ion conductivities in the range
time and safety33−37 due to the greater electrochemical stability of 10−2 to 10−3 S/cm at room temperature, and lithium-ion
voltage window,31,38−40 enhanced thermal stability,37,41 and conductivity can vary greatly by up to 5−6 orders of magnitude
141 DOI: 10.1021/acs.chemrev.5b00563
Chem. Rev. 2016, 116, 140−162
Figure 2. Periodic table with mobile ions in blue, ligands in red, and cations that have been used to build crystal structures to provide ionic
conduction in green.
Figure 3. (a) Reported cationic diffusion coefficients of monovalent, divalent, and trivalent ions in Li2SO4 at 550 °C as a function of cation valency.58
The diffusion coefficients of these ions in aqueous solutions at 25 °C are also included for comparison.59 (b) Activation energies for cation migration
in Li2SO4.58 (c) Diffusion coefficients of monovalent ions in substituted β-alumina at 400 °C and (d) activation energies for cations as a function of
ionic radius.61
within each family. Of significance, we highlight that increasing tailored space charge regions to develop highly conducting
the lattice volume or lithium-ion diffusion bottleneck size has nanostructured lithium-ion conductors.
been exploited effectively to enhance lithium-ion conductivity
in LISICON-like, NASICON-like, and perovskite families while 2. FUNDAMENTALS OF SOLID-STATE ION
disordering lithium in tetrahedral and octahedral sites is CONDUCTORS
essential to achieve high lithium-ion conductivity in the garnet 2.1. Known Chemistry of Solid-State Ion Conductors
structure. Solid-state ion conductors consist of mobile ions as well as
Third, we discuss opportunities in establishing the volume of metal and nonmetal ions that typically form polyhedra with
the diffusion pathway and parameters of lattice dynamics such ligands that create the skeleton of the crystal structure. More
as low-energy phonon frequency as universal descriptors for than half of the elements in the periodic table have been
conduction of lithium and other ions among different structural exploited in solid-state conductors to date. A number of cations
families. Lastly, we show opportunities in exploiting size- and anions have been shown to be mobile in solids including
142 DOI: 10.1021/acs.chemrev.5b00563
Chem. Rev. 2016, 116, 140−162
H+, Li+, Na+, K+, Cu+, Ag+, Mg2+, F−, Cl− and O2−, and these optimum ion size (sodium ions) gives rise to the highest
are blue in Figure 2. One of the first solid-state ion conductors diffusivity and lowest activation energy for monovalent ions for
with a high ionic conductivity was AgI,8 which was followed by a given structure (β-alumina), as shown in parts c and d of
the development of sodium-ion-conducting β-alumina51 and Figure 3, respectively. The highest diffusivities can be obtained
NASICON,10 and then several fast lithium-ion conductors. for ions that are not too small nor too large for a given
Very recent works have suggested that divalent cations, for structure.61 When the mobile cation is too small, the cation
example, Mg2+ in mixed electron- and ion-conducting occupies a site with a large electrostatic well, which contains
MgxMo6T8 (T being S or Se)52 and ion-conducting Mg(BH4)- closer near-neighboring counterions, resulting in high activation
(NH2),53 can have reasonable mobility in solids. Several anionic energies and slow diffusion. On the other hand, when the
species can also be mobile in halides54,55 and oxides,12 such as mobile cation becomes too large, the cation experiences larger
oxygen-ion conductors at elevated temperatures. A large forces when diffusing between the bottlenecks of the skeleton
number of metal and nonmetal ions have been used for the structure, yielding reduced diffusivities and large activation
skeleton of the polyhedral network, while chalcogens, halogens,
energies. Therefore, design of fast lithium-ion conductors, on
and nitrogen are used as ligands, as shown in green and red,
which we focus this Review, requires an understanding of how
respectively, in Figure 2. Early transition-metal ions in the first
and second rows such as Ti4+, Zr4+, Nb5+, or Ta5+ (which are to tune the crystal structures to obtain optimum site sizes and
[Ne]3s23p63d0 and have no electrons in d-orbitals and thus do diffusion channels for lithium diffusion, which will be discussed
not have significant electronic conductivity) and ions from in section 3.
groups 13 (e.g., Al3+ and Ga3+), 14 (e.g., Si4+ and Ge4+), and 15 2.2. Ion-Transport Mechanisms and Properties
(e.g., P5+) are used to create polyhedra in 12-fold, 8-fold, 6-fold, The ion-conduction mechanisms in solid-state conductors are
or 4-fold coordination with the ligand. To form the backbone significantly different from those in liquid electrolytes. We focus
of the crystals, these polyhedra can be organized in different
our discussion on comparing lithium conduction in crystalline
ways, for example, by ordering into isolated polyhedral units as
solids versus in aprotic electrolytes. Lithium-ion transport in
in γ-Li3PO4, by corner sharing as in NASICON, or by edge/
corner sharing as in garnets. Details on these lithium aprotic liquid electrolytes involves moving solvated lithium ions
conductors will be presented in later sections. These polyhedra in the solvent medium.31 The lithium-ion conductivity in
can also be present in amorphous solids but will lack the long- aprotic electrolytes can be enhanced by increasing salt/ion
range ordering found in crystalline materials, with one example dissociation in solvents with greater dielectric constants as well
being amorphous lithium phosphorus oxynitride.56 Although as by promoting the mobility of solvated ions by lowering the
amorphous solids are promising ion conductors,57 in this viscosity of solvents as shown in the Stokes−Einstein
Review we will focus on crystalline materials and the equation.31 Due to reasonably fast exchange between the
information they provide on the diffusion process in solid- solvating molecules and the solvent molecules and uniform
state electrolytes. surroundings, the potential energy profile of mobile lithium
Both ion valency and size can greatly influence ionic ions in aprotic electrolytes can be considered flat (Figure 1, top
conductivity in crystalline solids. Because of the increased right). In contrast, the diffusion of mobile species in a
electrostatic interactions between mobile ions and cations crystalline solid needs to pass through periodic bottleneck
forming the structural skeleton, ionic conductivity and points, which define an energetic barrier that separates the two
diffusivity decrease with increasing valency. The valency effect local minima (typically crystallographic sites for lithium) along
on the diffusion coefficient of monovalent, divalent, and the minimum energy pathway62,63 (Figure 1, top left). This
trivalent ions is well-illustrated in Li2SO4 and aliovalent- energy barrier, which is often referred to as migration or
substituted lithium sulfates at 550 °C.58,59 The diffusion motional energy, Em, greatly influences ionic mobility and ionic
coefficient can decrease by 3 orders of magnitude from conductivity, where low migration energies leads to high ionic
monovalent to trivalent ions in lithium sulfates, which is mobility and conductivity.
accompanied by a considerable increase in the activation The ionic conductivity of crystalline solids is also dependent
energies, as shown in parts a and b of Figure 3, respectively. It is on the amount of interstitials, vacancies, and partial occupancy
not surprising to note that ion conductors of monovalent ions on lattice sites or interstices, which is determined by the ionic
such as silver ions, sodium ions, and lithium ions have the energy gap or defect formation energy (Ef) in stoichiometric
highest conductivities reported to date. In contrast, a similar
ion conductors (known as the intrinsic regime). In addition,
trend in the diffusion coefficient as a function of valency is
interstitials and vacancies can be created by substitution of
noted for these ions in aqueous solutions at room temperature
aliovalent cations, whose formation energetics is governed by
in Figure 3a, but the dependence on valency is much weaker as
a result of a different ion-conduction mechanism from those in the trapping energy, Et (known as extrinsic regime).63 In both
crystalline solids.60 intrinsic and extrinsic regimes, the apparent activation energy
In addition to the migrating ion’s valency, ionic size can EA of ion conductivity contains contributions from both the
greatly change the ionic conductivity. As shown in Figure 3a defect formation energy Ef or Et and the migration energy Em
and b, considerable spread is noted for diffusion coefficients (see Supporting Information for examples of types of defects).
and activation energies for monovalent, divalent, and trivalent Lithium-ion conductivity in a crystalline solid can be
ions with identical valencies. For instance, Pb2+ diffusion is an described by the product of the number of mobile lithium
order of magnitude larger than the Mg2+ diffusion in Li2SO4 ions per unit volume, the square of the charge of each lithium
(Figure 3a), and the activation energy is ∼2 times smaller ion, and the absolute mobility of lithium ions. Considering
(Figure 3b). Interestingly, the dependence of diffusivity on the noninteracting lithium ions, the lithium-ion absolute mobility,
ionic radius, in many cases, is not monotonic58,61 in contrast to μ, can be related to the lithium diffusion coefficient D = D0
reduced diffusivity with increasing valency. For example, the e−Ea/kBT by the Nernst−Einstein equation,
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D NASICON-like structure such as Li1+xLaxTi2−x(PO4)368 and

μ=
kBT (1) oxygen-ion conduction in the fluorite structure such as (1 −
x)ZrO2−(x)Y2O3,69 as shown in Figure 4. Therefore, the
with T as the temperature in Kelvin and kB as the Boltzmann
constant. Thus, the lithium-ion conductivity can be expressed
as
σo −EA / kBT
σ= e
T (2)
where EA is the activation energy of diffusion. In the superionic

phase, the concentration of mobile species is independent of
temperature and EA can be identified with the energy of
migration Em. An example is α-AgI, stable above 146 °C, where
a conductivity 104 higher than that for the low-temperature AgI
phase can be attributed to the presence of a partially occupied,
molten-like cation sublattice.64 EA is equal to Em + Ef/2 or Em +
Et/2 for temperature-dependent concentrations of mobile
lithium ions in intrinsic and substituted lithium-ion conductors,
respectively. Plotting the logarithm of the product of
conductivity and temperature as a function of the reciprocal
of temperature yields apparent activation energy of lithium-ion
conduction. Different methods used to measure ion con-
ductivity and diffusion coefficients in solids reported in the Figure 4. Reported conductivity of lithium ions at room temperature
literature can be found in the Supporting Information. and oxygen ions at 800 °C as a function of the substitution
Moreover, the lithium-ion transference number (tLi+, which is concentration, x × 100%, in oxygen-conducting (1 − x)ZrO2−
equal to the ratio of the mobility of lithium ions to the sum of (x)Y2O369 and lithium-conducting Li1+xLaxTi2−x(PO4)3 NASICON-
mobilities of all ions) of a crystalline solid can be close to like68 and Li3xLa2/3−x□1/3−2xTiO3 perovskite.21,66
unity.24 However, the lithium-ion transference numbers of
common liquid organic electrolytes are 0.2−0.5,31,32 making coupling between mobile-ion concentration and lithium-ion
solid-state conductors with ionic conductivities on the order of mobility or extrinsic defect concentrations highlights challenges
2−5 times smaller than aprotic electrolytes equivalently in using aliovalent substitution to greatly enhance the
conductive to lithium ions. conductivity of lithium-ion conductors.
Although the lithium-ion conductivity can increase with
greater concentrations of mobile lithium ions by aliovalent 3. ENHANCING LITHIUM CONDUCTIVITY BY
substitution to create interstitial atoms or vacancies, the STRUCTURE TUNING
conductivity often passes through a maximum and starts to
decrease as more mobile species are added into the lattice, Lithium-ion conductivity has been exploited in a large number
where lithium ions are interacting and the mobility of lithium of crystal structures and a vast composition space within each
ions is not independent of lithium concentration.65 The family of crystal structures. Room-temperature total lithium-ion
decrease in the ionic conductivity past the optimum aliovalent conductivities of well-known structures and compositions are
substitution can be attributed to increases in the migration shown in Figure 5a. As lithium-ion conductivity measurements
energy associated with the local structural distortion induced by are obtained from polycrystalline samples, the presence of grain
the substitution or from passing the optimum concentration of boundaries (Figure 6a), which is well-known to exhibit greater
mobile ions and extrinsic defects. Above a critical concentration resistance to ion conduction than the bulk,70−75 can give rise to
of substitution, the distortion of the lattice is so strong that the reduced conductivity values. For example, the bulk and grain-
increase in the migration energy or the decrease in extrinsic boundary conductivities of LISICON Li2+2xZn1−xGeO4 (x =
defects surpasses the effect of increasing the concentration of 0.55)72 and perovskite Li0.34La0.51TiO349 are shown as a
mobile species and the ionic conductivity decreases. For function of temperature in Figure 6b, where the grain-boundary
instance, lithium-ion conductivity in Li3xLa2/3−x□1/3−2xTiO3 conductivities are significantly lower. Controlling the grain-
perovskites exhibits a dome shape as a function of lithium boundary contribution to the total ionic conductivity is still a
substitution, x.21,66 The lithium-ion conductivity becomes large concern in solid-state electrolytes and is still an area that is
greater with increasing lithium concentration for x ≤ 0.12 heavily researched.76−78 It should be cautioned that reported
(corresponding to an A-site vacancy concentration of ∼10%), total conductivities of some ion conductors in Figure 5a may
while a decrease in the conductivity is observed for higher consist of conductivities coming from bulk and grain
lithium content. Due to the smaller ionic radius of Li+ (0.92 Å, boundaries.
with a coordination number of 8) compared to La3+ (1.36 Å, Two important observations can be made from Figure 5a.
with a coordination number of 12),67 the large lithium-ion First, there are a number of structural families (LISICON-like,
concentration induces local distortions, which slows down the argyrodite, and garnet) achieving high ionic conductivities in
diffusion and ion conduction. Additionally, the product of the the range of 10−2 to 10−3 S/cm at room temperature. Of
concentration of vacancies and lithium ions reaches a maximum significance to note is that thio-LISICON Li3.25Ge0.25P0.75S4,79
at x = 1/12; if mobility was independent of substitution, one argyrodite Li6PS5Br,80 and garnet Li6.55La3Zr2Ga0.15O1250 have
would expect to find a maximum at this value. Similar the maximum conductivity in their structural family while a new
observations are also noted for lithium-ion conduction in the class of lithium conductors derived from the thio-LISICON
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Chem. Rev. 2016, 116, 140−162
Figure 5. (a) Reported total ionic conductivity of solid-state lithium-ion conductors at room temperature, including LISICON-like (LISICON, thio-
LISICON, and Li10GeP2S12),24,79,81−83 argyrodite,80,84−87 garnet,50,88−91 NASICON-like,68,92 Li-nitride,17,18,93 Li-hydride,94−97 perovskite,49,98−100
and Li-halide.101−103 The lithium-ion conductivity of EC/DMC 1 M LiPF6 is shown for comparison as a dashed gray line.27 *Li10GeP2S12 is placed in
the LISICON-like structural family for its chemical and structural similarity to the other compounds. ‡Compounds whose conductivity have been
extrapolated from higher temperatures to room temperature (see Table S1 for details of values used for extrapolation). (b) Activation energy derived
from bulk conductivity as a function of bottleneck size between M1 and M2 sites (see Figure 3d in the Supporting Information for the positions of
these sites in the NASICON-like structure) as estimated from simulated structures for the compositions LiGe2(PO4)3(Ge2), LiGeTi(PO4)3(GeTi),
LiGe0.5Ti1.5(PO4)3(Ge0.5Ti1.5), LiTi2(PO4)3(Ti2), LiSn2(PO4)3(Sn2), LiTiHf(PO4)3(TiHf), and LiHf2(PO4)3(Hf2) from Martinez-Juá́ rez et al.16 The
dashed lines are guides to the eye. (c) Ionic conductivity (blue) for Li3Tb3Te2O12 (extrapolated), Li5La3Ta2O12, Li6BaLa2Ta2O12, and Li7La3Zr2O12
and lithium site distribution in the 48g/96h octahedral positions (gray) and 24d tetrahedral positions (black) from Thangadurai et al.15
family, Li10MP2S12 (M being Si, Ge, or Sn),24−26 has been orthorhombic unit cell and Pnma space group (space group
shown to have the highest lithium-ion conductivity reported to number 62; all space group numbers are from the International
date. Second, the lithium-ion conductivity within each Union of Crystallography),104 where all cations are tetrahe-
structural family can vary greatly by up to 5−6 orders of drally coordinated.105 The structure can be thought of as a
magnitude, which suggests that tuning within a crystal structure distorted hexagonal close-packing of oxygen atoms whose
can be an effective strategy to enhance ionic conductivity. packing planes are perpendicular to the c-axis and in which
Although it is not straightforward to find the most conducting cations (for instance, lithium and phosphorus as in Li3PO4) are
compositions by design and the fastest ion conductors are often distributed in two crystallographically distinct tetrahedral
found through trial and error,79 structural tuning by cation interstices, forming parallel one-dimensional chains along the
substitution within a given structural framework to control a-axis. The lithium ions that are located in LiO4 tetrahedra
bottleneck size for lithium-ion diffusion and lattice volume has
diffuse between these tetrahedra and interstitial sites located in
been successful in enhancing ionic conductivities, which will be
the PO4 network.106 Aliovalent substitution of P5+ by Si4+ or
discussed in detail later; structural schematics are provided in
the Supporting Information. Ge 4+ in γ-Li 3 PO 4 can create compositions such as
Li3+x(P1−xSix)O4,107−109 which give rise to fast lithium-ion
3.1. LISICON-like conduction and the LISICON-like family. The excess lithium
The LISICON and thio-LISICON compounds crystallize into ions created by this substitution, which cannot be accom-
structures similar to the γ-Li 3 PO 4 structure with an modated in the tetrahedral sites of the structure, occupy
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Chem. Rev. 2016, 116, 140−162
Figure 6. (a) Schematic of conduction pathways in polycrystalline material (path on the left and middle where ions must move through the bulk and
grain-boundary regions or only through the grain boundaries, respectively) and layered single-crystal films (path in the middle and on the right
where ions can move parallel to the layers of material; this case is rarely found in application). (b) Separated bulk and grain-boundary conductivities
as a function of temperature for Li0.34La0.51TiO2.94,49 and LISICON, Li2+2xZn1−xGeO4 (x = 0.55).72
interstitial sites, making the adjacent lithium−lithium ion initio molecular dynamics.115 Both Li3.25Ge0.25P0.75S4 and
distance unusually short and resulting in a high conductivity Li10GeP2S12 were experimentally shown to have a wide
of 3 × 10−6 S/cm, as shown in Figure 5. Substituting O by S in electrochemical stability window with no electrochemical
Li3+x(P1−xSix)O4 to form Li3+x(P1−xSix)S4, giving rise to the reactions between 0 and 4 V versus Li/Li+.24,79 However,
thio-LISICON family, can further increase lithium-ion con- computational results have in some cases concluded that
ductivity by 3 orders of magnitude at room temperature82 Li10GeP2S12 is stable in some cases116 and unstable in
(ionic conductivity of 6 × 10−4 S/cm in Figure 5a). others.113,115 When in contact with lithium, Li10GeP2S12 from
The Li10MP2S12 (M = Si, Ge, or Sn)24−26 and Li11Si2PS12110 computational studies has been found to be unstable.113,115
family has the highest lithium-ion conductivities above 10−2 S/ 3.2. Argyrodite
cm at room temperature. The Li10GeP2S12 (LGPS) structure
has the space group P42/nmc (space group number 137) with a Lithium argyrodite Li6PS5X (with X = Cl, Br, or I) are newly
tetragonal unit cell made of isolated PS4 and GeS4 tetrahedra, discovered fast lithium-ion conductors (the ionic conductivities
which occupy two distinct crystallographic sites: the 2b sites approach as high as 7 × 10−3 S/cm as reported by Deiseroth et
that are fully occupied by phosphorus and the 4d sites that are al.14) isostructural to the Cu- and Ag-argyrodite compounds,
partially shared by germanium and phosphorus at the ratio 1:1. which crystallize into a structure based on tetrahedral close
Lithium atoms are distributed over 4 crystallographic sites (4c, packing of anions (cubic unit cell with space group F4̅3m, space
4d, 8f, and 16h). The octahedrally coordinated lithium (4d group number 216).14,80,84−86,117,118 Within this close-packed
sites) is edge-shared with 4d (P/Ge)S4 tetrahedra along the c- structure, phosphorus atoms fill tetrahedral interstices, forming
a network of isolated PS4 tetrahedron (similarly to the thio-
axis and corner-shared with 2b PS4 tetrahedra along the a- and
LISICON structure), while lithium ions are randomly
b-axes, forming the backbone of the structure. The lithium
distributed over the remaining tetrahedral interstices (48h
atoms in these 4d octahedral sites are believed to be less mobile
and 24g sites). Lithium-ion diffusion occurs through these
that those in the two other tetrahedrally coordinated sites (the
partially occupied positions, forming hexagonal cages, which are
8f and 16h sites), which form one-dimensional chains of edge-
connected to each other by an interstitial site around the halide
sharing tetrahedra.24,25,111,112 The calculated energy of
ions in the case of Li6PS5Cl and around the sulfur anions in
migration through the one-dimensional channel is low (0.17
Li6PS5I.80 The activation energy is rather low, in the range from
eV) whereas the diffusion in the ab plane is larger (0.28 eV),
0.2 to 0.3 eV, owing to facile diffusion in between the hexagons
owing to relatively less-mobile lithium ions in the LiS6
made of partially occupied positions.119 The difference in the
octahedra bridging the channels of diffusion.113 However, connectivity of the hexagonal cages and the distribution of
recent computational works suggests that the lithium diffusion lithium among the different sites as well as the disorder on the
in LGPS might be possible in the ab plane in addition to the S2−/X− sublattice, which exists in chloride and bromide but not
diffusion into the channels along the c-direction,112,113 which is in iodide, may explain why Li6PS5I has significantly lower ionic
made possible by the connection of the one-dimensional chains conductivity compared to Li6PS5Cl and Li6PS5Br (Figure 5a).
of diffusion through a position previously neglected (4c This variation in ionic conductivity highlights the importance of
sites).111 Having an optimum channel size for lithium-ion disorder in promoting high ionic conductivity.119 It is also
migration is critical to achieve high lithium-ion conductivity. important to note that the substitution of sulfur by oxygen
The tin-based compound Li10SnP2S1225 has a larger unit cell leads to a decrease by several order of magnitudes in
due to the larger size of tin than germanium but shows a lower conductivity, a trend similar to what is found in LISICON-
ionic conductivity (4 mS/cm at 300 K, compared to 12 mS/cm like and thio-LISICON conductors. Preliminary tests show that
at 300 K for LGPS). While the volume of the unit cell increases the electrochemical stability windows of Li6PS5X (X = Cl, Br, I)
steadily as one goes from Si to Ge to Sn, the solid solutions argyrodite compounds are very wide (0−7 V versus Li/Li+).84
Li10(Ge1−xMx)P2S12 (M = Si, Sn) with 0 ≤ x ≤ 1 for Sn and 0
≤ x < 1 for Si114 exhibit a conductivity maximum at the 3.3. NASICON-like
composition Li10Ge0.95Si0.05P2S12 reaching 8.6 mS/cm, which The NASICON framework, generally with a rhombohedral unit
has the optimum tunnel size close to LGPS, as supported by ab cell and space group R3̅ c although monoclinic and
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Chem. Rev. 2016, 116, 140−162
orthorhombic phases have also been reported,92,120 of greater lithium-ion concentrations in Li6ALa2M2O12 and
L1+6xM4+2−xM′3+x(PO4)3 phosphates (L = Li or Na and M = Li7La3M2O12. Generally speaking, increasing the lithium-ion
Ti, Ge, Sn, Hf, or Zr and M′ = Cr, Al, Ga, Sc, Y, In, or La) concentration in the garnet structure renders faster lithium-ion
consists of isolated MO6 octahedra interconnected via corner conduction.132 However, the aliovalent substitution of La by Ba
sharing with PO4 tetrahedra in alternating sequences.68,120−124 increases the conductivity, where the extent of increase cannot
Lithium can occupy two different sites in the structure: the M1 be explained by the increase of lithium concentration.89,133,134
sites that are 6-fold coordinated (octahehedral symmetry) For example, an order of magnitude increase in the ionic
located directly between two MO6 octahedra, and the M2 sites conductivity is noted on going from Li 5La3Ta2O12 to
that are 8-fold coordinated and located between two columns Li6BaLa2Ta2O12, as shown in Figure 5a. The aliovalent
of MO6 octahedra. Lithium migration occurs via hopping substitution can induce changes in the lithium-ion distribution
between these two sites, and partial occupancies of lithium ions in the tetrahedral and octahedral sites.135,136 Having lithium
on those two sites are crucial for fast lithium-ion conduction, ions occupy the distorted octahedral sites is crucial to increase
especially as vacancies are required at the intersection of the the total ionic conductivities by 9 orders of magnitude from
conduction pathways to give access to three-dimensional Li3Ln3Te2O12 to Li7La3M2O12, as shown in Figure 5c.15
diffusion within the structure.125−127 We summarize two Moreover, the aliovalent substitution of Zr by Sb (20%),137
strategies reported to increase lithium-ion conductivity. First, Ta (50%),138 or Nb (100%) can significantly improve the
changing the size of the network can greatly influence lithium- conductivity of Li7La3Zr2O12 (LLZO) through modification of
ion conductivity, where the bottleneck of lithium-ion the lithium distribution, as in the case of Sb, or through the
conduction often resides in the migration between these two increase in lithium concentration, as in the case of Ta. The
sites. For example, making the bottleneck size larger by using effect of aliovalent substitution is shown in Figure 5 and Figure
greater M ion sizes in LiMM′(PO4)3 from M/M′ = Ge4+ (0.53 7 with the increase in conductivity through substitution of Zr
Å), Ti4+ (0.605 Å), to Hf4+ (0.71 Å) can increase lithium-ion by Nb in Li5La3Nb2O12.90 Having the cubic structure for LLZO
conductivity up to 4 orders of magnitude,16 as shown in Figure is also critical to achieve high ionic conductivity, where lithium
5a. Of significance to note, the activation energy of lithium-ion ions are disordered on the tetrahedral and octahedral sites.
conduction for these LiMM′(PO4)3 decreases linearly with the Aluminum doping (0.9 wt %) stabilizing LLZO in the cubic
bottleneck size between the M1 and M2 sites,16 which further form enhances the lithium-ion conductivity by 2 orders of
supports optimizing bottleneck sizes for mobile ions being magnitude and lowers the activation energy (0.34 eV for Al-
critical to generate fast ion conduction, as shown in Figure 5b. doped garnet vs 0.49 eV for undoped) relative to the tetragonal
Second, aliovalent substitution68 by M′3+ cations such as Al3+ undoped Li7La3Zr2O12, where lithium ions are ordered on
and Sc3+ in LiMM′(PO4)3 can greatly increase the conductivity tetrahedral and octahedral sites,139,140 as shown in Figure 5a.88
by increasing the mobile lithium concentration and mobility. Furthermore, the formation of LiAlSiO4 and LiGaO2 at the
However, the substitution level is limited to ∼15% (x = 0.3) grain boundaries can also contribute to the high conductivities
due to the large ionic radius mismatch; above this level the of the Al-doped LLZO141 and Ga-substituted LLZO.142
formation of a secondary phase is observed for Al3+ or Sc3+, for Further, these garnet lithium electrolytes have been found to
instance.68 Li1.3Al0.3Ti1.7(PO4)3 has the highest bulk con- have high thermal stabilities up to 900 °C and to be stable
ductivity (σ ≈ 3 × 10−3 S/cm) for NASICON lithium-ion against lithium metal,143 although some reports of instabilities
conductors at room temperature reported to date.68 Addition- against positive electrodes have been shown.15,144
ally, NASICON-like conductors are typically stable with air and 3.5. Perovskite
water and are stable at high potentials.128 However, similar to
perovskites, titanium-containing compounds can be reduced at The ideal perovskite structure with a general formula ABO3,
low potentials.45,128,129 cubic unit cell, and space group Pm3̅m (space group number
221) consists of A-site ions (typically alkaline-earth or rare-
3.4. Garnet earth elements) at the corners of a cube, B ions (typically
These oxides are derived from the ideal garnet structure with transition metal ions) at the center, and oxygen atoms at the
the general formula A3B2(XO4)3 such as Ca3Al2(SiO4)3 (cubic face-center positions, where A sites are in 12-fold coordination
unit cell and space group Ia3̅d, space group number 230). A- and B sites are in 6-fold coordination (BO6) that share corners
sites are 8-fold coordinated (antiprismatic sites), B-sites are 6- with each other. Lithium can be introduced in the perovskite on
fold coordinated (octahedral sites), and X-sites are 4-fold the A site through aliovalent doping, creating compositions
coordinated (tetrahedral sites). In lithium-conducting garnets, such as Li3xLa2/3−x□1/3−2xTiO3. Introduction of lithium
lithium ions occupy the tetrahedral positions as in modifies the concentrations of both lithium and vacancies,
Li3Nd3Te2O12. However, to obtain appreciable ionic con- and the concentration of vacancies and their interactions145
ductivity at room temperature, more lithium can be added into (which can lead to ordering of lithium/vacancies in the planes
the structure by adjusting the valence of the A and B cations, perpendicular to the c-axis) can significantly influence ionic
leading to several stoichiometries of lithium-conducting garnets conductivity. Lithium ions can diffuse by jumping in the ab
such as Li3Ln3Te2O12 (Ln = Y, Pr, Nd, Sm−Lu), Li5La3M2O12 plane to an adjacent vacancy through a square-planar
(M = Nb, Ta, Sb), Li6ALa2M2O12 (A = Mg, Ca, Sr, Ba; M = bottleneck made of oxygen forming the corners of the
Nb, Ta), and Li7La3M2O12 (M = Zr, Sn).15 Li3Ln3Te2O12 octahedra at room temperature.20,21 A recent computational
garnets, where lithium ions reside only in the tetrahedral sites, study suggests that, in the case where there is not significant
have low ionic conductivities.130,131 In addition, introducing ordering of the A-site cations in layers normal to the c-axis,
M5+ ions in the garnet structure introduces extra lithium ions in lithium ions could also diffuse along c-axis, which is in better
Li5La3M2O12, which are distributed over tetrahedral (24d) and agreement with experimental conductivity results.146 The
distorted octahedral (48g/96h) sites. Moreover, replacing La3+ bottleneck size can be increased by using large rare-earth or
with divalent ions and M with Zr4+ in Li5La3M2O12 leads to alkaline-earth metal ions in the A site, which can lead to
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the perovskite family was found for Li0.34La0.56TiO3 with a total

lithium-ion conductivity of 7 × 10−5 S/cm and bulk ionic
conductivity of 10−3 S/cm. In addition to the tuning of the
bottleneck size, changing the bond strength between the B-site
cation and the oxygen has been suggested to influence the
conductivity. However, this effect has been reported for a
narrow concentration range of Ti4+ substitution by Al3+,147
which results in an increased conductivity. While lithium
lanthanum titanates have been shown to be stable at high
potentials, they are known to be reduced around 1.5 V versus
Li/Li+, making it unsuitable for use with lithium and graphite
negative electrodes.20,148
3.6. Relating Lattice Volume to Lithium-Ion Conductivity
3.6.1. Tuning Lattice Volume by Substitution. Increas-
ing the lattice volume can increase the lithium-ion conductivity
and reduce the activation energy for several structural families.
By comparing the lithium-ion conductivity with isovalent
substitution, increasing the lattice volume per lithium atom
within a given crystal structure leads to increased ionic
conductivity and lowered activation energy for LISICON-like
Li3.5 M0.5 M′ 0.5O 413,108,149,150 (Figure 7a), NASICON-like
LiM x M′ 2− x (PO 4 ) 3 16 ,151 (Figure 7b), and perovksite
Li3xM2/3−x□1/3−2xTiO3100 (Figure 7c). Of significance to note
is that increasing lattice volume per lithium atom in
NASICON-like LiMxM′2−x(PO4)3 in Figure 7b correlates
with larger bottleneck size for lithium ion diffusion (Figure
5b and Figure S3). Moreover, increasing lattice volume with
larger A-site rare-earth metal ions (Sm < Nd < Pr < La) in the
perovskite structure has been correlated with increased lithium-
ion conductivity and reduced activation energy.100
3.6.2. Tuning Lattice Volume by Mechanical Strain.
Changing lattice volume also can be exploited by imposing
tensile or compressive strains in ion conductors.152−155 Density
functional theory (DFT) studies on cubic Li7La3Zr2O12 (c-
LLZO),138 and LGPS115 (Figure 8a) show that isotropic
compressive strain can greatly decrease lithium-ion conductivity
while tensile strain does not lead to any significant enhance-
ment in the ionic conductivity, suggesting that the lattice
volume per formula unit of these two conductors is near
optimal or further increasing lattice volume does not greatly
reduce the activation energy of lithium ions passing through
bottleneck points in the structure. Experimental validation of
strain-tailored lithium-ion conductivity is scarce, which can be
attributed to the difficulty to make epitaxial thin films due to
Figure 7. (a and b) Lithium-ion conductivity of LISICON-like the high vapor pressure of lithium156 and the growth of
Li3.5M0.5M′0.5O4 and NASICON-like LiMxM′1−x(PO4)3 with different secondary phases during the deposition.157 Recent advances in
cationic radii at room temperature (adapted from refs 13, 108, 149, thin-film growth of lithium-ion conductors158−160 suggest that
and 150 for LISICON-like and refs 16 and 151 for NASICON-like) as it is possible to tailor lithium conductivity by strains imposed by
a function of lattice volume per lithium atom. (c) Ionic conductivity at lattice mismatch relative to the substrate. For example, epitaxial
400 K and activation energy as a function of lattice volume per lithium Li0.33La0.56TiO3 thin films grown on NdGaO3 (NGO) show an
atom for perovskites Li0.5M0.5TiO3 with A-site rare-earth metal ions M anisotropy of ionic conductivity along the a- and b-axes of
= Sm, Nd, Pr, and La adapted from Itoh et al.100 The average ionic Li0.33La0.56TiO3, which may result from different strains
radius was calculated using Shannon’s radii; Pr3+ in 12-fold
imposed by NGO along these two crystallographic direc-
coordination is not available and is shown as NA.67
tions.161 However, due to the small variation in the measured
ionic conductivity, further studies are needed to firmly establish
significant increases in the ionic conductivity. A systematic the influence of strain on lithium conductivity.
increase in the bulk ionic conductivity at 400 K and lowered More compelling examples of ionic-conductivity tuning using
activation energy correlates with increasing rare-earth metal ion strains can be found ion oxygen-ion-conducting thin
size (Sm3+ < Nd3+ < Pr3+ < La3+).12,100 For example, replacing films.162−164 For example, the migration energy for oxygen-
Nd3+ with La3+ in Li0.34M 0.55TiO 3 increases the ionic ion diffusion in yttrium stabilized zirconia (YSZ) thin films of 1
conductivity by 4 orders of magnitude at room temperature, nm in thickness significantly decreases with increasing tensile
as shown in Figure 5. The highest lithium-ion conductivity in strains imposed from Al2O3 to KTaO3 substrate, as shown in
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Chem. Rev. 2016, 116, 140−162
activation energy. As the tensile strain is increased the

activation energy is decreased, as is found for YSZ/Al2O3 and
YSZ/Y2O3 with a lower nominal strain of 4 and 3%,
respectively.162,163,167 As the strains imposed from the substrate
reduce with increasing film thickness, the observed changes in
the activation energy decrease with increasing thickness, as
shown in Figure 8c. The lowest activation energy is observed
for the thinnest YSZ film of 6 nm on Al2O3, translating to an
increase in the conductivity of 1.5 orders of magnitude at 300
°C. 166 Caution should be taken when assessing ion-
conductivity changes of these thin-film studies. First, thin
films grown on different substrates can greatly vary from study
to study. For example, no change is observed for oxygen-ion
conductivity for YSZ thin films (30−300 nm) grown on MgO,
Al2O3, or SrTiO3168 single-crystal substrate and YSZ/CeO2
multilayers.169 Second, other factors besides strain, such as
changes in the nature of metal−oxygen bonds between oxygen
sublattices at the interface,170 mobile ion concentration,171 and
new phases170 created at the interface, should also be
considered.
3.7. Comparison of Normalized Lithium Ion Conductivity
Here we compare the normalized ionic conductivity and the
activation energy of lithium-ion conduction among selected
structural families (Figure 9). The ionic conductivities were
normalized by dividing the ionic conductivity by (cq2/kBT),
resulting in the so-called normalized ion conductivity, with kB
being the Boltzmann constant, T being the temperature, c being
the concentration of lithium, and q being the charge of each
lithium ion, shown in Table 1 and Figure 9. The lithium
concentration was calculated using the formula c = NZ/V, with
N being the number of lithium per formula unit (for example,
N = 3 in Li3PO4), V being the volume of the unit cell in cm3,
and Z being the number of formula units per unit cell (for
example, Z = 4 for Li3PO4 because the unit cell contains 12
lithium atoms). This quantity deviates from the diffusion
coefficient as not all of the lithium in the formula unit is
necessarily mobile, and thus the normalized ionic conductivities
reported are the lower bound for the diffusion coefficients,
providing some insights into lithium mobility of the mobile
species in a given structure. It should also be noted that the
Haven ratio (ratio of self-diffusion to charge diffusion; the
charge diffusion is the diffusion coefficient calculated through
measurements of the ionic conductivity) would also need to be
Figure 8. (a) Variation of computed ionic conductivities in LGPS115
and cubic LLZO138 as a function of applied isotropic strain. The ionic taken into account, although this value is typically on the order
conductivity decreases dramatically under applied compressive strain, of unity. Although we use bulk conductivities for ion
while only a relatively moderate improvement is obtained under tensile conductors when available (NASICON-like and perovskite
strain. (b) Activation energy of YSZ as a function of lattice mismatch families), it should be cautioned that reported conductivities of
computed from ab initio molecular dynamics (AIMD).164 The some ion conductors may consist of conductivities coming
structure used in the calculation was 1 nm of YSZ sandwiched from bulk and interfacial or grain boundaries (LISICON-like
between different substrates (KTaO3 (KTO), Al2O3, and SrTiO3 and garnet families).
(STO)). (c) Activation energy of YSZ on different substrates After normalizing the ionic conductivity, one can note that
measured experimentally as a function of film thickness: Y2O3/YSZ
the differences among conductors within a family is not
multilayers,163 Sc2O3/YSZ multilayers,165 and Al2O3/YSZ thin
films.166 The horizontal gray bar represents the activation energy of significantly altered, which results from the concentration of
bulk YSZ. As the interfaces between layers are semicoherent, the lattice lithium ions within each family not significantly changing
mismatch Δ cannot be directly identified as the lattice strain. (although we are unable to take into account the change in the
true mobile charge carriers between compounds). However,
after normalization, the difference between the LISICON-like
Figure 8b.164 This trend is supported by experimentally family and the NASICON-like and perovskite families
measured activation energies of oxygen-ion conductivity of significantly decreases and the difference between the garnet
YSZ thin films shown in Figure 8c, where negative strain family increases. As the concentration of lithium is higher in
imposed by Sc2O3165 increases the activation energy while LISICON-like than in NASICON-like and perovskites families,
tensile strain imposed by Y2O3163 or Al2O3166decreases the after normalization the difference decreases. This suggests that
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Chem. Rev. 2016, 116, 140−162
Figure 9. Normalized ionic conductivities and activation energies at room temperature and structures for select lithium-ion conductors. The values
are taken from literature for LISICON-like and Li10GeP2S12,24,79,82,83 NASICON-like,16,68 perovskite,49,98,100,172 and garnet.50,88−91,139,173 See Table
1 for details of the normalization of the ionic conductivity. The bulk conductivity of the perovskite and NASICON-like conductors are used as they
are available in the literature, while the total conductivities are used for LISICON-like and garnet conductors. In the structure schematics, gray balls
represent lithium ions and red balls represent oxygen ions. For more detailed schematics, see Supporting Information. *Li10GeP2S12 is placed in the
LISICON-like family for its chemical and structural similarity to the other compounds. ‡Compounds whose conductivity have been extrapolated
from higher temperatures to room temperature (see Table S1 for details of values used for extrapolation).
the mobility of lithium ions in the NASICON-like and Additionally, the perovskite materials require high-temperature
perovskite families is not significantly different from that in sintering where Li2O loss can be an issue, and they have a
the LISICON-like family. With a similar argument, one can decreased stability against lithium metal as Ti4+ cations are
note that the garnet family falls below all the others, which easily reduced when in contact with lithium metal.45,148 Similar
indicates that, in general, the garnet family has a very high problems with NASICON-like compounds are found as the
concentration of lithium but the lithium ions are less mobile Ti4+ cations can be reduced.45,128,129 The NASICON-like
compared to the other families. In addition, assuming that close materials also are in general less conductive than the LISICON-
to all the lithium ions are mobile in the compounds with the like and garnet materials. Garnet solid-state electrolytes are a
highest conductivity within LISICON-like, NASICON-like, and promising class of conductors that do not seem to suffer from
perovskite families, the approximate diffusion coefficients for some of the hindrances of the other conductors such as
the best conductor in each family all approach 10−7 cm/s2 at chemical instability or synthesis concerns, although recent
room temperature. reports do suggest that careful attention must be paid to
When comparing the different families of solid-state sintering conditions, including the sintering atmosphere, in
electrolytes, some general trends can be found. The order to achieve high densities and conductivities.15,174
LISICON-like and LMPS electrolytes typically have very high
conductivities, but only when sulfur is used as the anion within 4. REPORTED DESCRIPTORS OF IONIC
the structure. These sulfides have the drawback that they are CONDUCTIVITY
water-sensitive, must be handled under an inert atmosphere, Fundamental understanding of physical parameters governing
and also are in general less stable.128 Additionally, the high lithium-ion conductivity among different families of crystal
volatility of sulfur compounds makes the stoichiometry harder structures is critical to design new solid-state electrolytes with
to control when synthesizing these compounds. Similar enhanced conductivity and stability. Here we seek and discuss
complications are to be expected for the sulfide argyrodite some of the physical parameters that can be drawn to
conductors, which also require handling to be done in inert rationalize ionic conductivity trends among different crystal
environments.80 However, both the LISICON-like and structures.
argyrodite families, with their high conductivities, are sure to
remain heavily researched structures for lithium solid-state 4.1. Volume of Diffusion Pathway
electrolytes. The perovskites have lower total conductivities The volume accessible to lithium in the structure might be used
(that from bulk and grain boundaries) than other families. as a descriptor for lithium-ion conductivity among different
150 DOI: 10.1021/acs.chemrev.5b00563
Chem. Rev. 2016, 116, 140−162
Table 1. Calculations of Normalized Ionic Conductivities Shown in Figure 9

lattice parameters
normalized
ionic lattice ionic
conductivity volume temperature conductivity
(S/cm) a (Å) b (Å) c (Å) (Å3) Z (K) (cm2/s) ref
LISICON- Li10GeP2S12* 1.20 × 10−2 8.69 8.69 12.60 952.35 2 300 9.25 × 10−8 Kamaya et al. 201124
like Li3.25Ge0.25P0.75S4 2.20 × 10−3 13.40 7.66 6.07 621.75 4 298 1.69 × 10−8 Kanno and
Murayama 200179
Li3.4Si0.4P0.6S4 6.40 × 10−4 13.37 7.88 6.11 643.50 4 300 4.90 × 10−9 Murayama et al.
200282
Li3.5Si0.5P0.5O4‡ 1.31 × 10−7 10.60 6.12 5.01 324.83 4 300 5.06 × 10−13 Deng et al. 201583
NASICON- Li1.3Al0.3Ti1.7(PO4)3 3.00 × 10−3 8.50 8.50 20.82 1302.71 6 298 8.05 × 10−8 Aono et al. 199068
like LiHf2(PO4)3‡ 1.29 × 10−5 8.83 8.83 22.03 1487.53 6 300 5.17 × 10−10 Martinez-Juarez et al.
199816
LiTi2(PO4)3‡ 3.83 × 10−7 8.51 8.51 20.85 1307.54 6 300 1.35 × 10−11 Martinez-Juarez et al.
199816
LiGeTi(PO4)3 3.48 × 10−8 8.41 8.41 20.58 1259.86 6 300 1.18 × 10−12 Martinez-Juarez et al.
199816
LiGe2(PO4)3‡ 6.62 × 10−9 8.28 8.28 20.47 1213.90 6 300 2.17 × 10−13 Martinez-Juarez et al.
199816
perovskite Li0.34La0.51TiO2.94 1.00 × 10−3 3.87 3.87 3.87 58.01 1 300 2.76 × 10−8 Inaguma et al. 199349
Li0.067La0.64TiO2.99 7.90 × 10−5 3.87 3.88 3.89 58.41 1 300 2.20 × 10−9 Inaguma et al.
1994172
Li0.06La0.66Ti0.93Al0.06O3 1.68 × 10−6 3.87 3.87 3.89 58.33 1 300 2.65 × 10−10 Morata-Orrantia et
al. 200298
Li0.34Nd0.55TiO3 7.00 × 10−8 3.83 3.83 3.83 56.05 1 300 1.87 × 10−12 Itoh et al. 1994100
garnet Li6.55La3Zr2Ga0.15□0.3O12 1.30 × 10−3 12.98 12.98 12.98 2187.38 8 297 8.13 × 10−9 Bernuy-Lopez et al.
201450 and
Rettenwander et al.
2014173
Li7La3Zr2O12/0.9% Al 3.55 × 10−4 12.97 12.97 12.97 2183.19 8 300 2.24 × 10−9 Buschmann et al.
201188
Li6BaLa2Ta2O12 4.00 × 10−5 12.95 12.95 12.95 2169.74 8 295 2.88 × 10−10 Thangadurai and
Weppner 200589
Li5La3Nb2O12 1.00 × 10−5 12.81 12.81 12.81 2099.61 8 295 8.35 × 10−11 Peng et al. 201390
Li7La3Zr2O12 2.00 × 10−6 13.13 13.13 12.66 2184.39 8 300 1.26 × 10−11 Buschmann et al.
201188 and Awaka
et al. 2009139
Li5La3Ta2O12 1.54 × 10−6 12.85 12.85 12.85 2121.82 8 298 1.31 × 10−11 Gao et al. 201091
*
Li10GeP2S12 is placed in the LISICON-like family for its chemical and structural similarity to the other compounds. ‡Compounds that have been
extrapolated from higher temperatures to room temperature (see Table S1 for details of values used for extrapolation).
Figure 10. (a) Lithium diffusion pathway in Li6PS5Cl. The yellow, orange, and cyan spheres represent sulfur, phosphorus, and chlorine atoms,
respectively. Different colors of diffusion pathway correspond to different values of bond valence mismatch, from the highest in light blue to the
lowest in red. Reprinted with permission from ref 180. Copyright 2012 Springer. (b). Correlation between the activation energy and the ionic
conductivity of Ag-, Li-, and Na-conducting glasses with the fractional volume of diffusion pathway F scaled by the square root of the mass of the
mobile species M (e.g., M is the mass of Ag+ in Ag-conducting glasses).181
structural families. In the previous section, we show that the method to determine the diffusion pathway using the bond
ionic conductivity and activation energy correlate with the
valence method.175 The main concept in the bond valence
lattice volume and/or bottleneck sizes within a given structure
(Figure 5 and Figure 7). Adam and Swenson proposed a new method is the notion of the “valence” of a chemical bond
151 DOI: 10.1021/acs.chemrev.5b00563
Chem. Rev. 2016, 116, 140−162
Figure 11. (a) Ionic conductivity for structures with varying anions/ligands (crystalline lithium halides (T = 400 K),182 olivine Li2ZnM4 (M = Cl,183
Br,184 and I185) (T = 523 K), and lithium superionic conductors Li10GeP2L12 (L = O, S, and Se) at room temperature115). (b) Halogen-atom
polarizability (Å3),186 Li-halide bond distance (Å),186 and halogen electronegativity (Pauling scale)187 as a function of lithium-ion conductivity at 400
K for lithium halides (F, Cl, Br, and I).182 Bond length and polarizability values were obtained from the National Institute of Standards and
Technology (NIST).186 Electronegativity values are presented in Pauling scale and were obtained from ref 187.
between the atoms i and j, si−j, which can be calculated using holds for crystalline compounds. Recently, this descriptor has
the formula been used in a high-throughput calculation to find possible
candidates of lithium-, sodium-, potassium-, silver-, and copper-
⎡R − R⎤ ion conductors having potentially higher ionic conductivity.177
si − j = exp⎢ o
⎣ b ⎥⎦ (3) This method has also been used to study crystalline lithium-ion
conductors and electrodes, and by varying the threshold of the
where R is the bond length and Ro and b can be considered, to a bond valence mismatch, researchers can get information not
good approximation, as constants that do not depend on the only about the diffusion pathways178 but also about the fraction
crystal structure being considered. It has been found of mobile lithium contributing to conduction as well as possible
empirically176 that, if a crystal is stable, the bond valence sum diffusion mechanisms that are dominant in these materials.179
of each atom i, Vi = ∑jsi−j, where j runs over all nearest The volume of the percolating diffusion pathway can also be
neighbors, will be very close to the formal charge of that atom. determined by molecular dynamics simulations. Classical
To determine the diffusion pathway, the unit cell is divided into molecular dynamics was used to validate the threshold method
a fine 3D grid. At each node of this grid, the bond valence sum reported in Figure 10, but the determination of the volume of
of the diffusing species is calculated. The diffusion pathway in the diffusion pathway by the more accurate ab initio molecular
crystalline and amorphous solids corresponds to a percolating dynamics is still lacking and deserves future work. However, it
region, where the bond valence mismatch of the mobile species, is interesting to note that the shape of the percolating diffusion
defined as the difference between the bond valence sum and the volume as estimated by the bond valence method is in close
formal charge, is below a certain threshold.175 agreement with the lithium-ion distribution estimated by
The value of this threshold can significantly influence the neutron diffraction data.177
volume and the topology of the diffusion pathway in a given
4.2. Lattice Dynamics
structure. If the threshold is too small then there will be no
percolating diffusion pathway but only disconnected regions, as When changing the ligand by moving down in the periodic
can be seen in magenta in Figure 10a in the case of Li6PS5Cl. table (i.e., chalcogens or halogens), the ionic conductivity of
On the contrary, if the threshold is too large, then the entire monovalent cations typically increases. As the electronegativity
unit cell will become part of the diffusion pathway, a situation of the ligand decreases, we expect weaker attractive forces
obviously nonphysical. Unfortunately, there is no unique way to between the ligand and the mobile cation. For example, when
determine the value of this critical parameter. One possibility is changing the ligand from F− to I−, Ag+ and Li+ conductivity
to choose the lowest value of the bond valence mismatch at increases by many orders of magnitude in halides LiX (X = F,
which a percolating pathway starts to appear (which is shown in Cl, Br, and I) and the olivine Li2ZnM4 (M = Cl, Br, and I), as
cyan in Figure 10a). A fixed value of the bond valence shown in Figure 11a. Interestingly, the increasing lithium-ion
mismatch of 0.2 has also been used to determine the diffusion conductivity in halides from LiF to LiI can be correlated with
pathway in Li+, Na+, K+, Ag+, and Cu+ conductors.177 increasing Li−X distance, halogen atom polarizability, and
The ionic conductivity as well as the activation energy of reduced electronegativity of the halogen atom, as shown in
diffusion in silver-, sodium-, and lithium-ion-conducting glasses Figure 11b. Notice that the ionic conductivity of the lithium
correlate linearly with the cube root of the product of the argyrodites family seems to contradict this trend as the
fractional volume of diffusion pathway (F), defined as the ratio conductivity of Li6PS5I is the lowest in the series while,
between the volume of diffusion pathway and the volume of the according to this trend, we expect it to be the highest (Figure
unit cell, and the square root of the mass of the mobile species, 5). The reason for this apparent contradiction is the fact that, in
as shown in Figure 10b. The activation energy (the ionic this family, in addition to halide anions there are also sulfur
conductivity) decreases (increases) as the fractional volume (F) anions that outnumber the halide anions by a ratio 5 to 1 per
increases. It would be very interesting to see if this trend also formula unit. Therefore, we expect the S2− to have a more
152 DOI: 10.1021/acs.chemrev.5b00563
Chem. Rev. 2016, 116, 140−162
Figure 12. Correlation between activation energy and (a) high-frequency dielectric constant ϵ∞192and (b) frequency of low-energy optical phonon
ωLEO.193 The activation energy increases with increasing ωLEO and decreasing ϵ∞. Lithium-halide activation energies are from ref 182, dielectric
constants are from ref 191, and phonon low-energy optical frequency is from a previous work.195 The equations in each figure correspond to the
solid lines that were fitted with the data in the figures and plotted as guides to the eyes.
significant impact on ionic conductivity than the halide anions. ωTO2 ε∞

Indeed, the conductivity of Li6PO5Cl is several order of 2
=
ωLO εo (5)
magnitudes lower than its sulfur-containing counterpart (see
Figure 5). where ωLO is the frequency of the longitudinal optical mode
The substitution of oxygen by sulfur in the γ-Li3PO4-type
and εo is the static dielectric constant. As expected, a correlation
structure to form thio-LISICON leads to an increase of several between the activation energy and ωTO (equivalent to ωLEO,
orders of magnitude in the lithium-ion conductivity.81 Several frequency of the low-energy optical mode) has been found, as
computational studies,188,189 mostly using density functional shown in Figure 12b. The activation energy decreases with
theory (DFT), are in agreement with this experimental finding. decreasing ωTO, in agreement with the idea that low phonon
These studies have also revealed that the enhancement of ionic frequency is associated with large vibration amplitude, hence
conductivity upon substitution of O by S is a generic feature in increasing the probability of the mobile species to hop to the
phosphate compounds as it has been shown to be equally valid neighboring lattice site.193 It is interesting to note that a similar
for the compounds Li7P3O11 and Li7P3S11 as well as Li4P2O7 correlation also exists between the enthalpy of migration and
and Li4P2S7.190 Similar trends in enhanced lithium-ion mobility the frequency of longitudinal acoustic phonon at 2/3 [111] in
(reduced activation energy) have been found computationally the Brillouin zone in body-centered cubic metals.194
for the Li10GeP2X12 (X = O, S, or Se) family going from O to S The above descriptors could be used to screen and design
or Se.115 Again, this trend is in agreement with the concept crystalline materials with increased bulk ionic conductivity.
shown in Figure 11b as S2− and Se2− are larger and have a However, the progress in the experimental technique in terms
higher polarizability than O2−, confirming this approach as an of materials synthesis and nanostructure preparation opens
effective strategy to increase ionic conductivity in solid-state additional routes to design optimized lithium conductors by
lithium-ion conductors. engineering the interfacial properties. The modification of the
The existence of a correlation between the polarizability and lattice volume by means of interfacial strain described in section
the activation energy hints at other related correlations because 3.6 is an example, and other examples are described in the
the polarizability can be linked to other physical parameters. In following section.
particular, it can be related to the high-frequency dielectric
constant ε∞ via the well-known Clausius−Mossotti relation (in
the case of cubic binary compounds),191 5. SIZE-TAILORED IONIC CONDUCTIVITIES
The interfaces between materials (grain boundaries, separation
ε∞ − 1 4πα between different phases, or surfaces) represent a structural
=
ε∞ + 2 3Va (4) discontinuity that is accompanied by changes in charge-carrier
concentration. Ionic conductivity can be influenced by the net
where α is the sum of the polarizability of the ions in the electrostatic charge present at the interface.196 At grain
primitive cell and Va is the volume of the primitive cell. Indeed, boundaries the resulting effect is often detrimental for the
Wakamura found that there is nonlinear correlation between conductivity. On the interface between two different materials,
the activation energy and the high-frequency dielectric constant such an unbalanced charge would generate space charge regions
ε∞ for Ag+, F−, Li+, and a few Na+, Cu+, and Cl− conductors in the proximity of the interface, with an accumulation of
shown in Figure 12a,192 with the activation energy being (interstitial) mobile species (for example, lithium ions in
decreased with increasing ε∞. Similarly, the correlation between lithium conductors) on one side and a depletion of mobile
activation energy and ε∞ hints at the existence of other species (or equivalently, an accumulation of vacancies) on the
descriptors that are related to ε∞. In particular, the frequency of other side.196−200 This charge accumulation/depletion is due to
the transverse optical phonon ωTO can be related to ε∞ using the difference in the electrochemical potential of the mobile
the Lyddane−Sachs−Teller relation,191 species at the interface, causing a net migration of charge across
153 DOI: 10.1021/acs.chemrev.5b00563
Chem. Rev. 2016, 116, 140−162
Figure 13. (a) Conductivity as a function of temperature for CaF2−BaF2 superlattices (dotted lines) as well as bulk CaF2 and BaF2 (solid lines).201
(Inset) Space charge layers for distances (D) between interfaces on the order of the Debye length (Ld) and for distances much larger than the Debye
length. (b) Lithium conductivity as a function of LiI204 or Li2ZnI4103 fraction in ordered mesoporous alumina (Al2O3) composite for different pore
sizes. The conductivity of LiI−Al2O3 homogeneous mixture is also shown for comparison.206
the boundary, a phenomenon similar to the buildup of p−n trend with the ionic radius within a given structure, where the
junction, which is well-known in semiconductor physics. maximum diffusion coefficients and lowest activation energies
The increase in the concentration of the mobile species at can be achieved with an optimum size. This observation can be
the interfaces enhances the ionic conductivity. This concept is rationalized by the arguments that the diffusion of ions that are
supported by the ionic conductivities and activation energy of too large can be limited by moving through structural
undoped epitaxial BaF2/CaF2 multilayers with different layer bottlenecks and ions that are too small can become trapped
thicknesses, as shown in Figure 13a.201 As the layers become in potential minima. This concept has been used extensively to
thinner, the relative volume affected by the space charge layer enhance lithium-ion conductivity within the LISICON-like,
becomes increasingly large, resulting in a higher concentration NASICON-like, and perovskite families, where increasing
of charge carriers and increased ionic conductivity.201 However, lattice volume by substitution can be correlated with larger
in heavily doped ion conductors such as YSZ, the space charge bottleneck sizes, reduced activation energies, and greater ionic
layer is expected to be very thin, and its effect on conductivity conductivities by several orders of magnitude. In addition to
becomes negligible. For example, 8 mol % YSZ has the space controlling lattice volume by substitution, ionic conductivity
charge thickness on the order of 2−3 nm at 500 °C.202 can be enhanced by increasing lattice volume via mechanically
Recent advances on nanosized bulk ion conductors can imposed strains, which has been shown to enhance oxygen-ion
potentially take advantage of ion conduction along inter- conduction but not yet lithium-ion conduction.
faces.197 In nanosized systems, where the volume of the We discuss opportunities in establishing descriptors of ionic
interfacial zones constitutes several tenths of the total volume, conductivities, which can universally correlate with ionic
interfacial ion conductivity can dominate.196,203 Examples can conductivity across different families of structures, which have
be found in the heterogeneous doping of halides (LiX) and the potential to greatly accelerate the discovery of new ion
Li2ZnI4 when nanoporous alumina is employed as second conductors with superionic conductivity. Electrolytes with
phase, where 3 or 4 orders of magnitude of lithium-ion body-centered cubic anion sublattices207 and structures where
conductivity enhancement can be obtained, as shown in Figure the mobile species is not in its preferred coordination have
13b.103,203,204 been correlated with high ionic conductivity208 and suggested
A similar effect has been recently observed for nanoporous to be a promising route for locating new superionic conductors.
Li3PS4, which shows an ionic conductivity of 1.6 × 10−4 S/cm Increasing the volume of the ion diffusion pathway determined
at room temperature,205 much higher than the reported ionic from the bond valence method of silver-, sodium-, and lithium-
conductivity for this material in bulk form (Figure 5a). This ion-conducting glasses correlates with reduced activation
drastic increase in ionic conductivity has been attributed partly
energy and enhanced ionic conductivity.181 In addition,
to a preference for the more conductive β-Li3PS4 phase
increasing the high-frequency dielectric constant and lowering
(intrinsic bulk ionic conductivity of 8.93 × 10−7 S/cm),205 but
the frequency of the low-energy optical phonons is shown to
especially to the surface conductivity. The surface conductivity,
enhance ionic conductivities among different ionic conductors
demonstrated by the correlation between the surface area and
including silver-, sodium-, lithium-, and fluorine-ion con-
the ionic conductivity, is believed to be triggered by the space
duction.192,193 Further experimental and computational work
charge at the surface, which promotes lithium vacancy
diffusion.205 is needed to test these hypotheses.
While a number of solid-state electrolytes have ionic
conductivities approaching that of liquid electrolytes, the
6. CONCLUSION AND FUTURE PERSPECTIVES reactivity between solid-state electrolytes and electrode
In this Review, we highlight the interplay between ionic size materials115,144,148 limits the practical use of solid-state
and lattice volume that is shown to greatly influence ionic electrolytes in lithium-ion batteries, which is poorly understood.
conductivity in a number of structural families. Diffusion Future work is needed to understand the reaction mechanisms
coefficients of mobile monovalent ions can exhibit a volcano at the interface between fast lithium-ion conductors and
154 DOI: 10.1021/acs.chemrev.5b00563
Chem. Rev. 2016, 116, 140−162
conventional lithium-ion electrode materials, as well as between

two different fast lithium-ion conductors, and to develop
solutions to stabilize these interfaces. Such understanding and
control of interfacial reactivity is essential to realize the
opportunities of exploiting space charge layers created in
multicomponent ion conductors to enhance ion conductivity
by nanostructural designs196 and of minimizing interface
reactivity by protecting lithium-ion conductors with surface
coatings.
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the Sokseiha Muy received his B.S. and M.S. degrees in Material Sciences
ACS Publications website at DOI: 10.1021/acs.chem- from École Polytechnique, France. He is currently a Ph.D. student in
the Department of Materials Science and Engineering at MIT, working
rev.5b00563.
in the Electrochemical Energy Lab under Prof. Yang Shao-Horn. His
Details on types of defects, measurement techniques, and research interest includes the design principle of new solid-state
structural schematics; tables of the values used to electrolytes for Li-ion battery.
extrapolate conductivities from high to low temperatures;
figure on the relation between the bottleneck size and
lattice volume for NASICON-like conductors (PDF)
AUTHOR INFORMATION
Corresponding Author
*E-mail: [email protected].
Present Address
A.G.: Chimie du Solide et Energie, FRE 3677, Collège de
France, 75231 Paris Cedex 05, France, or Réseau sur le
Stockage Electrochimique de l’Energie (RS2E), FR CNRS
3459, 80039 Amiens Cedex, France.
Author Contributions Alexis Grimaud is an associate researcher at Collège de France in Paris,
France. He received his physical-chemistry engineering diploma from
J.C.B., S.M., and A.G. contributed equally. the Graduate School of Chemistry and Physics of Bordeaux in 2008
Notes and his Ph.D. from the University of Bordeaux in 2011. He then was
postdoctoral associate at MIT from 2012 to 2014, working in the
The authors declare no competing financial interest.
Electrochemical Energy Lab with Prof. Yang Shao-Horn. In 2014, he
Biographies joined Prof. Jean-Marie Tarascon’s research group at Collège de
France, Paris, France, as an associate researcher. His research interests
are in the understanding of anionic redox and the design of new
materials for water splitting, metal−air, and Li-ion batteries.
John Christopher Bachman holds B.S and M.S. degrees in Mechanical

Engineering from University of California, Davis. He is currently a
Ph.D. candidate in Mechanical Engineering at MIT, working in the Hao-Hsun Chang received his B.S., M.S., and Ph.D. degrees in
Electrochemical Energy Lab under Prof. Yang Shao-Horn, studying chemical engineering from National Taiwan University. He is now a
lithium solid-state electrolytes. postdoctoral fellow/associate in Prof. Yang Shao-Horn’s group at MIT.
155 DOI: 10.1021/acs.chemrev.5b00563

Chem. Rev. 2016, 116, 140−162
Prior to joining the Electrochemical Energy Lab, he was a senior

engineer at China Petrochemical Development Corporation from
2010 to 2012 and a principal engineer at Taiwan Semiconductor
Manufacturing Company in 2013. His current research centers on
synthesis and characterizations of solid-state electrolytes for lithium-
ion and metal−air batteries.
Odysseas Paschos has studied Physics at the Aristotle University of

Thessaloniki in Greece. In 2008 he obtained his Ph.D. on Materials
Science from College of Nanoscale Science and Engineering at SUNY
Albany and moved to Munich, Germany, where he worked at the
Technische Universität München (TUM) as a Post-Doctoral Associate
in the Physics Department. During this period, he worked on several
aspects of electrical conversion of storage including synthesis and
electrochemical characterization of materials related to fuel cells and
Nir Pour is currently a postdoctoral associate at MIT in the batteries. Since 2012 he is working at BMW in the group Research
Battery Technology lead by Dr. Peter Lamp and is in charge of the
Electrochemical Energy Lab. His research centers on vanadium
Material projects, investigating potential candidates and technologies
redox flow batteries. He hold a B.Sc. degree in Biophysics and an M.Sc. for future automotive cells.
and Ph.D. in chemistry, researching magnesium batteries under the
supervision of Prof. Doron Aurbach, from Bar-Ilan University in Israel.
Saskia Lupart received her M.Sc. degree in Chemistry from the

Ludwig-Maximilians-Universität München (LMU), Germany. In 2012
she completed her Ph.D. studies in solid-state chemistry at the LMU.
Peter Lamp received his M.Sc. in physics from the Technical Since 2012 she is working at BMW AG at the group of Dr. Peter Lamp
University of Munich in 1989. In 1993, he obtained his Ph.D. in in the “Research Battery Technology” section, where she is in charge
of solid-state electrolytes for lithium batteries.
general physics. His Ph.D. thesis “Investigation of photoelectric
injection of electrons in liquid argon” was prepared at the Max Planck
Institute for Physics, Munich. Between 1994 and 2000 he was group
leader at the Department of Energy Conversion and Storage of the
Bayerischen Zentrum für angewandte Energieforschung (ZAE) in
Garching. After a short period as project leader for fuel cell systems at
Webasto Thermo Systems International GmbH, he joined BMW AG
in 2001 as a development engineer for fuel cell systems. Since 2004 he
has been leader of the “Technology and Concepts Electric Energy
Storage” group and, since 2012, of the “Battery Technology”
department at BMW.
156 DOI: 10.1021/acs.chemrev.5b00563

Chem. Rev. 2016, 116, 140−162
Simon Lux obtained a M.Sc. degree in Technical Chemistry from the

Technical University of Graz, Austria, and completed his Ph.D. studies
in Physical Chemistry at the University of Muenster, Germany. After
two years at the Lawrence Berkeley National Laboratory, Simon joined
BMW of North America as Advanced Battery Engineer. In his current
role, he is responsible for the coordination and management of the
lithium-ion battery technology projects from the material to the cell
level in the NAFTA region and engages in technology scouting in the
United States.
Yang Shao-Horn is W.M. Keck Professor of Energy, Professor of

Mechanical Engineering, and Professor of Materials Science and
Engineering at MIT. Her interests include surface science, catalysis/
electrocatalysis, and design of electron and phonon structures of
materials for electrochemical energy storage, solid-state ionics,
photoelectrochemical conversion, and clean environmental applica-
tions. Professor Shao-Horn has published around 200 research articles
and mentored/trained over 50 M.S. and Ph.D. graduate students and
postdoctoral associates at MIT.
ACKNOWLEDGMENTS
Filippo Maglia was an assistant professor at the Chemistry Department
J.C.B. is supported in part from the National Science
of the University of Pavia, Italy, between 2005 and 2012. He received Foundation Graduate Research Fellowship (1122374) and
his Ph.D. in chemistry from the University of Pavia in 1998. Dr. Maglia H.-H.C. is in part supported from the Ministry of Science and
has spent several periods as visiting scientist between 1998 and 2005 at Technology of Taiwan (102-2917-I-564-006-A1). Research
the Department of Chemical Engineering and Materials Science of the support at MIT from BMW and the Skoltech-MIT Center on
University of California, Davis. In 2009 he was DAAD fellow at the
Electrochemical Energy is acknowledged.
Technische Universität München, Germany. In 2013 he joined BMW
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162 DOI: 10.1021/acs.chemrev.5b00563

Chem. Rev. 2016, 116, 140−162

Inorganic Solid-State Electrolytes For Lithium Batteries - Mechanisms and Properties Governing Ion Conduction

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Inorganic Solid-State Electrolytes for Lithium Batteries:

Mechanisms and Properties Governing Ion Conduction

Citation Bachman, John Christopher, Sokseiha Muy, Alexis Grimaud,

Publisher American Chemical Society (ACS)

Version Author's final manuscript

Citable link http://hdl.handle.net/1721.1/109539

Terms of Use Article is made available in accordance with the publisher's

Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms

ABSTRACT: This Review is focused on ion-transport mechanisms and fundamental

CONTENTS 4.2. Lattice Dynamics 152

© 2015 American Chemical Society 140 DOI: 10.1021/acs.chemrev.5b00563

D NASICON-like structure such as Li1+xLaxTi2−x(PO4)368 and

where EA is the activation energy of diﬀusion. In the superionic

the perovskite family was found for Li0.34La0.56TiO3 with a total

activation energy. As the tensile strain is increased the

Table 1. Calculations of Normalized Ionic Conductivities Shown in Figure 9

signiﬁcant impact on ionic conductivity than the halide anions. ωTO2 ε∞

conventional lithium-ion electrode materials, as well as between

John Christopher Bachman holds B.S and M.S. degrees in Mechanical

155 DOI: 10.1021/acs.chemrev.5b00563

Prior to joining the Electrochemical Energy Lab, he was a senior

Odysseas Paschos has studied Physics at the Aristotle University of

Saskia Lupart received her M.Sc. degree in Chemistry from the

156 DOI: 10.1021/acs.chemrev.5b00563

Simon Lux obtained a M.Sc. degree in Technical Chemistry from the

Yang Shao-Horn is W.M. Keck Professor of Energy, Professor of

157 DOI: 10.1021/acs.chemrev.5b00563

158 DOI: 10.1021/acs.chemrev.5b00563

159 DOI: 10.1021/acs.chemrev.5b00563

160 DOI: 10.1021/acs.chemrev.5b00563

161 DOI: 10.1021/acs.chemrev.5b00563

(188) Du, Y. A.; Holzwarth, N. A. W. Li Ion Diffusion Mechanisms in

162 DOI: 10.1021/acs.chemrev.5b00563

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