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org/CR Review

New Concepts in Electrolytes

Matthew Li, Chunsheng Wang, Zhongwei Chen, Kang Xu,* and Jun Lu*

Cite This: Chem. Rev. 2020, 120, 6783−6819 Read Online

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ABSTRACT: Over the past decades, Li-ion battery (LIB) has turned into one of the most
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important advances in the history of technology due to its extensive and in-depth impact on
our life. Its omnipresence in all electric vehicles, consumer electronics and electric grids
relies on the precisely tuned electrochemical dynamics and interactions among the
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electrolytes and the diversified anode and cathode chemistries therein. With consumers’
demand for battery performance ever increasing, more and more stringent requirements are
being imposed upon the established equilibria among these LIB components, and it became
clear that the state-of-the-art electrolyte systems could no longer sustain the desired
technological trajectory. Driven by such gap, researchers started to explore more
unconventional electrolyte systems. From superconcentrated solvent-in-salt electrolytes to
solid-state electrolytes, the current research realm of novel electrolyte systems has grown to
unprecedented levels. In this review, we will avoid discussions on current state-of-the-art
electrolytes but instead focus exclusively on unconventional electrolyte systems that
represent new concepts.

CONTENTS Biographies 6809

Acknowledgments 6810
1. Introduction and Scope 6783 References 6810
2. New Concepts in Liquids 6784
2.1. Superconcentration 6785
2.2. Ethers 6786 1. INTRODUCTION AND SCOPE
2.3. Esters 6788
2.4. Exotic Solvents 6789 Over the past decade, interest in electrochemical energy
2.5. Water 6790 storage technologies has experienced an exponential increase.
2.6. Hybrids 6793 Governments and commercial entities around the world have
2.7. Beyond Liquid Phases 6794 dedicated enormous resources to the study of battery
3. Semisolids 6794 chemistries and materials of higher performance based on
3.1. Polymers, Polymer−Liquid, or Polymer− the success of Li-ion batteries (LIBs).1 While most research
Polymer Hybrids 6794 has centered on the design of chemistry and structure for
3.2. Liquid Inorganic Hybrids 6797 either intercalation- or conversion-type electrode materials, the
4. Solid Ionic Conductors 6797 electrolyte, which insulates the electron but conducts ionic
4.1. Garnet-Type Solid-State Electrolytes 6798 current between the two electrodes, has been increasingly
4.2. Antiperovskite-Type Solid-State Electrolytes 6800 recognized as a key component in enabling these new
4.3. Sulfide-Type Solid-State Electrolytes 6801 electrode materials and chemistries.2 Historically it was the
4.4. Beta-Alumina 6802 knowledge deficiency in electrolyte formulation and the
4.5. First-Principles Calculation-Driven Design 6803 accompanying interphase chemistry that significantly delayed
5. Redox-Active Electrolytes 6804 the emergence of LIBs.3 State-of-the-art (SOA) electrolytes in
5.1. Flow Cell Anolytes/Catholytes 6804 any battery systems have been tailored to the specific chemistry
6. Open Systems 6806 and structure of the electrodes and reactions present in the cell.
6.1. Li−Air(O2) Electrolyte 6806
6.2. Zn−Air Electrolytes 6808 Special Issue: Beyond Li-Ion Battery Chemistry
7. Concluding Remarks and Perspectives 6809
Author Information 6809 Received: August 28, 2019
Corresponding Authors 6809 Published: February 5, 2020
Authors 6809
Notes 6809

© 2020 American Chemical Society https://dx.doi.org/10.1021/acs.chemrev.9b00531

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Although the requirements vary with the electrodes, the past decade, were designed to support battery chemistries
overarching design goals of an ideal electrolyte remain the aiming to achieve significant improvements in the aforemen-
same across all technologies: formation of desired interphases tioned 5 metrics. They should very likely become a part of or
at the central stage together with considerations of safety, rate directly bring forward the next generation of energy storage
performance, (electro)chemical stability, and cost. Only when technology. Thus, instead of comprehensiveness, we intend to
all of these requirements are met can any electrolyte system place emphasis on topics and concepts that were deemed by
become competitive for commercial success, as exemplified by the authors as significant breakthroughs in the knowledge of
the carbonate-based electrolytes adopted by LIBs. electrolytes. Meeting such high bars are liquid electrolytes that
A spider chart, where each parameter is ranked out of five, ventured into the superconcentration regime, where estab-
displays how the SOA electrolyte formulations perform when lished conventional wisdom of interphasial chemistry no longer
evaluated against these multifaceted requirements made by holds true. Another potentially ground-breaking electrolyte
various exploratory electrochemical systems, Li−S battery technology is solid electrolytes based on sulfide, garnet,
(LSB), Zn−air battery (ZAB), and Li−air battery (LAB), with antiperovskite, and Beta-alumina polymer materials that
LIB as the benchmark for comparison (Figure 1).4 Compared displayed liquid-like ion transport, or semisolid electrolytes
that exist between the conventional liquids and solids but
inherit merits from both, or electrolytes carrying redox-active
species on their structure that are designed for flow
configurations, or electrolytes for open battery systems such
as metal air chemistries (M−O2, M = Li, Zn, etc.). The use of
first-principle calculations to drive the design of these new
electrolytes will also be discussed briefly.

2. NEW CONCEPTS IN LIQUIDS

In any electrochemical device, electrolyte is the indispensable
ionic conductor between the two electrodes which must
provide ionic current to support the cell reactions. Most
electrolytes used today in batteries are in the liquid state for
apparent design convenience because almost all active
electrode materials are in the solid state, and a liquid
electrolyte can access these active materials much easier
(better wetting) and transport charges much faster (low
impedance across the liquid/solid interface). With the only
exception of ionic liquids (salts in molten state), these liquid
ionic conductors are formed by dissolving salt in polar solvents,
no matter aqueous or nonaqueous, which dissociate the cations
Figure 1. SOA electrolytes for four energy storage technologies
and anions, respectively, and stabilize these separate ions via
ranked by their SEI formation, safety, price, rate performance, and
electrochemical stability. solvation sheaths. As a legacy of pursuing optimum ion
conductivity, the salt concentrations used in nonaqueous
electrolytes have remained in the neighborhood of ∼1 M.
to LIB, the LSB system is still far from commercial realization, In the traditional electrochemical configuration, an electro-
because polysulfide reactivity rules out the carbonate solvents, lyte not only supports the transfer of mass and ionic charge
while the low boiling point/flash point of ether solvents across the cell but must also insulate electron transfer. In other
renders the system highly volatile and flammable.5,6 The low words, it must remain electrochemically inert at the surfaces of
anodic stability of ethers and the dissolution/shuttling of both the cathode and the anode, where redox reactions occur.
polysulfide species further worsen its perspective.7 Similar This latter requirement does not apply for the electrolytes in
challenges exist for LAB systems, where the high overpotential redox flow cells, where the electrochemically active species are
required for the delithiation of large-sized Li2O2 inevitably in the mobile phases either as dissolved species in the
induces irreversible oxidation of carbonate or ether solvents, a electrolytes or covalently bonded to electrolyte solvents.
process responsible for false capacities reported in early LAB However, the majority of the electrolytes still maintain
literature.8,9 Even within the rather matured realm of LIB, electrochemical inactivity as well as insulation toward electron
recent interest in higher voltage and higher capacity cathode conduction.
chemistries (5 V class LiNi0.5Mn1.5O2, LiCoPO4, or high nickel Given the extreme potentials where the electrodes of
as represented by LiNi0.8Mn0.1Co0.1) have pushed the SOA modern batteries operate, the electrochemical stability usually
carbonate electrolytes to the brinks of instabilities and side cannot be achieved in a thermodynamic manner but rather via
reactions,10 not to mention that the renaissance of the a passivation process. The sacrificial decomposition of
demanding Li metal as the ultimate anode presents the most electrolyte components (solvent, salt, additives) leads to the
aggressive challenge to electrolytes.11 To this end, new formation of an independent entity known as “interphase”,
electrolyte concepts hold the key to enabling new battery which is a thin film that separates the electrolyte from the
chemistries of higher power and energy, higher safety, lower electrode. For LIBs and batteries based on a Li-metal anode,
cost, and better cycle/calendar lives. the most important interphase is on the anode surface, which
In this review, we will discuss unconventional electrolyte was named the solid electrolyte interphase (SEI) to reflect its
systems that significantly deviate from the conventional state- electrolyte nature: a solid passivation layer that not only allows
of-the-art. These electrolyte systems, mostly reported in the Li+ to pass but also insulates electron tunneling. On the
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cathode side, an alternative term cathode electrolyte interphase Superconcentration is a relative term and therefore
(CEI) was created recently, but the existence of CEI is not as inaccurate by nature. It describes the general approach of
undisputable as SEI. It depends on the operating potential as formulating electrolytes deliberately at higher salt concen-
well as the chemistry of the cathode materials. Complications tration than maximum ion conductivity would require. Unlike
sometimes arise, especially when the active species in the the conventional electrolytes typically residing near the “1 M
cathode are involved in reactions with electrolyte components regime”, where sufficient population of solvent molecules
(solvents, salt anion, and additives). ensures the classical three-layer solvation structure,16,17 the
Since most modern battery chemistries involve electrode deficiency of solvent molecules in superconcentrated electro-
materials operating at extreme potentials, an important metric lytes leads to ion solvation structures that are not well solvated
that modern electrolyte must satisfy is the effectiveness of the in the classical sense. Instead, the individual ion solvation
kinetic protection of electrode surfaces provided by the sheaths are so compressed that they are forced to share solvent
interphase it forms in addition to the myriads of design molecules, and counterions inevitably appear at distances that
principles that conventional electrolyte must follow, such as are considered to be within the classical primary solvation
ion transport, (electro)chemical stability, viscosity, wettability sheaths (∼0.2 nm). Such phenomenon significantly alters the
toward electrodes and separator, intercomponent chemical ion solvation structure and in turn induces a series of new
stability, safety, cost, etc. Unfortunately, for a long period, the properties not usually seen in the conventional concentration
interphase has remained the least understood component in regime, which, besides new interphasial chemistry, also include
the batteries.12 Rational design of the interphase has been thermal, mechanical, ion, and mass transport, (electro)-
impossible. Even with the current knowledge accumulated chemical stability, as well as interfacial assembly at electrode
during the intensive research over the last two decades, it is still surfaces. Most of these properties bring certain benefits among
difficult to manipulate, let alone predict, interphasial chemistry. the 5 metrics illustrated in Figure 1, as summarized by the a
In a sense, the efforts to develop a new electrolyte are those to number of review articles published in the past 5 years.18−20
find out how well a new interphase chemistry works with the McKinnon and Dahn were perhaps the first pioneers who
electrode materials. ventured into the superconcentration regime. They reported in
2.1. Superconcentration 1985 that a saturated solution of LiAsF6 in PC could
One key piece of knowledge achieved in the past decade is how circumvent the cointercalation of PC into the layered host
ion solvation dictates the formation chemistry of SEI in LIBs. and predicted that superconcentration could be used to extend
Numerous experimental and computational studies confirmed the practical application range of such electrolytes even in
that there is a close correlation between the structure of the commercial cells.21 More attention was attracted by a later
primary solvation sheath of Li+ and the eventual interphase venture made by Angell et al., who at the time were struggling
chemistry (Figure 2),13,14 while systematic quantification of the to resolve the insurmountable conflict between the ion
conduction and the mechanical strength of polymer electro-
lytes. While this entanglement is still not well resolved even
today due to the intrinsic reliance of ion conduction on
polymeric segmental motion, Angell et al. reported in 1993
that by increasing the salt concentration above a certain
threshold level, a decreasing trend in ionic conductivity was
reversed (Figure 3).22 Here, the polymer can be viewed as a
macromolecular solvent with extremely high viscosity. The
resultant electrolyte actually inherited the merits of both high

Figure 2. Correlation between Li+ solvation sheath and interphasial

chemistry. Reproduced with permission from ref 13. Copyright 2007
American Chemical Society.

solvating power has been established for the most frequently

used solvent molecules in the battery industry.15 In such
context, once the classical solvation sheath structure achieved
in conventional electrolyte is altered, corresponding changes Figure 3. Venture into the superconcentration regime: the polymer-
are anticipated in the interphasial chemistry. It was this in-salt approach represents an early attempt to breach the
correlation that enabled the superconcentration concept, concentration confinement imposed by the pursuit of maximum ion
although many pioneers in superconcentrated electrolytes did conductivity. Here, the polymer serves as the macromolecular solvent
not necessarily realize the underlying mechanism responsible for lithium salts. Reprinted with permission from ref 22. Copyright
when reporting their work. 1993 Springer Nature.

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Figure 4. Unusual properties of superconcentrated ether electrolytes. (A) Thermogravimetric behavior of LiX dissolved in glyme (G3), which is
volatile in the absence of salt. Reproduced with permission from ref 30. Copyright 2012 American Chemical Society. (B) Charge−discharge profiles
of the graphite anode in LiFSI-G3 electrolyte. Reprinted with permission from ref 31. Copyright 2011 Electrochemical Society.

ion conduction of ionic liquids and mechanical resilience of a ether based.18,22 Highly concentrated ether-based electrolyte
typical polymer rubber. The term created for this new class of will ensure that the ether molecules are tightly bound to the
polymer electrolyte, polymer-in-salt, serves as the predecessor salt molecules and decrease the volatility of the system.21
of the latter solvent-in-salt, water-in-salt, or water-in-bisalt Highly concentrated ether-based electrolyte will ensure that
electrolytes.23−26 the ether molecules are tightly bound to the salt molecules and
2.2. Ethers decrease the volatility of the system.27
In the early 2000s, Pappenfus et al. discovered that
In strong contrast with carbonates, ethers have found much equimolar mixtures of either LiTFSI or LiBeti with tetraglyme
less commercial success, which can be attributed to their (G4) maintain the liquid state in a rather wide temperature
intrinsic interphasial disadvantages at both cathodes and range between 31 and 200 °C, while supercooling could extend
anodes. Their intrinsic chemical instability against oxidation the lower limit of the range even further down to −61 °C.28,29
naturally rules out their application with any high-voltage (>4 The extraordinarily low vapor pressure of G4, a rather volatile
V) cathode materials unless other stabilization means are solvent in neat state, in such equimolar mixtures reveals its
adopted, such as superconcentration. On the other hand, strong interaction with the salt. The authors considered the
although most ethers are chemically stable against reduction complexes of (Li-G4)+, a new cation in a quasi-ionic liquid,
(especially when compared with esters), their stability prevents which displayed ion conductivities of 1.0 mS/cm along with
them from forming SEI over graphite but instead enables anodic stability windows higher than 4.5 V. The latter has been
cointercalation, an undesirable scenario leading to clumsy hardly possible with any ether-based electrolytes.
intercalation chemistry of mediocre potential, low capacity, Watanabe and co-workers furthered the exploration of this
and poor reversibility. Those disadvantages on the anode alone class of electrolytes based on ether in a more systematic
has thus excluded the presence of ether-based electrolytes in manner and revealed the unusual properties exhibited when
LIBs. Only in the special case of the Li−sulfur battery does salt concentration crossed a certain threshold (Figure 4a).30−55
ether find a niche, because sulfur does not operate at especially Besides the materials perspective, the most significant
high potential, while Li-metal anode requires better chemical contributions from Watanabe were the efforts made to
stability from the electrolytes. More importantly, the reactivity understand these abnormal properties on a fundamental
of polysulfides (intermediate of a Li−S battery) with esters level. Thermal (DSC, TGA), spectroscopic (NMR, FTIR), as
through a nucleophilic attack20 forces researchers to rely on well as computational characterization unequivocally evi-
ethers denced that all ether solvents in these superconcentrated
While ethers generally possesses low viscosity and high systems are tightly harnessed by Li+. Such strong interaction
solvating power, thanks to the combination of moderate led to a high thermal stability up to 200 °C. Particularly
dielectric constant, high electron donicity, and denticity (a surprising were the improvements in their electrochemical
parameter describing molecules with polychelating capabil- stabilities toward the cathode and graphitic anode, as it had
ities), they are also typically much more volatile and flammable been well established that ether-based electrolytes were
than esters. In particular, in the case of Li−S batteries, the vulnerable to oxidation at potentials ranging from only 3.5−4
commonly used 1,3-dioxolane and dimethoxyethane solvents V and tend to cointercalate with Li+ into graphitic structures,
will easily evaporate during cell construction. This often alters forming the undesirable ternary graphite intercalation com-
the designed composition of the electrolytes and introduces pounds (Figure 4b).56 The emergence of these unusual
hard-to-control variables in the eventual performance of the properties can be attributed to the competitive solvation of
cells. Nevertheless, with these advantages and disadvantages, Li+ by solvent (glyme) molecules and anions, which does not
ethers constitute one of the two major polar solvent systems exist in diluted salt systems. This intimate interaction between
that have been extensively used as electrolyte solvents in cation and anion is of particular significance to the interfacial/
laboratories. interphasial properties that often dictate the electrochemical
The excellent solvating power of ethers made them the first stabilities of the electrolytes.
superconcentrated electrolytes explored, even if one excludes The deviation of ether-based superconcentrated electrolytes
polymer-in-salt electrolyte based on poly(ethylene oxide) as from their diluted counterparts provided opportunities for
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Figure 5. Solvent-in-salt electrolytes based on mixed ethers DOL/DME (1:1 by volume). (a) Weight and volume ratios of LiTFSI, and definition
of solvent-in-salt. (b) Corresponding ion conductivity and viscosity. Reprinted with permission from ref 23. Copyright 2013 Springer Nature.

Figure 6. Li-metal deposition and morphology as obtained from a Li//Cu cell in different electrolytes. (a) Cycling stability. (b−g) SEM top view
(b, d, and f) and cross-sectional view (c, e, and g) of deposited Li from a conventional electrolyte (1.0 M LiPF6 in EC/EMC 30:70) with 2% VC (b
and c), highly concentrated electrolyte (HCE, LiFSI-1.2 DME, d and e), and locally highly concentrated electrolyte (LHCE, LiFSI-1.2DME-TTE, e
and g). Reprinted with permission from ref 56. Copyright 2019 Cell Press.

various electrolyte designs aimed at practical applications is mainly enabled by the densely packed Li-metal morphology
(Figure 5a). Suo et al. demonstrated that when the when deposited underneath the new interphasial chemistry
concentration of LiTFSI approaches 7 M in ether mixtures, that is otherwise unavailable in diluted electrolytes (Figure 6).
the Li/S chemistry could benefit from a series of new The new SEI on the Li-metal surface now carries the chemical
properties including the low solubility of polysulfides, a high signature from the anions, made possible by the combination
Li+ transference number (>0.7), as well as the suppression of of two factors: (1) the high presence of anion in the primary
Li dendrite growth (Figure 5b).23 As Li metal was revisited in Li+ solvation sheath, which fluorinated the resultant interphase,
the early 2010s as a viable pathway to high energy densities,57 and (2) the relative inertness of ether molecules toward the Li
ether-based superconcentrated electrolytes induced a signifi- surface.
cant amount of interest due to the stability of ethereal species Similar benefits were also extended to the cathode side. As
against reduction. Thus far, the best Coulombic efficiencies of Li+ is tightly solvated by ether molecules, the (electro)chemical
the rechargeable Li-metal anode came from the ether-based activity of the latter, especially the donicity of its lone electron
electrolytes (99.3% at 0.5 mA cm−2 and 1 mAh cm−2),58 which pair on oxygen, is significantly reduced, leading to less
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Figure 7. Unusual properties of superconcentrated electrolytes using carbonate or exotic solvents. (a) Exfoliation and reversible lithiation behaviors
of graphite in dilute (0.82 M) and superconcentrated (2.72 M) LiBeti in PC. Reprinted with permission from ref 62. Copyright 2003
Electrochemical Society. (b) Change of Li+ solvation structure when Li salt concentration crosses a certain level. Reprinted with permission from
ref 13. Copyright 2014 American Chemical Society. (c) Formation of an anion-containing Li+ solvation sheath in AN. Reprinted with permission
from ref 64. Copyright 2014 American Chemical Society.

susceptibility of ethers toward oxidation on the cathode. The is high enough, the characteristic graphite exfoliation would be
higher than usual anodic stability has been described by replaced by reversible lithiation/delithiation of graphite
Watanabe et al.20 and further confirmed by Jiao et al. and Ren (Figure 7a).62 Although no comparative chemical analysis
et al. on a highly oxidative surface of fully charged NMC up to was performed on the graphite surface at the time, it is
4.3−4.5 V.58,59 apparent that an entirely different interphase must have been
2.3. Esters generated due to the superconcentration. This connection was
finally made by Nie et al., who showed that an anion-originated
The state-of-the-art electrolytes employed in LIBs consist of (LiF-rich) interphase will result from the high salt concen-
carbonate esters. This class of electrolytes is blessed by both a tration (3.0−3.5 M LiPF6 in PC)63 in accordance with the SEI-
high dielectric constant and donicity, exhibiting excellent formation mechanism proposed earlier by Xu et al. where the
solvating capability toward most Li salts. However, a limited Li+ solvation sheath structure is considered the central factor
number of superconcentrated electrolytes have been developed dictating interphasial chemistry (Figure 7b)13
based on this class of solvents. The major restriction stems An innovative departure from the conventional avenue of
from the difficulty in dissolving a high concentration of salts using cyclic carbonate as an indispensable cosolvent was made
while still maintaining the liquid state. This is especially true by Wang et al., which was made possible by a new salt lithium
when the most favored carbonate solvent, EC (mp 36.4 °C), bisfluorosulfonyl imide (LiFSI) that does not require the high
often solidifies with a salt concentration above 1 M, as dielectric constant of a cyclic carbonate to reach super-
indicated by the diversified crystalline solvate compounds as concentration.65 The simple electrolyte consisting of ∼10 m
identified by Henderson and co-workers.60 More freedom was LiFSI dissolved in a single solvent of linear carbonate dimethyl
offered by the lower molecular symmetry of PC, which comes carbonate (DMC) provides not only high ion conductivity and
with both low mp (−48.8 °C) and strong resistance against nonflammability but also an excellent electrochemical stability
crystallization; hence, among the earliest superconcentrated window that supports the reversible operation of both graphite
electrolytes explored was PC when McKinnon and Dahn anode and a 5 V class cathode material LiNi0.5Mn1.5O4, which
observed that the cointercalation of PC molecules into layered could have been otherwise impossible. The implication carried
ZrO2 was prevented at high salt concentration.21 The forward by this work is that superconcentration could induce
cointercalation of PC molecules into graphite caused far an alternative interphasial chemistry to circumvent the many
more serious issues, i.e., exfoliation of the graphitic structure restrictions that typical LIB electrolytes must subject to, the
following its cointercalation and hence preventing the use of most prominent of which is the presence of ethylene carbonate
graphite as a storage host for Li+.61 It took nearly two decades (EC). This opens opportunities to many “exotic” solvents that
for the superconcentration effect on graphite to be discovered, have been out of the question, especially considering the
when in 2003 and 2008 Jeong et al. described that as long as sensitive and fragile structure of graphitic anodes toward
the concentration of lithium salts (LiPF6, LiClO4, or LiTSFI) cointercalation and exfoliation.
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Figure 8. Extended electrochemical stability windows of aqueous electrolytes via superconcentration. (a) Redox potentials of the major anode and
cathode materials: Li metal, Mo6S8, Li4Ti5O12, LiMn2O4, LiFePO4, LiCoO2, and LiNi0.5Mn1.5O4. (b) Redox reactions of water molecules at pH = 7
evolve hydrogen and oxygen at the anode and cathode surfaces, respectively, giving rise to a thermodynamic stability window of 1.23 V, whereas
superconcentration (21 mol kg−1 LiTFSI in WiSE and 27.8 mol kg−1 LiTFSI + LiBeti in the hydrate melt electrolytes) significantly expands
windows to larger than 3.0 V. Reprinted with permission from ref 24. Copyright 2015 Springer Nature.

2.4. Exotic Solvents opportunity for many solvent molecules that would be
Because the electrolyte must interface with both electrodes in otherwise impossible due to the stringent requirements for
the battery, it is perhaps the component that has to satisfy the electrolytes. In fact, the benefit of such alternate interphasial
most stringent requirements, ranging from bulk (liquid range, chemistry was already more or less demonstrated in the above
salt solubility, solvation, and liquid structure), transport (ion cases of both ether and esters, but it will be most pronounced
transport, preferential diffusion), interfacial/interphasial stabil- for the exotic, noncarbonate solvents, because those solvents
ity, as well as peripheral (viscosity/wettability, safety, toxicity, were considered useless for advanced battery application,
and cost) properties. Accordingly, the result of such rigorous especially for Li metal or LIB.
selection matrix only provides us with a short list of electrolyte Examples of such exotic solvent systems started with
solvents as feasible candidates, which roughly fall into two dimethyl sulfoxide (DMSO), reported by Yamada et al. in
families of polar and aprotic organic compounds: ethers and 2010,67 who showed that 3.2 M LiTFSI in DMSO enables the
esters, with very few exceptions. The emergence of transition intercalation of Li+ into graphite while preventing the
metal oxide cathode materials essentially ruled out the ethers cointercalation of DMSO molecules. This concept was
due to their anodic instability at potentials beyond 4.0 V vs Li, subsequently expanded to other solvent candidates by Yamada
while the extensive adoption of graphitic anode materials in et al., who demonstrated that superconcentration of LiTFSI
LIB further narrows the candidates down to carbonate esters can achieve a similar interphasial chemistry on the graphitic
(alkyl esters of carbonic acid), with EC in particular as the anode in electrolytes based on tetrahydrofuran, sulfolane,68 as
indispensable source of interphasial chemistry to stabilize the well as acetonitrile (Figure 7c),64 none of which can support
graphitic anode. reversible Li+ intercalation at a conventional salt concentration
The reliance of LIB electrolytes on EC could be explained near 1.0 M. Although in earlier efforts researchers tried to
by the correlation between the Li+ solvation sheath structure rationalize the unusual electrochemical behaviors of the
and the interphasial chemistry. Numerous mechanistic studies graphite anode in these electrolytes by resorting to the
on interphases have established that as the Li+ dictates how the reduced solvation numbers of Li+ at these concentrations,
ternary graphite intercalation compound (GIC) forms during Yamada et al. were the first to correctly attribute the
the initial lithiation process and such GIC serves as the phenomenon to a new interphasial chemistry originated from
precursor for the eventual interphases (Figure 2), the solvent the reduction reactions of anions. This argument was
molecules in the primary solvation sheath of Li+ generate the supported not only in this work64 by X-ray photoelectron
major chemical source for an interphase.13,66 The necessity of spectroscopy (XPS) performed on the recovered electrodes
EC being present in almost all LIB electrolytes is therefore but also in the later works with numerous surface analyses,
determined by the facts that Li+ tends to be preferentially which all identified high abundance of fluorides (mostly LiF)
solvated by EC over linear carbonates (DMC, EMC, etc.) and as the major species in the new interphases.
that alkylcarbonate generated by the single-electron reduction While the applicability of these exotic electrolytes in
of EC proves to be the most efficient interphasial practical batteries remains to be further examined on “realistic”
component.61 Such correlation still holds true at super- electrodes, especially in terms of their stability against the
concentration, where the Li+ solvation sheath structure is cathode surface or corrosion of the substrates,69 the knowledge
now disturbed by the much higher anion population in the accumulated sets the foundation for the many superconcen-
electrolytes and the interphase chemistry hence is no longer trated electrolyte systems to follow. For example, super-
solvent derived but originated from anion reduction as well. concentrated LiFSI in sulfolane has been shown to be
The alternate interphasial chemistry opens a window of applicable toward high-voltage (4.5 V) LIBs,70 where the salt
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Figure 9. Interphase in superconcentrated aqueous electrolyte. (Left) TEM images (a and b) showing the presence of crystalline LiF or NaF on the
surface of anodes recovered from WiSE. Reprinted with permission from ref 24 Copyright 2015 AAAS. (Right) Correlation between the formation
of SEI on the anode and the suppression of water-splitting reactions, where a−d display the progressive change in voltage profiles for the first
charge−discharge profiles of a full Li-ion cell constructed with the Mo6S8 anode and LiMn2O4 cathode and e−h correspond to H2 and O2 evolution
monitored during the first charging process using differential electrochemical mass spectrometry (DEMS) in the same aqueous full Li-ion cells.
Four concentrations from dilute to superconcentration were used. Reprinted with permission from ref 93. Copyright 2017 American Chemical
Society.

anion provides interphasial chemistry sources for interphases at salt at even higher concentration (up to 28 m),25,75 or via the
both the anode and the cathode. Similar interphasial introduction of bivalent cation additives,76 or with the
chemistries were identified in concentrated LiFSI or NaFSI application of a hydrophobic interlayer that serves as precursor
in phosphate esters71 or phosphamides,72 where the solvents for a highly fluorinated interphase.77 The latter enabled the
themselves are flame-extinguishing agents, as well as the reversible lithiation/delithiation of graphite in aqueous electro-
sodium version of these electrolytes.73 lytes, making the 4 V class aqueous batteries a possibility. More
The switching of the interphasial chemistry source from recently, Ko et al. managed to further increase the salt
solvent molecules to anions renders significant flexibility in concentration to a new high level of 55.55 m, where the water/
selecting solvents; therefore, more interesting and exotic Li+ ratio reaches 1:1.78 Direct benefit of such high salt
solvent systems are anticipated to be developed in the near concentration is an electrochemical stability window of nearly
future. 4.8 V, which allows the operation of an Li−Al alloy anode
2.5. Water without any precoated interphase. In another direction, the
discovery of a unique graphite intercalation chemistry by Yang
Perhaps the most extreme extension of the superconcentration et al. for this class of aqueous electrolytes raises the possibility
concept is the new class of aqueous electrolytes where the salt for the first time that an aqueous battery chemistry could
anion completely resumes the responsibility of forming outperform that of nonaqueous LIBs.79 This new cathode
necessary interphases. The superconcentration widens the chemistry leverages the intercalation conversion of simple
originally narrow electrochemical stability window of water halides in the graphite structure at 4.2 V vs Li, which is only
(thermodynamically ∼1.23 V, with cathodic and anodic limits reversible in a derivative of WiSE and delivers a capacity higher
sitting at 2.6 and 3.8 V vs Li, respectively) to accommodate the than transition metal oxides.
diversified battery chemistry (Figure 8). The pioneering effort The aqueous version of superconcentrated electrolytes was
was made by Suo et al.,24 who described a water-in-salt also extended to other battery chemistries beyond the Li ion,
electrolyte (WiSE) consisting of 21 m LiTFSI dissolved in as evidenced by the diversified devices demonstrated by
water. An electrochemical stability window of ∼3.0 V was numerous researchers, among which are a unique chemistry
generated, with cathodic and anodic stability limits now sitting using a sulfur conversion reaction as the anode80 and
at 1.9 and 4.9 V vs Li, respectively, thanks to an interphase of intercalation chemistries of the sodium ion,81 potassium
LiF on the anode and low water activity due to the high salt ion,82−84 and bivalent Mg85 and Zn86−91ions. In particular, Ji
concentration. A similar system termed hydrate melt was soon and co-workers used a series of aqueous superconcentrated
independently reported by Yamada et al.,74 followed by further electrolytes based on ZnCl2 to enable a number of interesting
improvements in the stability of WiSE via the use of a second chemistries, not only providing the possibility of reconciling
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the high cost and beneficial properties brought by super- chemically attacks TFSI, leading to fluoride deposition in the
concentration but also revealing an unexpected new horizon form of interphase (Figure 9c).95 Lee et al. went even further
for this class of electrolytes in supporting exotic battery by stating that the formation of an aqueous interphase does not
chemistries that were otherwise impossible.91 necessarily require an anion to provide a chemical building
Aside from potential benefits in energy density and safety, block. By dissolving NaClO4 in water at superconcentrated
the aqueous nature of such electrolytes also brings the stability concentration (17 m), they found an interphase consisting of
against ambient environment. This advantage was most Na2CO3 and NaOH, neither of which seems to originate from
conspicuously demonstrated by an aqueous gel version of Zn anion reduction. Such an interphase expands the electro-
electrolytes, which was exposed to lab ambient conditions for chemical stability window up to 2.7 V without the expensive
40 days and experienced no weight loss.86 In sharp contrast TFSI or triflate (OTf) based salts.96 A new mechanism was
with nonaqueous electrolytes whose moisture sensitivity thus proposed involving reduction of dissolved oxygen and
requires device hermeticity that makes the device rigid and CO2 in the electrolyte, which had been identified earlier by
nonconformal, the ambient stability introduces unprecedented Suo et al. but was thought to be impurities in the interphase.93
flexibility as the device could now work in open configurations. Lee et al. suggested that it was these oxygen- and CO2-derived
Such flexibility has been demonstrated preliminarily on the ingredients, instead of anion reduction, that ensures the 2.0 V
pouch cell level using a symmetric Li-ion chemistry,92 but no class Na-ion battery to operate stably over 200 times. Still
doubt there are still plenty of possibilities to explore. further, Zheng et al. argued that the main contribution to the
Since interphases were never observed in aqueous electro- expansion of the electrochemical stability window for a
lytes before application of the superconcentration concept, superconcentrated (∼22.2 m) LiNO3 aqueous solution should
several attempts were already made to understand how such arise not from any interphase protection but from the kinetic
interphases could form and exist in aqueous media. These barrier associated with the energy that is required by a water
interphases should still maintain the two characteristics molecule to free itself from a polymer-like local structure
possessed by all solid electrolyte interphases known thus far: [Li+(H2O)2]n.97 Given the fundamental importance, this topic
(1) in solid form, i.e., remaining insoluble in water; and (2) is likely to excite more debate and intensive research.
with electrolyte nature, i.e., conducting ions but insulating The attempt to understand the chemistry and formation
electrons. The initial analyses conducted by Suo et al. on mechanism of aqueous interphases naturally prompted interest
recovered anode materials seem to reveal neat LiF as the in the interfacial structure at electrodes, which should, no
interphase component (Figure 9a),24 and this chemical matter in aqueous or nonaqueous systems, precede any
singularity becomes even more pronounced in the sodium chemical reactions that lead to the actual formation of any
version of WiSE, where under a high-resolution transmission interphases and therefore should in principle predict the
electron microscope (HR-TEM) the NaF on the anode surface interphasial chemistry. When Oleg and co-workers tried to
appears to adopt an almost ideal lattice arrangement.81 This rationalize the cathodic challenge, i.e., why the expanded
new interphasial chemistry apparently arises from the electrochemical stability windows of aqueous electrolytes are
reduction of the TFSI anions used and induces certain always “positively biased” (Figure 8), they held the electrode−
perplexity: while metal fluorides are indeed the least soluble anion interaction as mainly responsible.77 According to
salts for these alkaline metal cations in aqueous media, they are molecular dynamics (MD) simulations, such uneven position-
also ionic insulators. Thus, how Li+ or Na+ could migrate ing of the cathodic and anodic limits in electrolytes stems from
across such interphases at fast rates, as suggested by the rate the competitive distributions of water molecules and salt
capabilities of the Li- or Na-ion batteries constructed on such anions at the inner-Helmholtz interface of the electrode, which
electrolytes, becomes a mystery. More detailed analyses by Suo varies as a function of both salt concentration and applied
et al. later slightly modified the interphasial chemistry formed potential. While superconcentration ensures that the inner-
in WiSE, where a minor presence of Li2O and Li2CO3 Helmholtz layer of the electrode surface is populated by
embedded in the matrix of LiF was identified by both XPS anions, leading to an interface that favors the formation of
and secondary ion mass spectroscopy (SIMS).93 These anion-based interphase, any cathodic polarization would
“impurities”, by interfacing with the fluorides at the nanoscale, disrupt such preference by expelling anions and attracting
might have played the most significant role in creating ionic cations solvated by water molecules (Figure 10).
pathways and generating interstitials and excess Li+.94 A Another equally important question raised for super-
mechanism involving the mixed reductions of TFSI, water concentrated electrolytes is whether any long-range liquid
molecules, as well as a trace amount of CO2 dissolved in WiSE structure engenders from the unique local solvation structures
during the initial charging cycle was proposed by Suo et al., and how such structure affects the overall ion transport
which seemed to be supported by the in situ gas analysis properties. Oleg et al. calculated the ion solvation in WiSE and
performed during interphase formation using differential concluded that above a threshold salt concentration (10 m
electrochemical mass spectroscopy (Figure 9b). The generated LiTFSI) a significant disproportion of Li+ solvation sheath
hydrogen and oxygen at the anode and cathode surfaces, structure occurs, i.e., the distribution of solvent molecules and
respectively, quantitatively reflect how each electrode is anions around a Li+ is not averaged according to the bulk
progressively passivated as the salt concentration increases. composition; instead, some Li+ would only see water
More recently, an alternative mechanism was proposed to molecules, while others see anion (Figure 11a).99 This uneven
further modify the above arguments that have been centered distribution of solvation sheath structure results in a nanoscale
on direct electrochemical reduction of the anion (TFSI), which phase separation, although such a nanoheterogeneity would
generates LiF or NaF as the main ingredient of the interphase. experience exchanges on a time scale of picoseconds (Figure
Dubouis et al. suggested that the TFSI anion does not directly 11b). According to MD simulations, the nanoheterogeneity
experience electrochemical reduction; instead, the hydroxide should lead to a liquid structure with a characteristic length
generated by the reduction of interfacial water molecules scale of 1−2 nm, which was confirmed by small-angle neutron
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The direct consequence of the above liquid structure is the

preferred cationic transport because the anions are relatively
“immobilized” in such transient networks. This was further
supported by Li+ transference numbers measurement using
pulse-field nuclear magnetic resonance (Figure 12), which is
apparently higher (∼0.73) than what researchers are familiar
with in diluted electrolytes (0.2−0.4). Theoretically, the
preferential ion transport is believed to benefit the rate
performance of a battery chemistry based on the redox
reactions of this ion. Thus, the capability of WiSE to support
high rate charge/discharge (up to 60 C) in diversified
chemistries (Li+, Zn2+),86,92 despite the moderate ionic
conductivities, seems to stem from such preferential ion
transport that was enabled by the unique ion solvation
structures and the subsequent long-range liquid structures.
Figure 10. Interfacial distribution of Li+, water molecules, and anions More recently, Dokko et al. proposed a similar cation−anion
as a function of applied potential as revealed by molecular dynamics decoupling behavior in superconcentrated sulfolane electrolyte,
simulations performed for WiSE. Reprinted with permission from ref where Li+ was observed to hop from one coordination site to
98. Copyright 2018 American Chemical Society. another without concerted movements of the solvent
molecules or anion.101 This conclusion raises the possibility
of whether such long-range liquid structure could exist
scattering (SANS) with a low-Q peak at 0.45 Å−1 (Figure 11c). universally in all electrolytes, no matter aqueous or non-
The arguments made by Oleg et al. were supported by Lim et aqueous, as long as a certain threshold salt−solvent ratio is
al. with femtosecond pump−probe infrared spectroscopy,100 crossed. It should be pointed out that ion hopping, also named
who found that dissolved Li+ forms a three-dimensional, structural ion transport, as opposed to vehicular that is often
percolating network that is spontaneously intertwined with encountered in “dilute” electrolytes, does not necessarily
nanometric nonsolvating water molecules through which the involve a long-range liquid structure such as that observed in
solvated Li+ move as if they conduct via a fast lane that is little WiSE. Generally, the vehicular manner dominates when the
affected by the anions (Figure 11d). solvation sheath consists of solvent molecules that strongly

Figure 11. New liquid structure consisting of nanoheterogeneity at superconcentration. (a) Three-dimensional snapshot generated from molecular
simulations showing an interconnected water domain (red) and the TFSI anion. (b) Structure factor from small-angle neutron scattering
experiments that coincides well with that predicted by MD simulations. Reprinted with permission from ref 99. Copyright 2017 American Chemical
Society. (c) FTIR absorption spectra of OD in deuterated aqueous electrolytes, where Gaussian fitting results for a series of salt concentrations
were performed to reveal various water speciation (bulk vs interfacial). (d) Time-resolved IR-pump probe (normalized) spectra of concentrated
electrolytes at 5, 10 and 21 m of LiTFSI. Reprinted with permission from ref 100. Copyright 2018 American Chemical Society.

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Figure 12. Preferred Li+ transport in superconcentrated aqueous electrolyte. (a) Self-diffusion coefficients for ions (Li+ and TFSI) and water
molecules in WiSE from MD simulations at 25 °C and pfg-NMR experiments at 20 °C. (b) Li+ transference number as measured by pfg-NMR in
WiSE in comparison with nonaqueous electrolytes. Reprinted with permission from ref 87. Copyright 2017 American Chemical Society.

coordinate with cations, such as ethers, while weak cation− 13). Thus, while the local environment of cations (Li+ or Na+)
solvent interactions lead to more structural contributions. With still maintains the solvation structure of superconcentrated
the given salt and solvent species, superconcentration tends to
induce higher structural diffusion, as in the case of both
sulfolane101 and acetonitrile.64 The disproportionation of
cation solvation sheath structure in water might be an
exception, where the high cation transference number is
thought to be prevalent in the vehicular instead of the
structural mechanism, because most of the ion transport is
carried out by a Li+-rich phase consisting of Li+(H2O)4
speciation.99
In a broader perspective, the preferential ion transport
behavior observed at superconcentration, no matter arising
from structural ion transport or long-range liquid structure,
implies an effective approach to decouple cation transport from
the Coulombic traps of anions and solvent molecules with
potential significance going way beyond battery or even
electrochemical devices.
2.6. Hybrids
The most severe challenge faced by superconcentrated
electrolytes is their high cost. In the LIB industry, electrolyte
often constitutes the second most expensive component after
cathode materials, while lithium salt is often the most
expensive among all electrolyte components. While the imide
anions such as TFSI or FSI are often favored due to their
excellent solubility and electrochemical uniqueness, these
uncommon anions must be synthesized and purified via rather
sophisticated processes, which are costly at the current stage
due to limited market demand. Of course, more serious cost
pressure comes from the extremely high concentrations
involved. Besides cost concerns, superconcentration also brings Figure 13. Local superconcentration. (a) Schematic illustration of
the disadvantages of high bulk viscosity and poor wettability, dilution from a superconcentration to a local superconcentration. (b)
which make it difficult for the electrolytes to thoroughly access Raman spectra with different NaFSI concentrations. Reprinted with
the porous structures of both electrodes and separators. permission from ref 102. Copyright 2018 American Chemical Society.
A rather clever approach named localized high concentration
was proposed by Zheng et al., who attempted to maintain the
advantages of superconcentrated electrolytes (interphasial
chemistry, preferential cation transport, and safety) while electrolytes, which dictates the interphasial chemistries at
eliminating their disadvantages (cost, viscosity, ion conductiv- electrode surfaces, the bulk properties (ion transport, viscosity,
ity, and wettability).102−104 The essence of such approaches is or wettability toward the electrodes and separators) were
a nonsolvent, which does not directly dissolve the salt but mainly defined by the average composition of the bulk
should form, at least macroscopically, homogeneous mixtures electrolyte that still bears the nature of the diluted regime. This
with the bulk electrolyte solvents. This nonsolvent, usually a successful separation of the desired bulk from the interfacial
polyfluorinated ether with weak polarity, serves as both a properties via the engineered solvation structure and long-
diluent to reduce the overall salt concentration in bulk range liquid structures has enabled a number of exotic solvent
electrolyte and a structure interrupter that forces the salt- systems traditionally thought impossible105,106 and raised the
containing domains to be compressed so that a similar hope that more optimized electrolyte systems should be
solvation sheath structure can still be preserved locally (Figure expected from this effective concept.
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In a related approach, Wang et al. hybridized aqueous and Although only limited efforts have been made in this
nonaqueous electrolytes in the hope that the advantages of ion direction, the increasing demand for a wider service temper-
transport and nonflammability from the former and the ature will inevitably encourage more attempts to cross the
interphasial chemistry from the latter could be combined. conventional regimes confined by liquid boundaries.
Unexpectedly, an acyclic carbonate DMC was selected as the
nonaqueous component, despite the fact that DMC is 3. SEMISOLIDS
immiscible with water in the absence of Li salt. Apparently, Between the electrolytes in the liquid state and those in the
the water molecules in WiSE differ significantly from bulk true solid state (ceramic or glass) there is an intermediate class
water at the superconcentration of LiTFSI; hence, a where the electrolytes macroscopically behave as a solid with
homogeneous solution was formed between DMC and sufficient dimension stability but microscopically the ions in
WiSE.107 The overall concentration of LiTFSI is ∼14 M in them interact with the solvating environments or transport
the hybridized electrolyte, which also inherits the non- across them as they do in liquids. This intermediate class of
flammability from the aqueous nature. More importantly, the electrolytes includes solid polymer electrolytes (SPEs), gel
carbonate molecule introduced a significant amount of a polymer electrolytes (GPEs), or the many derivatives of these
second component (Li2CO3) into the SEI, expanding the two classes115,116,116,117
electrochemical stability window to ∼4.1 V, where even a high- The attempts of solidifying electrolyte have been driven by
voltage cathode material LiNi0.5Mn1.5O4 could be supported. the temptation of integrating the functions of an ionic
This approach was soon expanded to Na battery chemistry, conductor and a physical separator between the cathode and
where a hybrid was made between WiSE and PC,108 or the anode as well as the benefit of better safety. Although the
supercapacitor, where acetonitrile was used as the nonaqueous concept of SPEs was proposed by Armand in 1970s,118,119 this
component.109,110 Obscuring the once clear demarcation class of polymer electrolyte encountered the intrinsic dilemma
between aqueous and nonaqueous regimes, this new class of of relying on the polymeric linkage to provide both mechanical
hybrid electrolytes offers unlimited space to explore.111 strength and ion transport. Consequently, they only found
2.7. Beyond Liquid Phases limited applications in batteries, where elevated temperature
(>60 °C) is a prerequisite to achieve a decent ion conductivity
A few rather transformative concepts represent new frontiers (>10−4 S/cm) for practically feasible cell reaction rates.120
where the conventional phase boundaries have been breached, Furthermore, despite an early report that lithiated graphite can
allowing us to expand the temperature limits imposed by the be electrochemically formed in PEO-based SPEs,121 these
liquid state of electrolytes. A new class of electrolytes based on electrolytes are actually incapable of supporting graphitic
liquefied gas was reported by Rustomji et al. using a variety of anodes due to high interfacial resistances unless they are
hydrofluorocarbons (fluoromethane, difluoromethane, fluoro- plasticized with proper solvents. This essentially excludes
ethane, 1,1-difluoroethane, 1,1,2,-tetrafluoroethane, and 2- polyether-based SPEs from the LIBs and confines their
fluoropropane).112 Those unconventional “solvents” are all in opportunities to a narrow niche market of Li-metal anode
the gaseous state under ambient conditions. However, under batteries.122 On the other hand, GPEs have found much more
moderate pressure, their mixture with Li or ammonium salts extensive applications in commercial LIBs due to its liquid-like
(LiTFSI, 1-ethyl-3-methylimidazolium−TFSI, and tetrabuty- ion solvation and transport behaviors as well as better
lammonium−PF6) turns into liquefied states, which are stable interfacing with electrode surfaces than SPEs.123,124 Interest
with Li-metal anodes and can support the reversible operation in both SPE and GPE has been revived in the past few years in
of both electrochemical capacitors and a 4 V battery using an attempt to align to the new directions aiming at either
LiCoO2. Due to their high dielectric constant and low improving existing Li-ion batteries for new capabilities
viscosity, these electrolytes display exceptional performance, including extreme fast charging, where a high Li+ transference
especially at temperatures as low as −60 °C. It was believed number is desired,125 or new battery chemistries such as those
that a highly fluorinated interphase has been formed on the Li- based on the lithium-metal anode, where dendrite prevention
metal surface upon its contact with these fluorocarbons. requires a host of properties from mechanical strength, to
Compared to the SEIs generated in carbonate-based electro- preferred Li+ transport, to self-healing capabilities, and possess
lytes, the composition of these interphases was found to be intrinsic safety as well as capability of negative responsiveness
highly ceramic-like instead of polymeric/organic with LiF as to a hazard.126 Differing from the efforts placed on polymers
the major component. Further optimized electrolytes in this back in the 1970−1990s, most of those quests for new
class demonstrated stable cycling over 500 cycles with a semisolid electrolytes used nanomaterials and nanotechnolo-
Coulombic efficiency of 99.6%.113 gies that were only developed in recent decades, which allow
On the other side of the phase spectrum, Wu et al. reported for elegant design, control, and fabrication of ionic pathways
ion conduction behavior in solid ice, which opens the and chemical processes at the nanoscale with unprecedented
possibility of a new class of solid-state electrolyte for low- precision.
temperature applications.114 Conductivities of up to 10−3 S 3.1. Polymers, Polymer−Liquid, or Polymer−Polymer
cm−1 were reported for various sulfate salts at ∼−8 °C. The Hybrids
authors attributed the transport of Li+ and other alkali cations SPEs are essentially electrolyte solutions consisting of Li salts
to an ion-hopping mechanism through the ice lattice. including LiTFSI127 and LiTf128 among others dissolved in
Surprisingly, multivalent ions (Al3+, Mn2+, Zn2+, and Cu2+) macromolecular solvents, whose ether linkages (CH2CH2O)x
also displayed conductivities between 10−4 and 10−7 S cm−1 in serve as coordinating units for Li+ as in the ether-based liquid
the low-temperature range from −4 to ∼−10 °C, while Cu was electrolytes. Thus, most SPEs inherited the intrinsic problems
even demonstrated to be able to plate from such solid ice brought by these ether linkages, such as excessively strong
electrolyte onto an electrode. coordination with Li+, so that the solvation sheaths become a
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Figure 14. (a) Blending polymer electrolyte with Li1.5Al0.5Ge1.5(PO4)3 NASICON-type SSE. Reprinted with permission from ref 135. Copyright
2015 Electrochemical Society. (b) Depiction of the dual-layer polymer electrolyte system with a high-voltage stable polymer in contact with the
cathode and a low-voltage stable polymer electrolyte in contact with the anode. Adapted with permission from ref 127. Copyright 2019 Wiley
VCH. (c) Application of a polymer/inorganic blend electrolyte to create an artificial SEI layer for lean liquid electrolyte operation. Reprinted with
permission from ref 136. Copyright 2019 Springer Nature.

Figure 15. Single-particle ion-conducting membrane using polymer and solid-state electrolyte particles LATTP. (a) Schematic of the fabrication
and final architecture of the membrane. (b) Cross-section and top-view SEM images as well as optical photograph of a typical composite
membrane. Reprinted with permission from ref 144. Copyright 2015 Wiley VCH.

“solvation cage” that hinders efficient Li+ transport or low are still constructed upon ether linkages that are copoly-
stability against oxidation. Efforts seeking alternative polymer merized, grafted, or blended with other structural units.
unit structures rather than ether linkages to dissolve Li salts Depending on the salt concentration (which is usually lower
have been unsuccessful; hence, most SPEs under development than that of the corresponding liquid electrolyte due to the
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limited salt solubility in polymers) and average molecular of 2.3 × 10−4 S cm−1 at 30 °C was reported, which is far
weight of host polymers, the resultant polymer could be superior to the parental SPE. The authors attributed this
flexible, brittle, or rigid. enhancement to the forced alignment of polymer chains within
Compared to inorganic solid electrolytes that will be the nanosized channels (∼200 nm), where Li+ can find the
discussed in the following section, SPEs are significantly easier best pathway to transport.
to synthesize and process, while their “soft” nature offers Besides ion conductivity, a property more relevant to the
further advantages in not only flexibility and facile manufactur- high rate capability of the cell reaction is Li+ transference
ability but more importantly the intimate interfacing with solid number (t+). Theoretically, a unity Li+ transference number (t+
electrodes. The latter has been one of the most severe = 1.0) eliminates concentration polarization and limits the
challenges for the “hard” solid electrolytes such as ceramics opportunity of Li dendrite formation. However, in reality,
and glasses. In particular, the applications in emerging flexible there is always a significant compromise in both ion
electronics could benefit from this merit of SPEs, and film conductivity and polymer flexibility once the anions are
casting,129−131 UV curing,132 among other high-throughout immobilized onto polymeric chains via a covalent bond.146 To
economical techniques have been well investigated for resolve this compromise, liquid electrolytes have been
diversified classes of SPEs. However, the conductivity of embedded into single-ion-conducting polymers in a close
SPEs has always been the constraint,133,134 while the claimed simulation of fuel cell polyelectrolytes plasticized by water. Oh
safety advantage also becomes less significant due to the et al. described such a class of single-ion electrolytes based on
flammability of typical polyethers. In a sense, SPEs and GPEs aromatic poly(arylene ether)s with pendant lithium perfluor-
can be considered as a compromise between true liquid and oethyl sulfonates. This microporous polyelectrolyte, after being
true solid electrolytes, where conductivity and safety are often saturated with liquid electrolytes, exhibits a nearly unity t+
traded for cost, interfacial, and manufacturing benefits. along with high conductivities (>10−4 S/cm) even at low
There is a well-established correlation between the temperatures.147 According to Archer and co-workers, a high t+
amorphous phases of the polyethers and the conductivity of constitutes a key control over the reversible deposition and
the resultant electrolyte.115,137,138 Despite sporadic re- stripping of the Li-metal anode.148−150
ports,139,140 the crystalline domains in polyethers are known Given the instability of ether linkages at high potential, SPEs
to block Li+ transport.128,141 To minimize crystalline domains, usually cannot support cathode materials that operates at >4.0
inorganic nanoparticles such as TiO2 and Al2O3 have been V vs Li; thus, the most popular cathode chemistries (LCO,
used to kinetically inhibit the crystallization of ether linkages in NMC, and LMNO) are all excluded.151 Efforts were made to
SPEs.142 Since these nanoparticles are not intrinsically ionic circumvent this issue using a dual-layer SPE,127 where a
conductors, their benefits are limited. Accordingly, various polymer material of high anodic stability (polyamide based) is
approaches were adopted to improve the conductivity of SPEs, in contact with the cathode, allowing for a 4 V class cathode to
including blending with ceramic SSEs particles (Figure 14a). In be used, while ether-based SPE is interfaced with the anode
this manner, the nanoparticle can serve the dual purpose of (Figure 14b).127 The overall ion conductivity is now defined
hindering polymer crystallization while providing fast Li+- by the less conducting polymer here, i.e., <10−5 S/cm of
conducting pathways. Conductivities of up to 2.6 × 10−4 S polyamide at room temperature, if no additional interfacial
cm−1 at 55 °C were reported along with better thermal resistance arises from the junction of the two polymers. SPEs
stability.135,143 were also applied as artificial SEI over Li metal,136 as
In an alternative approach, Aetukuri et al. believed that exemplified by poly(vinylsulfonyl fluoride-ran-2-vinyl-1,3-diox-
simply blending ceramic solid electrolyte in a polymer matrix olane) blended with LiF and graphene oxide (Figure 14c).
actually did not fully leverage the high conductivity of the Such thin artificial SEI was key in achieving lean electrolyte
former because these particles are eventually embedded in the conditions ideal for high energy density cells, where a NMC
less conductive polymer matrix without forming an independ- 532 cathode charged to 4 V can cycle over 200 cycles with just
ent percolating pathway for Li+ transport.144 Leveraging a 7 μL mA h−1 electrolyte loading. Instead of relying on the in
casting−etching technique extensively used in semiconductor situ decompositions of liquid electrolyte and additives to form
and electronics fabrications to composite polymer−ceramic SEI,152−154 this approach successfully decouples the irrever-
electrolyte they were able to form a single solid electrolyte sible consumption of electrolyte during cycling from the
layer consisting of ceramic particles whose size dispersion is consumption needed for SEI formation on Li metal.
well within the narrow range of ±15 nm. These particles are The self-healing nature of certain polymers was also explored
firmly embedded in a polymer matrix with their top and to mitigate or even repair the mechanical failures that often
bottom surfaces exposed so that a direct ionic pathway is occur with electrodes during long-term cycling. This concept
established without going through the polymer matrix (Figure was initially applied by Wang et al. as a binder material, not
15). Such one-particle thin membrane (<100 μm) is a flexible electrolyte, on an alloy-type electrode (micrometer-sized Si
polymer−inorganic composite electrolyte that not only offers particles) that experiences tremendous volume changes.155
excellent ion conductivity and mechanical strength but also The design was quickly extended to electrolytes, where both
proved to be rather effective in suppressing Li dendrite. The reversible hydrogen and chemical bonding were designed into
latter benefit comes from the fact that the “soft” part (the polymer structures to enable mechanical stability156,157 with
polymer) is nearly insulating toward Li+ conduction. varying degrees of success in both interfacial stability with
Nanotechnology was also applied to address the con- electrodes and capability of self-healing at the system level
ductivity challenges, among which one particular innovation under cutting damage.
was reported by Wan et al., who created a polymer−polymer Aside from their own chemical and electrochemical
hybrid145 in which an 8.6-μm-thick nanoporous polyimide film properties as electrolytes, polymers were also used as structural
with vertically aligned channels was filled with SPE consisting platforms to support certain desired functions. One con-
of LiTFSI dissolved in PEO. A surprisingly high conductivity spicuous example is a core−shell microfiber separator
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consisting of PVdF-HFP, which encapsulated an effective targeted stabilization of the Li-metal anode surface, most of
flame-retardant triphenylphosphate (TPP),158 which would be which were reported by Archer and co-workers. These include
released into the battery upon thermal runaway to suppress excessive lithium halide salts suspended in nonaqueous
combustion. Here, the encapsulation is necessary to physically electrolytes,171 ionic liquids tethered to the surface of inorganic
isolate TPP from the functional electrolyte because TPP is particles,148,149,172 anions immobilized on nanoparticles that
known to induce unfavorable effects on battery performance. are dispersed in liquid electrolytes,150 or liquid electrolytes
Similar examples also include the thermal-responsive polymers, infused into composites of inorganic and polymers.173
which would undergo reversible phase separation/phase Improvements of varying degrees of success were reported in
transitions upon temperature hiking and consequently become the Li-metal cycling stability, with rationales based on the
insulators, so that a shut-down mechanism is provided.159−161 surface energy of the electrolyte/Li interface. More recently,
Of course, whether these novel concepts could work depend the concepts evolved and extended to many other inorganic
on the chemistries of the batteries as well as the thermal particles of meso-, nano-, or hierarchical structures, including
runaway condition. If the release or shutdown mechanisms oxides such as Al2O3, SiO2, ZrO2, and CeO2174−176 or even
cannot happen fast enough to decrease the rate of heat metal−organic frameworks (MOFs).177−181 Generally, the
propagation within the battery, catastrophic failure would still liquid electrolytes were thought to be trapped via either
occur. To address this critical temporal requirement, Chen et physical (noncovalent) forces or chemical interactions in the
al. developed a fast and reversible thermoresponsive polymer meso- or nanopores of these inorganic scaffolds with benefits
switch consisting of electrochemically stable graphene-coated such as decent ion conductivities (>1.0 mS/cm), improved Li+
spiky nickel nanoparticles embedded in a polymer matrix of transference numbers (∼0.6), or additional capability to
high thermal expansion coefficient. The composite polymer suppress Li-metal dendrites. In particular, Archer and co-
has an electronic conductivity of 50 S cm−1 at room workers described a so-called ionic rectifier where a liquid
temperature (hence, no longer an electrolyte by a strict electrolyte physically constrained in the narrow pores of α-
definition), which can decrease within 1 s by 7 or 8 orders of Al2O3 demonstrates nearly unity Li+ transference numbers due
magnitude upon temperature hike162 and allows for rapid to the blocking of anion transport by the pore wall that bears
shutdown in the case of accidental thermal runaway. the same charge.182
New manufacturing technologies were also used to pattern While the semisolid electrolyte approaches present them-
or etch polymer electrolytes or polymer-based separators for selves as a new class of promising materials for next-generation
various merits, leveraging the mature techniques in semi- battery chemistry, with high Li+ transference numbers as the
conductor and electronic industries, such as photopatterning main attraction, most of the materials still need to be
or lithography,163,164 or emerging 3D-printing technolo- rigorously characterized under electrochemical conditions
gies.165,166 Such approaches are regarded as highly valuable close to the real battery environment. In particular, their
in enabling 3D microbatteries directly on chips with fabricating stability against the high-capacity and high-voltage cathode
modulable arrays. chemistries remains to be manifested.
3.2. Liquid Inorganic Hybrids 4. SOLID IONIC CONDUCTORS
In 2004 a new class of hybrid electrolyte was created by Maier Although liquid electrolytes are the most prevalent due to the
and co-workers, who named it soggy-sand electrolyte, that simplicity of their interfaces with solid electrodes, it has been a
bridges conventional liquids with solids.167 This hybridization decade-long dream to solidify the electrolytes in view of the
strategy aims at combining the liquid-like fast ion transport potential benefits in terms of device robustness, volumetric
from conventional liquid electrolyte with the dimensional compactness, and safety. Immense attention has been drawn to
stability and high modulus of an inorganic solid framework, solid-state electrolytes (SSE). This is especially true after a
which is often based on nanosized inorganic particles such as series of high-profile fire hazards caused by the thermal
silicate, alumina, or even various ceramic electrolytes.168,169 runaway of LIBs, which, as an inevitable result of the extensive
Thus, the solid could be either an ion conductor itself or a application of LIBs in our daily life, should be attributed at
completely inert structural scaffold. These oxide solids often least in part to the nonaqueous electrolytes used therein. Many
serve as a preferential adsorption surface for the salt anions; new or near-commercialization battery chemistries can benefit
hence, the Li salts dissolved in the liquid phase would be from the use of SSE;183 for example, the well-known
further dissociated, rendering the Li+ more mobile than the polysulfide shuttle effect of the LSB could be circumvented
anions. The actual ion transport process in such hybrid or the persistent growth of Li dendrite could be suppressed if a
electrolytes is much more complicated, which involves surface solid-state electrolyte serves as the ionic conductor and
energy, space charge, and surface functionalities of the oxide physical barrier between the electrodes.184,185 To date, there
particles. The eventual dispersion of the particles in the liquid have been quite a few major advances within the field of
phase forms a fractal percolating network to accelerate the inorganic SSE: the garnet-type, antiperovskite-type, and
ionic transport. Such dispersion of nanoparticles in the liquid sulfide-type systems, each of which possesses its own
phase is not spatially immobilized; therefore, gravitational advantages and disadvantages. If these solid-state battery
precipitation could occur once the equilibrium is breached, systems can achieve their promises, higher energy density
putting an end to the ion transport network. Introduction of materials such as a Li anode, sulfur cathode, or oxygen/air
the proper fraction of inorganic solids into liquid electrolytes cathode become practically accessible. Furthermore, in the
usually induces a spike in ion conductivities, which could be absence of percolating liquid, solid-state batteries are not
improved as much as five times, in addition to improved Li+ susceptible to ionic short circuits and can be assembled into
transference number.170 higher voltage battery stacks without other external physical
Inspired by the soggy-sand concept, there have been separation between each cell.186 This allows for a significant
numerous variations of liquid inorganic hybrids that specifically reduction in the dead weight of packaging material and
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subsequently realizes a higher energy density at the device an appreciable interphase. Type II involves electrolyte
level. With the potential benefits in safety and energy density, decomposition products that are electrically conductive,
practical application of SSE in batteries, especially when the resulting in continuous decomposition of SSE. Type III occurs
aggressive Li-metal anode is involved, still faces ques- when the SSE is susceptible to decomposition against the
tions.187,188 electrode but will passivate electrically, in close resemblance to
Many of the key problems associated with SSE electrolytes the SEI that supports the operation of LIBs in liquid
still stem from the instability of the electrolyte materials against electrolytes. Besides those, we believe that Type IV might
the harsh reductive and oxidative environment provided by the also exist, where the SSE will decompose but the produced
anode and cathode, respectively. This can cause cell impedance interface between the SSE and the electrode either cannot or
to increase, loss of mechanical integrity, and promotion of only poorly conducts both electrons and ions. A Type IV
dendrite formation, leading to the eventual inability of the cell scenario will only propagate if Li plating/dendrites occurs,
to function. Decomposition of both garnet- and sulfide-based which induces decomposition of the STSSE upon exposure to
electrolytes has been well reported with both experimental and fresh Li. Obviously Type I interfaces are ideal but nearly
theoretical works.189−193 As shown by the theoretical impossible, while neither a Type II nor a Type IV interface is
calculation of the thermodynamic stability limits for these desired as they tend to build impedance. Unfortunately, these
SSEs (Figure 16),192 most will be either reduced by the anode types are also most commonly encountered. Hence, Type III
has been the direction of research for a large majority of
researchers.196,197
Furthermore, while it has been accepted that SSE can likely
enable the Li-metal anode, dendrite growth is still identified in
SSE from time to time. In contrast to its relatively free growth
in liquid electrolyte, Li dendrites grow exclusively through the
interconnect pores and grain boundaries of the SSE.198
Because dendrite growth begins with a depletion of Li-ion
concentration, it is to be expected that the relatively slower Li-
ion conductivity of some solid electrolyte materials will
promote the growth of dendrites. However, the dendrite
growth likely only follow the diffusion-controlled mode of
growth. This is in contrast to the mossy and diffusion-
controlled modes of liquid electrolyte systems.199 Since liquid
electrolyte can ensure good contact with newly formed Li
metal, mossy dendrite can be grown, which leads to constant
impedance build up. In the case of solid electrolyte, it is
expected that the contact between newly formed Li will not
have sufficient contact with the SSE to form mossy dendrites.
Instead, SSE are more prone to decomposition via either a
Type II or a Type IV interface, which will increase impedance.
When combined with the typically lower conductivity (as a
result of both bulk SSE ionic conductivity and interface
resistance between active material and SSE), it can be expected
that formation of a dendrite even at seemingly low current
densities will occur. However, under short-circuit conditions, it
is expected that SSE will be safer compared to the highly
flammable liquid electrolyte counterpart. As each different type
of SSE has different characteristics, we will now review some of
the leading SSE materials and strategies to increase their
overall performance.
4.1. Garnet-Type Solid-State Electrolytes
Garnet-type SSEs (GTSSE) are typically in the form of
Li7La3Zr2O12 (LLZO) and differ between one another mostly
Figure 16. Calculated theoretical thermodynamic voltage stability
windows of popular garnet-, antiperovskite-, and sulfide-type solid- from the addition of various metal dopants such as Ti4+ 200and
state electrolyte material. Reprinted with permission from ref 192. Ga3+.201 In contrast to the other popular type of SSE (sulfide-
Copyright 2016 American Chemical Society. type, following section), GTSSEs are significantly more stable
in both operating and ambient conditions. In this sense,
GTSSEs are more attractive in terms of processability. In fact,
or oxidized by the cathode at their typical operating potentials, the arguably most advantageous aspect of GTSSEs is their
while the specific chemistry and nature of the interphases vary stability against decomposition when paired with both the
with both SSE and electrode materials. The nature of how SSE cathode and the anode202 and is technically a Type I SSE
interfaces with electrode materials directly dictates the against Li metal.191 However, at higher voltages (such as in the
performance of the solid-state batteries with three possible case of LIB oxide-based cathodes) it will still decompose. On
scenarios.194,195 Type I involves electrolyte materials that are the other hand, GTSSEs typically lack in performance due to
inherently stable against the active material and will not form their comparatively lower Li-ion conductivity versus sulfide-
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Figure 17. SEM of the interface between Li and LLZO ((inset) optical image of molten Li in contact with LLZO) (a) without and (b) with the
Al2O3 layer. Reprinted with permission from ref 218. Copyright 2017 Springer Nature. (c) Schematic illustration of utilizing nanosized Li4Ti5O12 to
achieve a good interface layer with the Al-doped LLZO. Reprinted with permission from ref 219. Copyright 2016 Wiley VCH.

based SSEs.203The highest Li-ion conducting phase, the cubic interface severely hinders the Li-ion conduction. It was found
phase, is difficult to achieve without additives204,205 as it is still that precoating LLZO with a layer of Nb metal limited this
somewhat unstable in ambient conditions. Moisture can mutual diffusion of cation between LLZO and LiCoO2.215 An
exchange the Li ion with a proton, which has been shown alternate strategy reacted Li3BO3 with Li2CO3 to form a layer
even in the bulk structure.206,207 This can lead to the formation of Li3.3B0.7C0.3O3. This conductive layer was used to “solder”
of LiOH layers and in turn form Li2CO3, both of which are LiCoO2 with LLZO with significant enhancements in perform-
passivating to ions.208 However, it has been shown that ance.216 Another work paired the LLZO/LiNi0.6Mn0.2Co0.2O2
nanonization of the LLZO particle can increase both air (NMC-622) system with Li3BO3 as the artificial interface layer.
stability209 and the total area of the grain boundary and thus It was found the volume change experienced by NMC-622
enhanced the transport of Li ion.210,211 Compounding with the caused significant decay in the performance if its particles size
stability concerns of LLZO is the high sintering temperature is large. In contrast, when smaller particles were used, the
required for its synthesis, which will likely contribute to an mechanical deterioration slowed.217
increased manufacturing cost when compared to the sulfide- As Li metal is one of the most attractive anodes for solid-
based SSEs. Temperatures of up to 1230 °C are often required state batteries, the stability of LLZO against the metallic anode
to synthesize the cubic LLZO. Although doping of various is of upmost importance. While the stability of LLZO against
metal elements (W, Ta, Nb, etc.) has been suggested to help, it Li is still uncertain due to their rather close redox potentials,191
only decreased the temperature to around 1000 °C.212 convincing evidence has been found that supports formation of
A contact issue between LLZO and electrode material at least a so-called oxygen-deficient interphase (ODI) between
typically requires some form of a cosintering process to achieve deposited Li and mechanically polished LLZO.220 This ODI
intimate contact. In terms of the cathode, depositing the model layer is said to be formed via elimination of oxygen by reaction
GTSSE (LLZO) with the common cathode material LiCoO2 with Li, which is then charge compensated by the reduction of
facilitates the diffusion of Co from the LiCoO2 to the LLZO Zr4+ in LLZO. By changing the dopant, the composition and
and the diffusion of La and Zr from LLZO to LiCoO2. This the property of the ODI changes. Ta as dopant exhibited
occurs when depositing a thin film of LiCoO2 onto LLZO at decreased ODI formation compared to Nb and Al. Al exhibited
around 700 °C.213 In a similar study, more pronounced effects the highest degree of ODI formation out of the three, that is
were found for other common cathodes such as LiMn2O4 the severity of ODI formation has the following trend: Al > Nb
(LMO), LiFePO4 (LFP), and LiNi0.33Co0.33Mn0.33O2 (NMC- > Ta. However, the resistance of this layer was similar between
111), which is rather unfortunate as these are the more the Al-doped and the Ta-doped LLZO. It was found that the
technologically viable cathodes for electric vehicle applica- surface segregation of Nb resulted in the increased impedance
tions.214 For the Ta-doped LLZO (Li6.75La3Zr1.75Ta0.25O12), a of the Nb-doped LLZO.220 Accordingly, the existence of an
reaction was found at 500 °C when sintered with LMO and ODI does not automatically indicate poor ion conduction as
LFP, while a reaction was observed at 700 °C for LCO and other factors and phenomena can occur. In this case, Ta
NMC-111. This exchange of cations at the LLZO and cathode dopants have a similar energy state when in the bulk or at the
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interface which is in contrast to Nb, which was much more anion in the middle.228 This type of SSE typically possesses
stable when segregated to the surface of LLZO. LLZO with comparatively higher ionic conductivity, synthesized at a lower
decreased amounts of Li2CO3 contaminants (from mechanical temperature, and has a lower melting point than the GTSSE.
polishing) possessed an increased level of reduction with Li ApTSSE or specifically the Li3OCl is also thermodynamically
metal.220 predicted to be stable against Li metal as shown in Figure
Another problem of LLZO is the lack of wettability with Li 16.192 Furthermore, the lower melting point will help in
metal.221 Accordingly, one of the major recent advances in reducing grain boundaries during synthesis. Taken together,
GTSSE research is the development of artificial coating layers these properties are highly attractive for solid-state battery
over SSEs. Bare GTSSE has very poor wettability with molten applications. Unfortunately, Li3OCl was also calculated by
Li (as shown in Figure 17a), and it is also difficult to achieve a DFT to be unstable in ambient conditions and will decompose
smooth polish to produce intimate contact with electrodes.222 into Li2O and LiCl at room temperature.229 This is similar to
As shown in Figure 17a, without any modifications, there exists the sulfide-type SSEs; ApTSSE materials are rather hydro-
a large contact void between Li and the LLZO. Work by Han scopic and will absorb water from the ambient atmosphere,
et al. demonstrated a significant decrease in the interfacial altering their conductivity at different degrees of hydra-
impedance (from 1710 to 1 Ω cm−2) by introducing an atomic tion.230,231 Interestingly, increased conductivity was found for
layer-deposited Al2O3 coating.218 This layer allowed for the samples that were allowed to absorb moisture from the air.232
wetting of LLZO with molten Li (inset of Figure 17b). Moreover, the degree to which this material absorbs water has
Accordingly, no appreciable void space is found at the Li and created confusion throughout the literature regarding the form
LLZO interface from scanning electron microscopy. In another of the ApTSSE.233,234 Besides ambient decomposition, at
work, Li3N is also used to enhance wettability toward Li with higher voltages (>3 V as shown in Figure 16192), Li3OCl is also
corresponding increases in conductivity and cycling stabil- predicted to decompose at >2.5 V into Li2O2 and LiClO4.229
ity.223 These provide a method to smoothen the Livtransport Another very similar ApTSSE, lithium halide hydroxide, or
pathway from Li metal to the SSE in addition to acting as a Li2OHX has become very popular in the literature in recent
protective layer for the SSE against decomposition.224 Other years. The synthesis conditions of Li2OHX become even more
anodes such as Li4Ti5O12 (LTO) also required interface challenging due to the material’s tendency to strip metal ion
engineering. As shown in Figure 17c, using nanosized LTO, from reaction vessels,231,233,235 furthering the confusion in the
the authors were able to achieve good contact with an Al- literature by changing the ionic conductivity of the material in
doped LLZO via a layer where the SSE and LTO are mixed an uncontrolled way. It was suggested that a standard method
together before reaching the bulk LTO phase. Similar should be employed to clarify the composition and structure of
corresponding increases in Li-ion conductivity were also every tested ApTSSE. This method consisted of a combination
reported.219 of 1H nuclear magnetic resonance (NMR), energy-dispersive
Beyond achieving good contact between Li and the GTSSE, spectroscopy (EDS), time-of-flight secondary ion mass spec-
Li dendrites have become one of the key hurdles for GTSSE. troscopy (TOF-SIMS), X-ray photoelectron spectroscopy
Limiting Li dendrites required modifications to the grain (XPS), and in situ temperature-dependent X-ray diffraction.234
boundaries and pore structure.198 It was found that the Each technique was used to carefully characterize the ApTSSE
commonly considered undesirable Li2CO3 and LiOH by- to identify any contamination. Furthermore, the coin cell used
products of LLZO synthesis are actually useful when placed at for electrochemical testing was weighed before and after testing
the grain boundaries.225 As Li dendrite growth tends to travel to ensure no mass was gained from leakage. Only in this way
along the grain boundary and pore network, these electron and
can the source of performance enhancement be reliably
ion insulating materials can serve to directly limit the
identified and further studied.
propagation of Li dendrites when formed at the right spots.
The main benefit of the Li2OHX class of materials is their
Another group demonstrated that by controlling the micro-
relatively higher conductivity compared to Li2OCl. Only
structure of the 0.8 Ta−LLZO pellet dendrites can be
recently was the addition of proton into the Li2OX
eliminated.226 The authors obtained 0.8 Ta−LLZO with
convincingly proved to be beneficial for Li-ion conduction
small grain size by restricting the rapid crystal growth portion
by Song et al.234 It was discovered that there is likely to be a
of the sintering process, creating a pellet with a relative density
rotating motion of the OH− groups. This creates a Frenkel
of ∼96.2%. With smaller grain size, the chance of a connected
defect, which creates a more dynamic space for Li-ion
pore network is decreased in addition to increased pore
tortuosity. Taken together, these factors resulted in GTSSE transport.234 An analogy was drawn between Li-ion transport
that resisted short circuit at 0.5 mA cm−2 for more than 8 h. through the rotating OH− and a revolving door of a building. It
Moreover, in addition to facilitating dendrite formation, the was also understood that the proton can block the Li-ion
existence of a connected pore network can also severely hinder conduction by sterically and Coulombically limiting the Li ion
the total ionic conductivity of the GTSSE.227 In contrast to from transporting through the oxygen sites.230 Substitution of
liquid systems, creation of a network that is tortuous for Li the OH− groups with fluorine (i.e., reducing proton levels) was
dendrite growth is not intrinsically coupled with a network that found to increase the Li-ion conductivity in addition to
is also Li-ion tortuous. This is a key difference that can be increasing the voltage stability.232 The fluorine ion can pull the
leveraged in solid-state configurations. proton away from the Li-ion conducting oxygen sites. Further
modifications led to the Li3−2xMxOCl, where M is a higher
4.2. Antiperovskite-Type Solid-State Electrolytes valent cation: Ca2+, Mg2+, and Ba2+. This type of composition
Li-rich antiperovskite-type SSEs (ApTSSEs) usually contain was reported to have an exceptionally high Li-ion conductivity
oxygen and a halide as the anions in the form of Li3OX (X = of up to 25 mS cm−1 at 25 °C.236 It is interesting that at
Cl, Br, etc.) with a similar but inverted ABO3 cubic, Pm-3m elevated temperatures good cycle performance was shown even
perovskite structure. A 3D framework is formed with the halide with molten Li with Li3OHCl-based solid electrolyte.233 A
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Figure 18. Oxygen analog with some corresponding conductivity values of LISION and thio-LISICON solid electrolyte material. Reprinted with
permission from ref 238. Copyright 2001 Electrochemical Society.

Figure 19. (a) Conductivity versus temperature of various P-, S-, and Ge-based STSSE. (b) Large irreversible capacity due to interfacial reactions.
Reprinted with permission from ref 186. Copyright 2016 Springer Nature.

dense SEI layer was formed and appeared to remain stable (did based LISICON or STSSE consistently possesses significantly
not continue to grow) after 40 cycles. higher conductivities due to the more polarizable electron
To the best of our knowledge, there have not been any cloud of sulfur. In fact, STSSEs are among the highest Li-ion
reports of Li dendrites occurring in an ApTSSEs. However, this conducting solid systems with the Li7P3S11 and the Li10GeP2S12
could simply be an indication of the lack of any serious (LGPS) possessing conductivities of 1.7 × 10−2 239 and 1.2 mS
attempts to study dendrite characteristics (formation/mecha- cm−1,240 respectively, well into the realm of liquid systems.
nism) regarding this type of SSE. Interestingly, no dendrite was Accordingly, STSSEs have become a very popular and
found in an ApTSSE-based cell at 0.1 mA cm−2 for 20 min. promising class of contemporary SSEs. Various dopants have
This is likely due to the low current density and areal been applied to tune the electrochemical properties of STSSEs
capacity.237 Due to the relatively new nature of ApTSSE, it is to further enhance performance.
understandable that pure bulk ionic conductivity has continued Cation substitution in the form of Ge into the more
to receive attention from interested researchers. However, if traditional/baseline composition of Li3PS4 (LPS) has offered
dendrites were to form and short circuits the cell, hydrogen gas significant improvements in conductivity. Similar results were
evolution might occur for the Li2OHX composition if the obtained with Si and Sn.241 However, upon decomposition via
temperature is elevated.233 lithiation, this type of STSSE will form conductive lithiated
phases such as Li−Ge, Li−Si, and Li−Sn which are Type II
4.3. Sulfide-Type Solid-State Electrolytes
decomposition interfaces, i.e., not desirable. On the other
Sulfide-type SSEs (STSSE) stemmed from the original hand, a boost in Li-ion conductivity was also obtained from
LISICON structure composed of various cations paired with anion substitution, making the Argyrodite-type LPS in the
oxygen. Compared to oxygen analogs (Figure 18238), the thio- form of Li6PS5X (X = I, Br, Cl).242 Li6PS5Cl was shown to have
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higher stability against complete delithiation in the cathodic LiPF6 in fluorinated-EC/DMC liquid electrolyte systems, a Li-
region but very poor anodic stability against metal oxide-based metal anode was found to maintain stable cycling even at 2 mA
cathodes.243,244 More recently, discovery of the highly cm−2 over hundreds of hours.259 In contrast, efforts to limit
defective Li1+2xZn1−xPS4 at x ≥ 0.5 has a computationally dendrite formation in STSSE in the form hot-pressing Li3PS4
predicted conductivity of more than 50 mS cm−1 at room at 170−250 °C was found to exhibit enhanced critical short-
temperature.245 However, experimental results have only circuit current densities to only 1 mA cm−2.258 Like the
achieved 0.8 mS cm−1, which is still exceptionally high.246,247 GTSSE, the microstructure of STSSE played a key role in
Alternatively, the Li7P2.9Mn0.1S10.7I0.3 composition exhibited an extending the onset of Li dendrite. The authors suggested that
extremely high ionic conductivity of 5.6 mS cm−1 at room the hot-pressing process enhanced the conductivity by creating
temperature, whereas the Li9.54Si1.74P1.44S11.7Cl0.3 composition a thio-LISICON III analog. However, the pressure experienced
demonstrated even higher Li-ion conductivity of up to 25 mS by the STSSE from cold pressing likely reduced the bulk pore
cm−1 at room temperature, significantly higher than the volume and as such the percolating pore structures.
conventional Li10GeP2S12 (as shown in Figure 19a).186 Synthesis techniques of STSSE have developed from solid−
Unfortunately, a large interface resistance was generated solid mechanical mixing to an organic solvent-based precip-
from the poor contact between Li9.54Si1.74P1.44S11.7Cl0.3 and itation technique that produces higher conductivity through
the electrode active material. This is further amplified by the nanostructuring.242,260,261 In fact, solution-based synthesis
instability of this material and its decomposition into a Type techniques are preferable from a production standpoint due
IV interface (both ionically and electronically insulating). In to low temperature and ease of mixing.262 Furthermore, the
contrast, the Li9.6P3S12 composition exhibited a high anodic possibility of controlled precipitation onto the surface of the
stability (as shown in Figure 19b) but with decreased the Li- active anode/cathode material will be useful to ensure intimate
ion conductivity (about 1 mS cm−1). interfacial contact. As solid−liquid mixing can facilitate a much
Like LLZO, a space charge layer, is formed when sulfide more homogeneous final STSSE/active material distribution,
electrodes are in contact with high-voltage LiCoO2.248 To
STSSEs that are soluble in organic solvent. Furthermore, the
tackle this problem, many researchers have developed coatings
contact between the different materials will also likely be
to buffer the space charge layer. Li4Ti5O12 (LTO) was an early
enhanced. Since Li3PS4 is often synthesized by means of
interposing coating layer used to cover the surface of
evaporating a solution of P2S5 and Li2S in various organic
LiCoO2.249 However, it was found that if the LTO was too
uniform, a significant amount of resistance stemming from the solvents,260,263 it can be a perfect candidate for this type of
LTO itself would begin to surface. Later work was conducted solid-state battery manufacturing method.264 This strategy is
on coating materials that were ionically conductive materials also taken advantage of in the ApTSSE where pulsed laser
even in the amorphous state. Specifically, LiNbO3 (a relatively deposition (PLD) was employed to deposit crystalline layers of
high Li-ion conductivity material250) was used as a coating Li3OCl over electrode materials.265 On top of the problem of
over LiCoO2 to enable a STSSE-based LiCoO2 solid-state the contact of STSE, sulfide-based systems are highly reactive
cell.251 Formation of a Type IV, i.e., a Li2S- and Li3P-based to moisture and oxygen. Not only will decomposition occur
interface with no electronic and little ionic conductivity, but also the formed products are typically a poisonous gas,
promotes the formation of Li dendrite due to the poor Li-ion making it impossible to process in ambient conditions due to
transfer. Accordingly, one group investigated the trans- both safety and technical concerns.264 Much effort has been
formation of the Type IV interface to Type III, that is, from placed in searching for alternative STSSEs that possess high Li-
a poorly electron and Li-ion conducting interface to an ion conductivity but increased chemical and interface stability.
interface with only good Li-ion conduction. Through the The phosphorus present in typical STSEEs is highly reactive to
incorporation of LiI into the composition of the electrolyte, the oxygen species in ambient air. Sn substitution was found to
significant enhancements were obtained in the critical short- improve the air stability due to its relative softness (acid) in
circuit density.252 The group achieved a 3.9 mA cm−2 critical comparison to the hard acid compatibility of O and P.266
current density at 100 °C with 30 mol % LiI. With the addition 4.4. Beta-Alumina
of I into the STSSE, LiI was formed as one of the reduction
decomposition products at the interface with Li metal. The Beta-alumina (β-Al2O3) has traditionally been employed as a
authors claimed that the LiI created an interface with increased high-temperature solid electrolyte. However, there have been
Li-ion conductivity, effectively transforming Type IV toward recent reports on near-room- to room-temperature operation
Type III. However, it should be noted that the inherent bulk of β-Al2O3 with exceptionally high ionic conductivities.267,268
conductivity of a LiI-doped Li3PS4 STSSE is also higher, which This is particularly exciting because β-Al2O3 (specifically Na
could convolute the observed enhancement in perform- doped) has been established as a rather stable electrolyte
ance.253,254 It should be further noted that the conductivity against Na metal anode in early work on high-temperature
of pure LiI is <10−7 S cm−1, which is unlikely to significantly sodium−sulfur batteries.269,270 At room temperature, Na-β-
shift the Type IV interface to Type III.255 Regardless of the Al2O3 can be tailored to achieve a low interfacial resistance
true reason for the observed enhanced performance, the with the Na metal. This technique increases the critical current
concept of transforming Type IV interfaces to Type III density of short circuit to 12 mA cm−2. Under a high stack
interfaces by tuning the decomposition products of the STSSE pressure, the conductivity and subsequently the cyclable
is clear. current density of Na-β-Al2O3 can also be drastically
The dendritic growth of Li metal has been reported to increased.271 This was revealed to be the effect of simply
propagate along the grain boundaries and throughout the pore suppressing void formation over cycling the Na metal.
network inside of the STSSE layer.256−258 In fact, dendrites in Apparently, the benefit of Na-β-Al2O3 for Na-based systems
STSSE have been found to be more apparent than liquid has been neglected over the years in comparison to other more
electrolyte systems in certain situations. For example, in 1 M commonly discussed solid electrolyte materials. It is expected
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that future work will place a much heavier emphasis toward β-

Al2O3-based materials.
4.5. First-Principles Calculation-Driven Design
Theoretical studies offer immense insight into the operating
principles of SSEs. The ion transport mechanism272−278 in
addition to the mechanical properties272 (softness to
accommodate cathode/anode expansion) have been thor-
oughly investigated throughout the literature. The decom-
position of SSE over the surface of the cathode or anode is
particularly difficult to monitor and is highly specific to the
system and mixture due to the kinetically limited nature of the
process. As such, theoretical studies can provide a worst-case
scenario of the thermodynamic stability limit of the SSE
material.272 Many recent works have focused on drawing
electrochemical stability windows of various types of
SSEs191,195and predicting the reactions occurring at the
interface of the SSE and the active material.272,279 More
detailed work on the mechanism of the Li3PS4/FePO4 interface
has been conducted based on functional molecular dynamic
simulations.280 It was concluded that a Li-depleted layer
around the sulfide interfaces is formed during delithiation of
the cathode. Without charge carriers present in this layer
(Type IV interface), Li-ion conduction is severely reduced.
With the growth in computational power, the use of data
mining coupled with neural network optimizations (i.e.,
machine learning)281 have begun to play a growing role in
the field of material science.282,283 Accordingly, application of Figure 20. Energy barrier (eV) versus volume per S atom (Å3) of
calculation-driven designs for SSE have also gained traction in computed (lines) and experimentally reported data. Reprinted with
recent years. Researchers have begun to develop computer permission from ref 273. Copyright 2015 Springer Nature.
programs with predictive power on the performance of new
materials. For example, work by Chen et al.284 used data To this end, Ceder et al. predicted new metal oxide materials
mining to understand the Li diffusion characteristics of LLZO. in 2010 with a data-mining-driven machine-learning process287
Aykol et al. computationally evaluated 180 combinations of (as shown in Figure 21) along with predicted245 and
Li3X3Y2O12-type GTSSE via high-throughput DFT,285 while experimentally validated Li-ion288 and Na-ion conductors.289
Kim et al. correlated lattice distortions with ion migration Specifically, using calculation-driven design, it was predicted
barriers with stability.286 A particularly critical technique that the LiZnPS4 composition should have outstanding Li-ion
known as the nudged elastic band (NEB) calculation was conduction properties due to its almost perfect bcc S
useful in predicting Li-ion conduction in new proposed lattice.245,273 It is predicted that the highly defective
materials via calculation of the activation barrier of ion transfer Li1+2xZn1−xPS4 at x ≥ 0.5 should have a conductivity of
throughout the material’s structure.273 In fact, it was this more than 50 mS cm−1 at room temperature.245 Interestingly,
computational method that led to the now understood role of corresponding syntheses by external research groups have
the anion arrangement/packing (particularly the body- achieved conductivities of up to 0.8 mS cm−1.246,247 Other
centered cubic, bcc framework) in the resulting Li-ion transfer groups have also successfully leveraged simulation studies to
properties. As shown in Figure 20a, the activation energy of Li- design new ApTSSE materials.290 This was achieved by, first,
ion transport is very low for the bcc S sublattice arrangement. identification of Li3AX (where A = chalcogen and X =
It was further explained that the Li-ion diffusion network halogen) via the universal structure predictor: evolutionary
within the conductor material should contain sites that are xtallography.291 It was found that when the Cl of the Li3OCl
energetically identical to the conduction channels. In other material is substituted by I (increasing the size of the halogen),
words, it is ideal if the space between the atoms has the same moderate increases in lattice parameters are found. This is in
energy levels as that at the original Li-ion sites, offering a contrast to increasing the size of the chalcogenide, where large
completely flat energy landscape, i.e., near-zero activation changes in the lattice parameters along with lattice distortion
energy. This specific criterion for high Li-ion conduction was were observed. Furthermore, the antiperovskite structure is
then used to screen various compounds from a crystal found to collapse if the size of the chalcogenide is increased
diffraction database and yielded only a handful of materials without also replacing the halide. From these simulations, the
that are predicted to exhibit this property (Figure 20b). More antiperovskite Li3SI and Li6OSI3 was discovered. Both of these
impressively, this method correctly predicted Li10GeP2S12, β- phases possess low energy barriers for Li-ion transport.
Li3PS4, and Li7P3S11 among other experimentally validated Calculations have also driven designs of new interfaces to
solid-state materials as Li-ion superconductors. It is expected mitigate the passivation problems of STSSEs.192 Compared to
that future discoveries of new SSE will be guided by the design of an ion conductor, the criteria for an ideal
simulation-based material prediction studies. This is in contrast interface are rather straightforward. The Type III interface is
to the previous expansion of a known superconductor material electron insulating but ionically conductive and is clearly ideal
via mere experimental element substitution. for application. It is therefore a promising direction to design
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possible because the decomposition of water occurs prior to

the decomposition of Na3SbS4, which was thermodynamically
predicted by the authors.224
Overall, it is expected that calculation-driven designs are
likely to play a pivotal role in the future of SSEs. Through the
higher efficiency in identifying new SSEs and predicting
efficacy of different additives, researchers can more selectively
choose their next candidates.

5. REDOX-ACTIVE ELECTROLYTES
Redox-active electrolytes can be classified as a broad range
battery electrolyte that contains species that are the active
redox centers of the battery. This type of electrolyte typically
leads to fundamentally different battery designs that resembled
fuel cells rather than the contemporary LIB technology. The
soluble nature of the redox-active material also leads to higher
reaction kinetics and typically high power densities. Flow
batteries with organic/inorganic anolyte/catholyte in addition
to redoxmers will be briefly discussed in regard to their
advantage and disadvantage and recent breakthroughs in
development.
5.1. Flow Cell Anolytes/Catholytes
With the emergence of stationary energy storage systems in the
form of both consumer and industrial markets, the price of a
battery has become increasingly more important. The common
use of redox-active metal oxides as cathode materials has led to
the price increase of transition metals such as Co and Ni,
restricting the economics of employing LIBs. Furthermore,
LIBs are limited by their power density and energy density,
which are solely based on the predetermined battery capsule
size. In contrast, recent interest into redox flow batteries
(RFB) can utilize much cheaper redox-active compounds.
Furthermore, RFBs have the advantage of decoupling the
reaction sites with the physical storage of cathode and anode
active materials.
Current commercial vanadium flow batteries have a cost that
is much too high due to the price of vanadium (6−22 € kg−1)
in addition to the low cell voltage (1.2−1.8 V) and resulting
energy density (15−30 Wh L−1). We would like to point to
another review article for details on the cost of vanadium
RFBs.293 Various new technologies have been pursued for
redox-flow batteries that incorporate the high design flexibility
of RFB but with reduced price points. RFB can be divided into
organic- and aqueous-based electrolyte systems. Purely
Figure 21. Data-mining-driven compound discovery algorithm. aqueous-based RFB will have lower output voltages and as
Reprinted with permission from ref 287. Copyright 2010 American such typically lower energy and power density. However, a
Chemical Society. water-based electrolyte offers significant advantages in terms of
conveniences and cost. Furthermore, recent work has
solid electrolytes based on their oxidative/reduction decom- demonstrated that by changing the aqueous electrolyte from
position products. As these products are thermodynamically acidic to basic, significant voltage gain was achieved in the form
predicted, Tian et al. looked to leverage the predicted products of a zinc iodide all aqueous RFB with an experimental energy
along with their properties to design appropriate near Type III density of 330.5 Wh L−1 (schematic shown in Figure 22a).294
interfaces.224 The Na3SbS4 composition STSSE is known to Dendrites were observed during the Zn plating cycle, which
decompose into Na2S and Na3Sb when reduced by elemental was mitigated by physically replacing the Zn plate with a fresh
Na (i.e., Na-metal anode).292 Being metallic, Na3Sb renders plate at periodic intervals.295,296 Regardless of the config-
the natural Na3SbS4/Na interface Type II, which is both uration, the use of aqueous electrolytes is inherently limited by
electronically and ionically conductive, leading to constant the narrow voltage window of water.
growth in the interface layer. Accordingly, it is interesting to Organic electrolytes are attractive due to their generally
pursue additional of chemical species that will induce higher voltage windows, allowing an overall higher energy and
formation of Type III interfaces. Tien et al. partially hydrated power output of the flow battery. Furthermore, the large
Na3SbS4 to Na3SBS4·6H2O to enable formation of a stable variety of organic redox-active molecules can be leveraged to
interface containing Na2O and NaH.224 This was made formulate an ideal catholyte/anolyte pair.299 However,
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Figure 22. (a) Schematic of a zinc−iodide flow battery. Reprinted with permission from ref 294. Copyright 2018 Royal Society of Chemistry. (b)
Schematic of the Na ion. Reprinted with permission from ref 297. Copyright 2018 Elsevier.

compared to the high solvating power of water, organic

electrolytes will typically only solvate redox-active species at
concentrations below 1 M.298 Researchers began to look into
aqueous/organic hybrid electrolytes where the catholyte is an
aqueous alkali-ion redox-active anion and the anode is a Li-
metal300 or Na-metal anode297 in organic electrolyte. The two
electrodes are separated by a solid ceramic electrolyte (such as
NASICON301) to prevent reaction between the alkali metal
and water as shown in Figure 22b (Na based).302 With the use
of an alkali metal, a second anolyte electrolyte tank is no longer
needed. As such, the energy density will undoubtedly increase.
However, other problems such as dendritic alkali-metal growth
coupled with anode corrosion (impedance build up) could
severely reduce the cycle life. In contrast to the Zn-metal
anode-based flow batteries where the Zn anode can be easily
physically replaced,295,296 the logistics of replacing an air-
sensitive Li- or Na-metal anode will be very challenging.
Furthermore, decomposition of organic electrolyte (unstable
SEI) on the surface of the alkali metal will also be much more
expensive to refresh compared to aqueous systems. Moreover,
even the high cost of the alkali metal itself will inevitably play a
significant role during the cost analysis of these systems.303
There are also inherent scalability issues with organic
Figure 23. (a) Schematic of a semisolid redox flow battery. (b)
electrolyte such as contamination with water leading to higher Operation reaction scheme of a semisolid redox flow battery.
price points. A very recent study on sulfur-based systems in the Reprinted with permission from ref 298. Copyright 2015 AAAS.
form of an organic electrolyte polysulfide flow battery304,305
and aqueous sulfur/oxygen redox pair RFB306 is especially targeting,313 Jia et al. incorporated the use of organic redox
attractive due to the low cost of S. However, like all redox mediators and static Li-ion storage particles. As shown in
molecule-based RFB and LSB, the shuttle effect is still present Figure 23a, only the organic-based redox mediators are
and requires a carefully designed membrane306,307 or other pumped around the cell. At the reservoir for the cathode,
strategies308 to limit polysulfide cross over. Furthermore, the LFP (redox potential of 3.45 V) is stored and submerged in a
current densities are also rather modest in these studies when solution of FcBr2 and Fc, which have redox potentials of 3.78
compared to vanadium flow batteries.309 and 3.40 V, respectively. For the anode, static TiO2 particles
A relatively new class of RFB is the semisolid RFBs. The (redox potential of 1.8 V) are immersed in a flowing electrolyte
advent of semisolid RFB represents quite a unique develop- solution containing CoCp2 and CoCP*2 (redox potentials of
ment in RFBs where the high energy density of solid particles 2.1 and 1.67 V, respectively) redox mediators. As described in
is combined with the physical benefits of a traditional RFB. the reaction schematic in Figure 23b, during the charge process
Figure 23a illustrates a schematic of a LFP-based cathode and (electron and Li-ion transfer from cathode to anode), LFP will
TiO2-based anode semisolid RFB.298 In this design Li ions are be oxidized by FcBr2 by physical contact. The reduced FcBr2
stored in solid particles suspended in solution, which have will be pumped to contact with the working electrode
much higher energy density than their molecular solvated containing a solid redox-active particle from which it will be
counterparts. Early iteration of this design attempted to oxidized by the redox mediator of the anode (CoCP*2). The
directly obtain redox activity from a solution of flowing now reduced anode redox mediator (CoCP*2) will then
particles.311,312 However, high viscosity will likely result in proceed to reduce the TiO2 (along with Li-ion insertion). This
higher pump pressure heads in addition to lower utilization of cascading redox system offers a very unique design that can
active material due to their relatively larger size. On the basis of bypass many of the physical limitations (and resulting energy
a concept developed by Wang et al. known as redox density limitation) of using pure organic molecules for RFB. As
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Figure 24. Redox-active species for a few RFB: (a) indigo carmine, (b) 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate), (c) (2,2,6,6-
tetramethylpiperidinyloxyl)/lithium, and (d) viologen/lithium. Reprinted with permission from ref 310. Copyright 2015 Springer Nature.

the redox-active molecules in both the anolyte and the 6. OPEN SYSTEMS
catholyte are merely “charge messengers” (redox mediators), An open system refers to a battery that operates with one
their concentration is decoupled from the energy density. electrode (usually the cathode) open to the ambient
Other works based on a similar concept also emerged.300,314 atmosphere. Depending on the battery technology, the
While this work utilized similar active materials as LIBs, the reduction products are either soluble or nonsoluble in the
concept is likely transferable to other material combinations. electrolyte. In contrast to commercial LIBs, the resulting
Beyond the cost of the electrode materials, a large portion of implications of the electrolyte composition on the capacity,
the cost of a RFB resides in the membrane separating the cycle stability, overpotential, and overall redox mechanism are
catholyte and anolyte while allowing mass transfer of charge significantly more profound. For example, depending on the
carrier. This type of membrane (usually in the form of stability and solubility of the superoxide anion in Li−O2
Nafion310,315,316) is expensive for widespread application. electrolyte, the obtained capacity can be drastically in-
Another type of RFB is the so-called redoxmers RFBs creased.321,322 Foreign redox mediators (RMs) such as
(schematic shown in Figure 24a). A redoxmers-based RFB 2,2,6,6-tetramethylpiperidinyl 1-oxyl (TEMPO)323 and tris[4-
entails the use of polymer grafted with redox-active functional (diethylamino)phenyl]amine (TDPA)324 can also be added to
groups (i.e., redoxmers). As shown in Figure 24b−e, various alter the charge mechanism. Furthermore, if LiI is added into
organic functional groups can be used to act as redox centers as the electrolyte, LiOH can be expected as the final discharge
long as their oxidation and reduction reactions are reversible. product in place of Li2O2.325,326 In the case of Zn−air battery,
These redoxmers are dispersed in an aqueous electrolyte (or the aqueous electrolyte allows for reduction of O2 completely
organic based317) and subsequently used as the active into Zn(OH)4, which precipitates out as ZnO when the
material.310,318,319 Due to the large size of polymers, membrane solubility limit is reached.327,328 Depending on the pH of the
design becomes comparatively trivial. Common dialysis electrolyte, the solubility limit of the Zn(OH)4 can be tuned.
membranes310 and microporous membranes such as Cel- However, changing the pH would also decrease the stability of
the electrolyte. To follow will be a more detailed description
gard320 have also been shown to be quite effective and cheap
on the effect of electrolyte for Li−O2 battery (LAB) and zinc−
selections for limiting anolyte/catholyte redoxmers crossover.
air battery (ZAB).
The cost advantages of redoxmers are accompanied by an
increase in anolyte/catholyte viscosity. In addition to the 6.1. Li−Air(O2) Electrolyte
increase in the required pump pressure head, the reaction rates Laboratories have attracted much attention due to their
and resulting power density will likely also be decreased. potential for high energy density. Compared to some of the
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Figure 25. Discharge/reduction mechanism of O2 in a Li−O2 system with regard to the role of LiO2. Reprinted with permission from ref 322.
Copyright 2014 Springer Nature.

Figure 26. (a) Mechanism of a redox mediator (RM) on the charging/oxidation process of Li2O2. Even without direct contact with a conductive
substrate, the Li2O2 can be oxidized by first allowing the soluble RM to oxidize on the conductive substrate followed by diffusion of RM to Li2O2
and subsequent reduction/oxidation of RM/Li2O2, respectively. (b) Reduction in charge overpotential when a RM is used. Reprinted with
permission from ref 332. Copyright 2016 Springer Nature.

other battery technologies (LIB, ZAB, and even LSB), energy density. Compared to LIB, the electrolyte plays an even
laboratories are still very far from any commercial application. more involved role in regulating the performance indices of
In fact, the common term “air battery” is technically incorrect LABs. LiO2 is known to be a crucial reaction intermediate that
as most of the literature still employs pure oxygen gas sources can dictate the morphology/degree of passivation of the
as their oxidant. When real or even simulated air is used, the cathode and as such the subsequent discharge capacity.322
H2O and CO2 present will usually react with the Li metal after Depending on the donor number (DN) of the electrolyte, the
transport from the cathode to the anode. Furthermore, the lifetime of the LiO2 changes. This in turns alters the O2
adsorption of H2O or CO2 onto surface defects of Li2O2 and reduction pathway as shown Figure 25. At higher donor
subsequent undesired side reactions is also known to numbers, LiO2 becomes more soluble and will dispropor-
occur.329,330 Only recently was a study able to achieve good tionate into Li2O2, depositing in a nonfilm-like manner. In
performance in a relatively real LAB system (simulated 25 °C contrast, the reduction of solid LiO2 to Li2O2 will dominate if
air at 45% relative humidity).331 This work employed the use the donor number of the electrolyte solvent is low. This
of a Li2CO3-protected anode and an electrolyte blend scenario will result in the formation of a thin film of insulating
consisting of an ionic liquid (1-ethyl-3-methylimidazolium Li2O2 on the surface of the conductive scaffold, effectively
tetrafluoroborate) and dimethyl sulfoxide. The strategy passivating the electrode for any further reduction process.
prevents the diffusion of H2O and CO2 to the Li-metal In the charge process, typical Li−O2 cells will exhibit a very
anode but allows for Li-ion transfer (much like a LIB SEI and a high overpotential for Li2O2 oxidation. The use of RMs has
Type II SSE interface). Furthermore, the solvation energy in been employed in LAB to enable a lower voltage charge cycle.
the ionic liquid-based electrolyte of H2O and CO2 is similar to As Li2O2 is electrically insulating, it is difficult for a LAB to
if not stronger than their adsorption energy to Li2O2. This is charge Li2O2 that is not in direct contact with a conductive
likely to help in preventing any side reaction involving H2O surface.333 For this reason, soluble charge carriers are required
and CO2 with the discharge products. to assist in the charge transfer from the various parties of the
Even in ideal operating conditions, there are still many poor oxidation process.323,324,334 As shown in Figure 26a, the RM is
performance metrics such as low round-trip efficiency and first oxidized by the conductive substrate and then diffuses to
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the surface of Li2O2, where the RM+ oxidizes Li2O2. In order to The use of minute amounts of polymer additives (parts per
be functional, an oxidation RM must have an equilibrium million levels) has demonstrated smoothened Zn plating. It is
oxidation potential higher than the equilibrium oxidation believed that the polymer will adsorb onto the tip of the Zn,
potential of Li2O2, that is, the oxidation of Li2O2 must be first reducing dendrite propagation.350,351 This work reported a
thermodynamically favored before the RM is to be oxidized. pronounced reduction in the morphology of the Zn dendrites
Interestingly, after passing this criteria, the oxidation potential upon injection of 100 ppm of low molecular weight
of the RM becomes less important. Instead, the specific steric polyethylenimine (PEI, 800 g mol−1). As shown in the optical
interaction between the RM and Li2O2 also plays an important images in Figure 27a and 27b, the thin tips created from a
role in the charging process.335 If these criteria are met, the
resulting charge potential should drastically decrease as shown
in Figure 26b, where the charge potential decreases ∼0.5 V
without and with a RM. It should be noted that similar
phenomena have also been seen in the oxidation of bulk
commercial Li2S, where a significant charge overpotential is
also observed.7,336 However, the stability of the RM (against
LiO2) and the protection of the anode against the internal
shuttling of RM (low Coulombic efficiency) will be the
limiting factors against the practical effectiveness of RMs in
LAB.
Another interesting aspect of LAB is the effect of H2O and
LiI on the composition of the discharge product. With H2O
and LiI present, the LAB will tend to reversibly form LiOH as
the main discharge product.325 While there has been much
debate in this area, the implications of this relatively slight
modification to the electrolyte are critical.326,337−339 LiOH is
significantly more active to oxidation than Li2O2 in the Figure 27. Optical image of zinc plating (a) before and (b) after
injection of polyethylenimine (PEI, MW = 800 g mol−1). Scanning
presence of H2O, which would mean a significantly lower electron microscopy of dendrite tips (c) before and (d) after addition
overpotential and as such higher energy efficiency. Further- of PEI. Reprinted with permission from ref 350. Copyright 2015
more, the four-electron transfer enabled from converting O2 Elsevier.
(oxidation state of 0) to LiOH (oxidation state of −2) would
also mean a possibility for higher energy density.
Taken together, the role of electrolyte on the current key fractal-like Zn dendrite growth were halted and became thicker
operating parameters of LAB (overpotentials, discharge in size when the PEI was added. Corroborating investigation
capacity, and overall energy efficiency) is likely to continue by scanning electron microscopy revealed a significant
to dominate much of the research field in the near future. reduction in the sharpness in the Zn dendrites when PEI
6.2. Zn−Air Electrolytes was added (Figure 27c and 27d). Future studies into this field
could achieve dendrite-free ZABs.
Although the majority of ZAB research has focused on a Recent interest into ZAB has also shifted to the application
bifunctional catalyst that is for both OER and ORR,340−345 in flexible energy storage devices. To this end, the flexibility of
there has been some work on the investigation into different the electrolyte has converged on the use of a gel-type PE. Gel
electrolytes. For a detailed review of the individual classes of electrolytes can offer capabilities in liquid retention and
electrolytes for secondary ZAB, we refer the readers to another prevent leakage of solvent upon application of mechanical
review.346 In this section, we will instead focus on unique stress.328 Conductivities of 1.76 × 10−2 S cm−1 have been
electrolyte designs that can be used to achieve certain achieved with a hierarchical polymer electrolyte based on
performance metrics. polyacrylonitrile-grafted gelatin filled into a polyacrylonitrile
A typical secondary ZAB operates in an aqueous electrolyte electrospun sheet. The highly hydrophilic nature of the
at alkaline conditions with KOH or NaOH as the main polymer electrolyte was able to retain its liquid electrolyte
electrolyte salt.347 KOH is typically preferred over NaOH due and function as a battery even after various mechanical abuse.
to the higher solubility of potassium-based carbonate species. This is in contrast to another similar work that only used a
The solubility limit of the discharge product can strongly gelatin-based gel electrolyte, which only obtained a con-
dictate the discharge capacity (energy density) and cyclability ductivity of 3.1 × 10−3 S cm−1.352 Another work demonstrated
of the ZAB. With solid product precipitates such as ZnO the use of poly(vinyl alcohol) gel electrolyte with a
forming throughout the battery, pore blockage and passivation conductivity of 15 × 10−2 S cm−1.353 Moreover, some of the
can occur.348 Changing the pH of the electrolyte can drastically power densities of published ZABs have measured values of
shift the complex and dynamic solubility and reaction well over 30 mW cm−2.354,355 However, demonstration of a
equilibriums occurring within the electrolyte solution through- higher energy (volumetric) and high power density ZAB
out the cycling protocol of the battery.349 For example, the remains to be seen.356 While some work has shown
main benefit of a neutral electrolyte is the lower capacity of the performance under mechanically stressed conditions, practical
electrolyte to absorb CO2 from the air in the form of operating conditions for flexible electronics, i.e., cyclic
carbonate. This in turn lowers the amount of insoluble mechanical deformations, need to be investigated. Only by
carbonate salts precipitation. However, hydrogen evolution the combined effect of proper liquid electrolyte retention,
also becomes a problem at lower pH in addition to decreased efficient ion transport, while maintaining a compact profile can
conductivity due to lower ion concentrations. flexible ZABs be realized.
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7. CONCLUDING REMARKS AND PERSPECTIVES AUTHOR INFORMATION

The developments of electrolytes always evolve around the Corresponding Authors
emergence of new battery chemistry; hence, the metrics Kang Xu − Energy Storage Branch, Sensor and Electron
represented in Figure 1 undergo rapid dynamic changes. The Directorate, U.S. Army Research Laboratory, Adelphi, Maryland
insatiable needs for higher energy and power densities, besides 20783, United States; orcid.org/0000-0002-6946-8635;
those for better safety, lower cost, and wider service Email: [email protected]
temperature range, keep pushing the boundaries of battery Jun Lu − Chemical Sciences and Engineering Division, Argonne
components to more challenging territories, and these National Laboratory, Lemont, Illinois 60439, United States;
orcid.org/0000-0003-0858-8577; Email: [email protected]
challenges eventually are passed on to electrolytes, partially
or entirely. In this context, the research of electrolyte materials Authors
and science, especially the fundamental understanding of Matthew Li − Chemical Sciences and Engineering Division,
interfacial/interphasial processes, constitutes the key areas for Argonne National Laboratory, Lemont, Illinois 60439, United
future energy storage science. States; Department of Chemical Engineering, Waterloo Institute
The advent of concentrated electrolyte systems will continue of Nanotechnology, University of Waterloo, Waterloo, Ontario
to draw research interest with potential application in the near N2L 3G1, Canada
future. Its application into battery systems will continue to Chunsheng Wang − Department of Chemical & Biomolecular
advance our understanding of both interfacial electrochemistry Engineering Department of Chemistry & Biochemistry,
and the nature of electrolyte solutions. Nanotechnology has University of Maryland, College Park, Maryland 20742, United
allowed for unprecedented advances in our ability to control States; orcid.org/0000-0002-8626-6381
material at very small scales, enabling the creation of new Zhongwei Chen − Department of Chemical Engineering,
Waterloo Institute of Nanotechnology, University of Waterloo,
electrolyte systems. In both redox flow systems and solid
Waterloo, Ontario N2L 3G1, Canada; orcid.org/0000-
electrolytes, our ability to control the morphology and particle 0003-3463-5509
size is critical in achieving future enhancements. Similarly,
theoretical studies assisted by large data sets, supercomputing Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.chemrev.9b00531
power, machine learning and artificial intelligence will likely
serve to quickly sieve through and extract useful next- Notes
generation electrolyte systems. Interestingly, the predictive
The authors declare no competing financial interest.
power of computational studies has only been rarely used.
Those frontiers will without a doubt receive unprecedented Biographies
attention in the coming decades. Matthew Li is a Ph.D. student from the University of Waterloo,
As each respective field in electrolyte design begins to currently at Argonne National Laboratory as a visiting scholar. His
approach and even surpass performance requirements imposed research focuses on the design and synthesis of cathode material for
by industry standards, practicality and scale will be of the Li−S and Li-ion batteries. He has extensive experience in applying
utmost concern. High-volume manufacturing of some of these synchrotron-based characterization techniques (X-ray diffraction,
electrolytes will no doubt pose a problem. Concentrated small-angle X-ray scattering, X-ray absorption spectroscopy) toward
electrolytes will inevitably incur additional cost, as the Li salts understanding battery operation and failure.
used are typically quite expensive and higher concentrations Chunsheng Wang is a Robert Franklin and Frances Riggs Wright
worsen the situation. Synthesis and processing of solid-state Distinguished Chair Professor in the Chemical & Biomolecular
electrolytes require careful high-temperature sintering proto- Engineering, Department of Chemistry and Biochemistry, at the
cols with little room for air contamination. Most of the solid University of Maryland. He is an associate editor of ACS Applied
electrolytes are also quite brittle, making their deployment into Energy Materials and UMD Director of The UMD-ARL Center for
a battery cell nontrivial. Recent reports that Li dendrite growth Research in Extreme Battery. His research focuses on reachable
batteries and fuel cells. He was ranked as the Global Highly Cited
through various solid-state electrolytes and the attribution of
Researchers (top 1% by citation) by Clarivate Analytics in 2018−
such behaviors to the high electronic conductivity of these
2019.
solid electrolytes raise concern over the use of a Li-metal
anode, which would cast a negative effect on the expected high Zhongwei Chen is a Canada Research Chair (Tier 1) in Advanced
energy densities of the corresponding solid-state batteries. Materials for Clean Energy at the University of Waterloo, Fellow of
the Canadian Academy of Engineering, Fellow of the Royal Society of
However, even with the conventional chemistries adopted by
Canada, and Vice President of the International Academy of
LIBs (graphitic anode, transition metal oxide cathodes), solid- Electrochemical Energy Science. His research focuses on advanced
state batteries still offer advantages in packaging density as well energy materials and electrodes for polymer electrolyte membrane
as safety. Much more focus must also be placed on decreasing fuel cells, Li-ion, metal−air, Li−S, and various next-generation
the cost of these electrolyte systems by designing different batteries. He received the 2016 E.W.R Steacie Memorial Fellowship
synthetic routes. An excellent example is the proposed and Rutherford Memorial Medal. In 2018−2019, he was ranked as the
solution-based synthesis of sulfide-type SSE, where the SSE Global Highly Cited Researchers (top 1% by citation for field and
is soluble in certain organic solvents, which could be year) by Clarivate Analytics.
potentially processed with the electrode active material and Kang Xu is ARL Fellow and Team Leader of Aqueous Electro-
conductive additive, leading to homogeneity throughout the chemistry, Energy Storage Branch, U.S. Army Research Laboratory,
electrode upon drying. and co-founder of the Center of Research on Extreme Batteries

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(CREB). With his Ph.D. degree in Chemistry, over 250 publications, Lithium−O2 Battery with Alkyl Carbonate Electrolytes. J. Am. Chem.
5 book chapters, and 25 U.S. Patents, he is best known in the field for Soc. 2011, 133, 8040−8047.
two comprehensive review articles on electrolytes published in (9) Zhang, X.; Mu, X.; Yang, S.; Wang, P.; Guo, S.; Han, M.; He, P.;
Chemical Reviews (2004 and 2014). Zhou, H. Research Progress for the Development of Li-Air Batteries:
Addressing Parasitic Reactions Arising from Air Composition. Energy
Jun Lu is a chemist at Argonne National Laboratory. His research Environ. Mater. 2018, 1, 61−74.
interests focus on the electrochemical energy storage and conversion (10) Tornheim, A.; Garcia, J. C.; Sahore, R.; Iddir, H.; Bloom, I.;
technology with the main focus on beyond Li-ion battery technology. Zhang, Z. Decomposition of Phosphorus-Containing Additives at a
He earned his B.S. degree in Chemistry Physics from the University of Charged Nmc Surface through Potentiostatic Holds. J. Electrochem.
Science and Technology of China (USTC) in 2000. He received his Soc. 2019, 166, A440−A447.
Ph.D. degree from the Department of Metallurgical Engineering at the (11) Albertus, P.; Babinec, S.; Litzelman, S.; Newman, A. Status and
University of Utah in 2009 with major research on metal hydrides for Challenges in Enabling the Lithium Metal Electrode for High-Energy
reversible hydrogen storage application. He is the awardee of the first and Low-Cost Rechargeable Batteries. Nat. Energy 2018, 3, 16−21.
DOE-EERE postdoctoral fellowship under the Vehicles Technology (12) Winter, M. The Solid Electrolyte Interphase − the Most
Important and the Least Understood Solid Electrolyte in Recharge-
Program from 2011 to 2013. He serves as Associate Editor of ACS
able Li Batteries. Z. Phys. Chem. 2009, 223, 1395.
Applied Materials and Interfaces. He was elected as Associate President (13) Xu, K.; Lam, Y.; Zhang, S. S.; Jow, T. R.; Curtis, T. B. Solvation
and Board Committee Member of the International Academy of Sheath of Li+ in Nonaqueous Electrolytes and Its Implication of
Electrochemical Energy Science (IAOEES). He was also the first Graphite/Electrolyte Interface Chemistry. J. Phys. Chem. C 2007, 111,
awardee of the IAOEES Award for Research Excellence in 7411−7421.
Electrochemistry Energy in 2016. He has authored/coauthored (14) Xu, K. Charge-Transfer” Process at Graphite/Electrolyte
more than 350 peer-reviewed research articles, published in Nature, Interface and the Solvation Sheath Structure of Li + in Nonaqueous
Nature Energy, Nature Nanotechnology, Chemical Reviews, Nature Electrolytes. J. Electrochem. Soc. 2007, 154, A162−A167.
Communications, Journal of the American Chemical Society, etc., and has (15) Su, C.-C.; He, M.; Amine, R.; Rojas, T.; Cheng, L.; Ngo, A. T.;
filed over 20 patents and patent applications. He was ranked as the Amine, K. Solvating Power Series of Electrolyte Solvents for Lithium
Global Highly Cited Researchers (top 1% by citation) by Clarivate Batteries. Energy Environ. Sci. 2019, 12, 1249−1254.
Analytics in 2018−2019. (16) Bockris, J. O. M.; Reddy, A. K. Modern Electrochemistry 2b:
Electrodics in Chemistry, Engineering, Biology and Environmental Science;
Springer Science & Business Media, 2000; Vol. 2.
ACKNOWLEDGMENTS (17) Bernal, J. D.; Fowler, R. H. A Theory of Water and Ionic
Solution, with Particular Reference to Hydrogen and Hydroxyl Ions. J.
This work was supported by the U.S. Department of Energy
Chem. Phys. 1933, 1, 515−548.
(DOE), Office of Energy Efficiency and Renewable Energy, (18) Yamada, Y.; Yamada, A. ReviewSuperconcentrated Electro-
Vehicle Technologies Office. Argonne National Laboratory is lytes for Lithium Batteries. J. Electrochem. Soc. 2015, 162, A2406−
operated for the DOE Office of Science by UChicago Argonne, A2423.
LLC, under contract number DE-AC02-06CH11357. Work at (19) Azov, V. A.; Egorova, K. S.; Seitkalieva, M. M.; Kashin, A. S.;
the Army Research Laboratory was supported as part of the Ananikov, V. P. Solvent-in-Salt” Systems for Design of New Materials
Joint Center for Energy Storage Research, an Energy in Chemistry, Biology and Energy Research. Chem. Soc. Rev. 2018, 47,
Innovation Hub funded by the U.S. Department of Energy, 1250−1284.
Office of Science, Basic Energy Sciences under the Interagency (20) Yamada, Y.; Wang, J.; Ko, S.; Watanabe, E.; Yamada, A.
Agreement No. IAA 89243019SSC000028. The authors would Advances and Issues in Developing Salt-Concentrated Battery
also like to acknowledge financial support from the Natural Electrolytes. Nat. Energy 2019, 4, 269−280.
Sciences and Engineering Research Council of Canada (21) McKinnon, W. R.; Dahn, J. R. How to Reduce the
Cointercalation of Propylene Carbonate in Li X Zrs2 and Other
(NSERC), the Waterloo Institute for Nanotechnology
Layered Compounds. J. Electrochem. Soc. 1985, 132, 364−366.
(WIN) and the University of Waterloo. (22) Angell, C. A.; Liu, C.; Sanchez, E. Rubbery Solid Electrolytes
with Dominant Cationic Transport and High Ambient Conductivity.
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