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Accepted Article

Title: A comprehensive insight into the electrolytes for rechargeable

lithium–air batteries

Authors: Jingning Lai, Yi Xing, Nan Chen, Li Li, Feng Wu, and Renjie
Chen

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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201903459

Angew. Chem. 10.1002/ange.201903459

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Angewandte Chemie International Edition 10.1002/anie.201903459

REVIEW

A comprehensive insight into the electrolytes for rechargeable

lithium–air batteries
Jingning Lai,[a] Yi Xing,[a] Nan Chen,[a] Li Li,[ab] Wu Feng,[ab] and Renjie Chen*[ab]

Accepted Manuscript

This article is protected by copyright. All rights reserved.

Angewandte Chemie International Edition
REVIEW
Abstract: Lithium (Li)–air batteries are promising devices for
electrochemical energy storage because of their ultra-high
energy density. However, it is still challenging to achieve
practical Li–air batteries because of their severe capacity fading
and poor rate capability. Electrolytes are the prime suspect for
cell failure. In this review, we focus on the opportunities and
challenges of electrolytes for rechargeable Li–air batteries. A
detailed summary including the reaction mechanisms, internal
compositions, instability factors, selection criteria, and design
ideas of the explored electrolytes is provided to obtain
appropriate strategies to meet the requirement of battery. In
particular, ionic liquid (IL) electrolytes and solid-state electrolytes
show exciting opportunities to control over both high energy
density and safety. It is hoped that this review will provide
guidelines to aid selection of suitable electrolytes for Li–air
batteries and encourage further research of electrolyte
optimization.
1. Introduction
Li–air batteries are promising devices for electrochemical energy
storage because of their ultra-high theoretical energy density
(about 3500 Wh kg−1), which is comparable with that of
gasoline.[1] However, Li–air batteries are still in their infancy and
face many challenges such as severe capacity fading and poor
rate capability.[2] The electrolyte in a Li–air battery can be
likened to blood in humans, playing a decisive role in
determining the battery performance by affecting factors such as
discharge capacity, rate capability, round-trip efficiency, and
cycling stability.[3] Therefore, it is necessary to develop suitable
electrolytes that coordinate with the whole battery system.
As presented in Figure 1, Li–air batteries are composed of
cathodes, electrolytes and Li anodes. The cathode should be
porous and contain enough space to accommodate the insoluble
discharge product Li2O2.[4-10] O2 as the active material of the
cathodes is supposed to be obtained from the open air to
facilitate high capacity.[1] In non-aqueous systems, pure O2 is
widely used in most laboratory-scale experiments to prevent
other components in air, especially H2O and CO2, from
interfering with the desired electrochemical behavior. These
systems with pure O2 are also called Li–O2 batteries. In addition,
electrocatalysts are usually added to facilitate the O2 reduction
reaction (ORR) and O2 evolution reaction (OER) during the
[a] J. Lai, Dr. Y. Xing, Dr. N. Chen, Prof. L. Li, Prof. F. Wu, Prof. R.
Chen
Beijing Key Laboratory of Environmental Science and Engineering
School of Materials Science and Engineering, Beijing Institute of
Technology, Beijing 100081, China.
Email address: chenrj@bit.edu.cn
[b] Prof. L. Li, Prof. F. Wu, Prof. R. Chen
Collaborative Innovation Center of Electric Vehicles in Beijing,
Beijing 100081, China.
This article is protected by copyright. All rights reserved.
10.1002/anie.201903459
discharge and charge processes. Electrolytes of Li–air batteries
can be divided into four types, including non-aqueous liquid and
solid-state electrolytes, as well as aqueous and hybrid
electrolytes. Li anodes of Li–air batteries display the same
electrochemical reaction:
Li ↔ Li+ (sol) + e− (1)
The chemistry at the cathode differs depending on the
electrolyte. [11-14] Non-aqueous liquid Li–air batteries have been
widely studied in the past decades because they can provide
extremely high energy density with a simple battery structure.
For non-aqueous liquid Li–air batteries, the desired
electrochemical reaction with Li2O2 as the discharge product is:
2Li+ + O2 + 2e− ↔ Li2 O2 E 0 = 2.96 V vs Li/Li+ (2)
Accepted Manuscript
However, the elemental steps are complicated and the
discharge/charge mechanisms are still controversial. Based on
experiments and theoretical calculations, two major discharge
reaction mechanisms for the ORR on the cathode surface of the
non-aqueous liquid system have been proposed.[15] The
solution-mediated mechanism involves the following reactions:
O2 (sol) + e− → O2 − (sol) (3)
2Li+ (sol) + 2O2 − (sol) → Li2 O2 + O2 (4)
2Li+ (sol) + O2 − (sol) + e− → Li2 O2 (5)
The surface-mediated mechanism (―*‖ denotes a surface site on
Li2O2) involves:
Li+ + O2 (sol) + e− → LiO2 ∗ (6)
Li+ + LiO2 ∗ + e− → Li2 O2 ∗ (7)
2LiO2 ∗ → Li2 O2 ∗ + O2 (8)
The solution-mediated mechanism, in which large quantity of
Li2O2 grows as toroidal-shaped particles from solution, displays
high capacity but sometimes poor cycle performance because of
the insulation of large particles of Li2O2. The surface-mediated
mechanism, in which film-like Li2O2 grows on the cathode
surface, shows low capacity because of the clogging of the
surface, but good cycle performance in the case of limited
capacity, which attribute to the few defect sites in the Li2O2 film.
Thus, controlling the formation route and morphology of Li2O2 is
important to improve the performance of Li–air batteries.[16]
Recent studies have shown that even small changes in
electrolytes, including differences in solvents, lithium salts, and
additives, can dramatically alter the pathway of discharge
reactions. [12, 17]
The charge process is not the reverse reaction of ORR, it is
accompanied by several metastable states that do not appear in
the ORR depending on the nature of discharge product.[18] The
following two major charge reaction mechanisms for the OER
have also been proposed.[19, 20]
Charge reaction mechanism I:
Li2 O2 → 2Li+ + O2 + 2e− (9)
Charge reaction mechanism II:
Li2 O2 → LiO2 + Li+ + e− (10)
LiO2 → Li+ + O2 + e− (11)
The mechanism I is a two-electron process, while mechanism II
contains two one-electron processes that involve the formation
of LiO2 from dissolved Li2O2. However, The mechanism II is
believed to be less dominant due to the poor solubility of current
electrolytes toward Li2O2. In a practical Li–air battery, the charge
overpotential is surprisingly high due to the insulating nature of
Angewandte Chemie International Edition
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Li2O2.[21, 22] In recent years, various of electrocatalysts and
soluble catalysts are developed to reduce the charge
overpotential of Li–air battery. Compared with an electrocatalyst
embedded in the cathode, a soluble catalyst that is
homogeneously dissolved in an electrolyte significantly reduce
the charge overpotential to a low value and circumvent the issue
of cathode passivation.
Unfortunately, most non-aqueous liquid electrolytes are
flammable and volatile aprotic electrolytes, which bring safety
issues, and hard to be applied in an open system. IL electrolytes
are good alternatives to conventional aprotic electrolytes
because they are non-volatile and non-flammable. IL electrolytes
are attracting increasing interest.
The use of solid-state electrolytes is another solution for
electrolyte volatilization and leakage. The operating mechanism
of solid-state Li–air batteries is still controversial. Some
researchers have suggested that solid-state Li–air batteries
follow a similar mechanism to that of non-aqueous liquid
systems; i.e., through the formation and decomposition of Li2O2.
However, this mechanism has not been widely studied in detail
because of the lack of a suitable solid-state electrolyte and
coordinated cathode.[23, 24] Wang et al.[25] observed similar
surface-mediated mechanisms to that of non-aqueous liquid
systems in an ingeniously designed solid-state Li–O2 battery.
The discharge process includes the formation of LiO2 and then a
disproportionation reaction that produces O2 and traps these
molecules inside the Li2O2 particle, which subsequently leads to
the inflation of the particles and formation of a hollow structure.
Notably, they observed the unique discharge product Li2O at the
outer surface of the hollow particles, where surplus O2 was in
direct contact with the discharge product.
4Li+ + O2 + 4e− → 2Li2 O (12)
Water-stable solid-state electrolyte materials are the key
component for hybrid and aqueous Li–air batteries. They act as
Li+-conducting membranes (LICMs) to protect the Li anode.[26]
The battery chemistry of hybrid and aqueous Li–air batteries at
the cathodes is obviously different from that of non-aqueous
systems, consisting of two reversible four-electron reactions that
depend on the pH of the aqueous electrolytes:
O2 + 4H + + 4e− ↔ 2H2 O E 0 = 4.26 V vs Li/Li+ (13)
O2 + 2H2 O + 4e− ↔ 4OH − E 0 = 3.43 V vs Li/Li+ (14)
Compared with those with non-aqueous electrolytes, hybrid and
aqueous Li–air batteries have higher cell voltages and they can
maintain their robust cell configurations in ambient atmospheres.
The discharge products of hybrid and aqueous Li–air batteries
are mostly soluble, which can avoid pore clogging and decrease
the polarization of the cathode. However, in the case of higher
pH, the solubility of the discharge product LiOH in aqueous
solution is limited at room temperature (a maximum of 12.8 g of
LiOH can dissolve in 100 g of H2O, which is accompanied with
the formation of LiOH∙H2O) , which results in clogging
phenomena similar to the case of non-aqueous Li–air batteries.
Moreover, the amount of discharge products is limited to the
amount of available solvent because the electrolyte components
are involved in the reaction. This results in hybrid and aqueous
Li–air batteries possessing lower theoretical energy densities
than those of non-aqueous ones.[27]
This article is protected by copyright. All rights reserved.
10.1002/anie.201903459
The classification and mechanisms mentioned above reveal
that the electrolyte plays extremely important role in determining
the performance of rechargeable Li–air batteries. Moreover,
Electrolytes should be optimized to solve other issues. For
example, decomposition of electrolyte, poor kinetics of Li+/O2
dissolution and transportation, negative effects of moisture and
carbon dioxide (CO2) in air, and the instability of Li anodes.
In this review, we divide the discussion of electrolytes for Li–
air batteries into: (Ⅰ) aprotic electrolytes, (Ⅱ) ionic liquid
electrolytes, (Ⅲ) solid-state electrolytes, and (Ⅳ) aqueous and
hybrid electrolytes. Details of recent research progress and
perspectives on electrolytes are discussed in the following
sections, including selection criteria of electrolyte materials, new
Accepted Manuscript
electrolyte compositions, effective design and use of electrolyte
additives, and innovation of battery structure. This review aims
to provide information to aid selection of suitable electrolytes for
Li–air batteries and highlight the existing challenges to find ways
to improve the performance of Li–air batteries through
electrolyte optimization.
2. Aprotic electrolytes
Aprotic electrolytes have attracted lots of research effort to date.
The typical requirements for electrolytes such as high Li+
conductivity, high boiling point/low vapor pressure, wide
electrochemical window, and electronic insulation are also
necessary in Li–air batteries.[28, 29] In addition, an ideal aprotic
electrolyte for Li–air batteries should satisfy the following
requirements.[30, 31] (1) High O2 solubility and diffusivity, (2) High
chemical and electrochemical stability in O2-rich conditions, (3)
Good coordination toward the intermediates to promote the
formation of toroidal-shaped Li2O2 via solution-mediated
mechanism and (4) Soluble towards Li2O2, which is not
absolutely necessary but can promote the Li2O2 decomposition.
Li–air batteries are still in their infancy. Although many relevant
publications and much progress has been achieved in the past
decades, ultimate aprotic electrolytes that meet all the above
requirements have not yet been found. Generally, aprotic
electrolytes are composed of aprotic solvents, Li salts, and
possibly additives.
2.1. Solvents
Solvent molecules coordinate with Li+/O2 to support fast Li+/O2
transport through Li–air batteries and facilitate electrochemical
reactions between Li and O2. Various aprotic solvents have been
researched for use in Li–air batteries including carbonates,
ethers, amides, sulfones, and nitriles.[28, 32] Their different
physical properties and calculated values are described in Table
1. Electrolyte decomposition is the main causes of capacity
fading. Solvent stability is threatened by reactive O2 species
such as LiO2, Li2O2, and especially O2 .[33-35] In general, the
－
decomposition pathways of the solvents in Li–air batteries can
be divided into five categories: nucleophilic attack, auto-
oxidation, acid/base reactions, proton-mediated reactions, and
－
reduction by Li, as shown in Table 2. First, O2 is a strong
Angewandte Chemie International Edition
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nucleophile, so it is prone to attack the electron-deficient part of
the solvent (i.e., the carbon atoms of carbonyl groups (C=O) and
sulfur atoms of sulfoxides (S=O)). This results in the formation of
a [solvent–O2]− complex, which subsequently undergoes a highly
exergonic decomposition reaction. Typically, alkyl carbonates
such as EC, PC, and dimethyl carbonate (DMC) are susceptible
to nucleophilic attack by O2−. Amines such as N,N-
dimethylacetamide (DMA), dimethylformamide (DMF),[36] and N-
methyl-2-pyrrolidone (NMP) as well as sulfoxides like DMSO
also suffer from nucleophilic attack.[37] Second, reactive O2
species tend to attack α-H or β-H as Lewis bases via acid–base
chemistry. For example, the H atom at the α position of DMSO is
readily deprotonated by superoxides and peroxides, resulting in
electrolyte decomposition and byproduct generation.[38-41] Ethers
such as tetraethylene glycol dimethyl ether (TEGDME) and 1,2-
dimethoxyethane (DME) are the most commonly used solvents
in Li–air batteries. These solvents are notable for their stability
against nucleophiles that originates from the lack of electron-
withdrawing functional groups in their molecular structures.
However, these solvents are susceptible to auto-oxidation.[8, 12,
42-44]
It has been found that the α-H of ethers can be easily
abstracted by simply mixing ethers with O2. Further studies
showed that the chain length of ether solvents also affect cell
performance. The cycling duration order of cells with electrolytes
consisting of lithium bis(trifluoromethane sulfonamide (LiTFSI) in
DME, diglyme, triglyme, and TEGDME) displayed this trend
(diglyme > DME >> triglyme, TEGDME). This indicates that cells
with longer glymes are less stable during cycling. It should be
noted that DME would evaporate during cycling because of its
high volatility.[3] Furthermore, H2O is an inevitable impurity in
electrolytes and an important source of protons. H2O interacts
strongly with O2 species such as O2− and peroxides to produce
protonated superoxides, peroxides, and hydroxides. The
protonated products are also nucleophiles and strong bases,
which participate in the various decomposition reactions of the
electrolyte discussed above (proton-mediated degradation). In
addition, the Li anode with a highly reducing nature promotes
the decomposition of most known electrolytes. Ethers and
carbonates can be decomposed by Li to form insoluble by-
products such as lithium oxide (Li2O), lithium carbonate (Li2CO3),
lithium alkyl carbonates, and lithium hydroxide (LiOH). These
insoluble by-products deposit on the surface of the Li anode to
form a solid–electrolyte interphase (SEI) layer, which helps to
prevent further electrolyte decomposition. However, stable SEI
formation in DMSO, amides, or nitrile solvents is still
challenging. [45, 46]
It is necessary to predict the stability of solvents in Li–air
batteries because of the large range of solvents available and
their various decomposition mechanisms. It has been reported
that the stability of solvents can be predicted by computational
modeling. Considering nucleophilic attack, solvents with a
[solvent–O2] reaction barrier (ΔGact) of more than 24 kcal mol−1
－ －
are supposed to be stable in Li–air batteries. Conversely,
solvents with both ΔGact and formation energy of the initial
[solvent–O2] complex (ΔGr) of less than 20 kcal mol−1 are not
－
stable in Li–air batteries.[47-49] In the case of acid–base reactions,
a solvent with weaker acidity (higher pKa value) is preferred to
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10.1002/anie.201903459
maintain stability.[48, 50] Moreover, the O2 solvating capability of
－
－
the solvent also affects the stability of O2 . Solvents with a low
donor number (DN) and low acceptor number (AN) generally
－
exhibit weak O2 solvating ability, which is beneficial to prevent
electrolyte decomposition by suppressing H abstraction.[21, 29]
DN and AN of solvents play a critical role during the discharge
process. It is noted that solvents with a high DN, which strongly
solvate Li+ and stabilize Li+-(solvent)n-O2− ion pairs, are preferred
for a solution-mediated mechanism (exhibit high capacity).
Conversely, solvents with a low DN weakly solvate Li+ tend to
display a surface-mediated mechanism (exhibit low capacity).
Solvents with high AN can improve the O2− solvation degree and
further promote the solvation of Li+-O2−. Therefore, the selection
Accepted Manuscript
of solvent requires consideration of the trade-off between the
capacity and electrolyte stability.[29]
Fortunately, there are still many options to explore to identify a
suitable solvent for use in aprotic electrolytes. Recently, a methyl
pivalate-based electrolyte with good chemical stability against
O2− in O2•− solution that worked well in a real Li–O2 battery
environment was reported.[51] Peng et al.[52] reported a high-
performance Li–O2 battery with a strongly solvating
hexamethylphosphoramide electrolyte that can dissolve up to
0.35, 0.36, and 1.11 × 10−3 M of Li2O2, Li2CO3, and LiOH,
respectively. The issues of porous cathode passivation or
clogging and high charge voltage can be solved by using this
strongly solvating electrolyte.
Mixed solvents should be very promising in Li–air batteries,
although this avenue has not yet been paid much attention.
Mixed solvents are composed of two or more solvents, which
can combine their merits and sometimes display synergistic
effects. It has been reported that a composition of 0.2 M
LiSO3CF3 in 1:3:1 PC/DME/methyl nonafluorobutyl ether has a
high specific capacity because of the fast dissolution kinetics
and high solubility of O2 in fluorinated solvent-containing
electrolytes.[53] Different contents of 1,2-(1,1,2,2-
tetrafluoroethoxy)ethane (FE1), which has a short (eight-atom)
backbone chain, were mixed with DMSO as an O2-enriching co-
solvent to investigate the relationship between O2 mass transfer
and cell discharge performance.[54] A cell with 0.1 M LiClO4 in
DMSO+FE1 (5:5) electrolyte displayed a high specific capacity
and fast O2 transport. Another partially fluorinated chemical, 3-
[2-(perfluorohexyl)ethoxy]-1,2-epoxypropane has also been
used as a co-solvent in Li–air batteries that showed improved
rate capability because of the enhancement of O2 solubility and
diffusivity in the electrolyte.[55]
2.2. Li salts
Li salts are an indispensable component of electrolytes and
should be not only highly soluble in the solvent to support ion
transport but also inert to the solvents, cell components, and
reaction products/intermediates such as Li2O2 and O2 .
Moreover, the ORR and OER processes in electrolytes are
strongly influenced by the presence of Li salts, leading to
markedly different reaction mechanisms compared with those in
pure solvents.[56] According to HSAB theory, Li+ renders O2−
unstable and promotes the formation of insoluble reaction
Angewandte Chemie International Edition
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products/intermediates that may passivate the cathode and
decompose the solvent.[57]
Li salts in Li–air batteries face the problem of instability. The
commonly used Li salts such as lithium hexafluorophosphate
(LiPF6),[52, 53] lithium bis(oxalato)borate, and lithium
tetrafluoroborate (LiBF4) decompose in the presence of reactive
O2 species.[41, 42] As shown in Figure 2a, several Li salts
including LiBF4, LiPF6, and LiTFSI were tested using X-ray
photoelectron spectroscopy (XPS), which revealed serious anion
decomposition during battery operation.[58] Lithium perchlorate
(LiClO4) and lithium bromide (LiBr) are supposed to be stable in
Li–air batteries with the formation of standard discharge product
Li2O2.[59] Recently, Peng et al.[60] reported the novel F-rich Li salt
Li[(CF3SO2)(n-C4F9SO2)N], which enables the formation of a
stable, uniform, and O2-resistant SEI layer on the Li anode of Li–
O2 batteries. Using this salt, the cross-talk between the Li anode
and O2 shuttled from the cathode is avoided, which was
attributed to the effective SEI layer. Thus, the parasitic side
reactions and dendrite growth of the Li anode were suppressed,
thereby the reversibility of the Li–O2 battery was enhanced
substantially.
The dissociation level of the salt in the electrolyte plays a
role in the discharge process that is as important as the effect of
the solvent DN.[61] As shown in Figure 2b, the first group is highly
dissociated (low DN) salts, which include LiTFSI and lithium
bis(fluorosulfonyl)imide. The next group is salts with intermediate
DN like lithium triflate (LiTf). The last group is highly associated
(high DN) salts, such as LiNO3 and lithium acetate. O2•− can be
stabilized indirectly by the counter anions of Li salts. In solutions
containing highly associated Li salts, counter anions are strongly
coordinated to the solvated Li+. Somewhat analogous to high-DN
solvents that strongly solvate Li+, this stabilizes LiO2 with highly
associated salts in solvents with low DN, results to high
discharge capacity. Abraham et al.[62] demonstrated that Li+ in
LiPF6-containing electrolytes were solvated to form solvent-
separated ion pairs such as Li+(DME)nPF6− and
Li (TEGDME)PF6 . In contrast, in LiTf-based electrolytes, O2−
+ −
was stabilized in solution by forming [(DME)m−1(O2−)]Li+(Tf−) and
[(TEGDME)(O2−)]Li+(Tf−) complexes. Because of the higher DN
of Tf− than that of PF6−, higher capacities were obtained for Li–
O2 batteries containing LiTf and solvents with low DN.
McCloskey and colleagues reported that Li–O2 batteries using
electrolytes consisting of LiNO3 and LiTFSI in DME displayed
increased capacity and increased toroidal particle formation with
increasing LiNO3 concentration. This behavior was attributed to
the enhanced stabilization of Li+ and O2− by NO3−, which has a
higher effective DN than that of DME. However, when anions
with high DN are combined with high-DN solvents such as
DMSO, the benefit of increased capacity is not obtained, which
has been proved by both theoretical and experimental
analyses.[63]
The concentration of Li salts also strongly affects the
performance of Li–air batteries. A high concentration (1 M) of
LiTFSI in different kinds of glymes exhibited better cycling
performance and slower decay than those of solutions with a low
LiTFSI concentration.[3] Moreover, the tailoring effects of Li+
concentration on the Li2O2 morphology formed during the
This article is protected by copyright. All rights reserved.
10.1002/anie.201903459
discharge process has also been investigated (Figure 2c and
2d). An appropriate electrolyte concentration (between 2 and 3
M) improved the volume utilization ratio of the cathode, because
of porous three-dimensional (3D) Li2O2 formation.[64] Cells with
highly concentrated electrolyte (3 M LiTFSI in DME) without free
DME solvent molecules have also been investigated.[65] The
cells presented greatly enhanced cycling stability under both full
discharge/charge (2.0–4.5 V vs. Li/Li+) and capacity-limited (at
1000 mAh g−1) conditions. These cells also exhibited much less
reaction residue on the charged cathode surface, lower internal
resistance, and much less corrosion of the Li anode than was
the case for equivalent cells with a low-concentration electrolyte.
The concentration of Li salts also influence the O2 solubility of
Accepted Manuscript
electrolytes. A decrease in discharge capacity was observed in a
Li–air battery when the concentration of LiPF6 in PC: DME (1:1)
electrolyte increased from 0.5 M to 1 M, because of the
decreased O2 solubility.[66]
The compatibility of Li salts with solvents strongly affects the
stability of Li–air battery electrolytes.[67] LiPF6 can trigger the
decomposition of tri(ethylene glycol)-substituted trimethylsilane-
based electrolytes, whereas other Li salts such as LiTFSI and
LiTf do not.[68] Thus, future studies should consider both the Li
salt and solvent as a whole electrolyte system and
comprehensively investigate its electrochemical behavior in Li–
air batteries. The types and concentrations of Li salts should be
coordinated with the selection of solvents to develop a practical
electrolyte that could realize Li–air batteries with high energy
density and long cycle life.
2.3. Additives
Additives are used to coordinate the capacity and stability of Li–
air batteries. In contrast to the co-solvent mentioned in Section
2.1, a small amount of an additive can affect the performance or
even mechanism of a Li–air battery. The purpose of early studies
on additives was to improve the capacity by increasing the
dissolution of O2 or content of discharge products in the
electrolyte.[28] O2 should first dissolve in the liquid electrolyte.
The abilities of electrolytes to dissolve and transport O2 strongly
affect battery performance. Fluorinated compounds, for example
methyl nonafluorobutyl ether, perfluorotributylamine, and
tris(2,2,2-trifluoroethyl)phosphite, have been used as additives
to increase O2 solubility in aprotic electrolyte systems.[53] Strong
Lewis acids such as tris(pentafluorophenyl) borane and boron
esters have been used to enhance the solubility of O22 in
－
electrolytes. [69, 70]
Unfortunately, most of these additives were
tested in carbonate electrolytes, which have been proved to
react with reactive O2 species. Relevant works should be re-
examined using more stable electrolytes. In addition, these
derivatives of fluorinated compounds are prone to irreversibly
degrade through chemical and electrochemical reactions during
cell operation unless they are replaced by the perfluorinated
compounds.[71] O2 crossover towards the Li anode and different
reaction mechanisms caused by a three-phase reaction zone
should also be considered because of the improved O2 solubility.
Redox mediators (RMs) have received much attention since
Bruce et al.[72] first reported tetrathiafulvalene (TTF) in 2013.
Angewandte Chemie International Edition
REVIEW
RMs are also called soluble catalysts because of their ability to
dissolve in electrolytes and mediate the electrochemical
reactions that occur in them. An RM that is homogeneously
dissolved in an electrolyte can be reduced or oxidized in the
solution phase and then react with O2 or the solid Li2O2 that
precipitates from the solution, allowing the catalytic effect to be
exerted on all the O2 in the cell or all the Li2O2 formed during the
ORR.[73] RMs can be divided into ORR mediators (ORRMs) and
OER mediators (OERMs), which are involved in the ORR and
OER, respectively, according to the mechanism of the reaction.
2.3.1. OER mediators
OERMs have been proved useful at lowering charge
overpotentials. They are reversible redox couples that travel
between the cathode and surface of Li2O2 and can oxidize Li2O2
via a chemical process instead of electrochemical oxidation.
OERMs exhibit the following mechanism
2(OERM) → 2(OERM)+ + 2e− (15)
2(OERM)+ + Li2 O2 → 2(OERM) + 2Li+ + O2 (16)
As shown in Equation (15, 16) and Figure 3a, during the charge
process, the RM is initially oxidized near the cathode surface via
an electrochemical reaction to form RM+, which can diffuse
through the electrolyte and chemically oxidize Li2O2 to two Li+
and O2 gas. Finally, RM+ is reduced to the initial state of RM. The
latter process is able to lower the OER overpotential to an
appropriate value, preventing decomposition of electrolytes at
high potential.[74, 75] The formation of highly reactive Li2−xO2
species can be avoided, which further suppresses electrolyte
decomposition.[76] The oxidation potential of OERMs needs to be
slightly higher than the theoretical decomposition potential of
Li2O2 (2.96 V vs. Li/Li+), and lower than the actual charge
plateau of Li–air battery.
A variety of organic, organometallic, and inorganic
compounds are sorted out as OERMs. [77] Organic OERMs such
as TTF [72, 78] and tetramethylpiperidinyloxyl (TEMPO) [79-81] are
molecules with double bonds and/or aromatic nature, which
undergo redox reactions through electron exchange of non-
covalent/resonance structures. Their electronic structures
strongly determine redox potentials; therefore, a large number of
organic materials can be designed to fulfill the requirements for
OERMs. Ionization energy is an important parameter according
to which possible rules for the design of organic OERMs have
been proposed.[75] Organic molecules with ionization energies of
approximately 6 eV in vacuum are believed as candidate
OERMs. Furthermore, effective use of organic OERMs also
requires careful optimization of the electrolyte solution.
Molecular orbital energies of several RMs and TEGDME are
displayed in Figure 3b. The RMs in the yellow region with
oxidation potentials slightly higher than 2.96 V are suitable for
use in Li–air batteries, whereas the RMs in the grey shaded area
with a singly occupied molecular orbital energy of the oxidized
RM lower than the highest occupied molecular orbital energy of
TEGDME would react with TEGDME. Other solvents, Li salts,
and RMs should also be explored to comprehensively consider
this issue.
Organometallic mediators usually consist of redox-active
transition metal cations and aromatic organic ligands, which are
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10.1002/anie.201903459
bound by coordinative bonds. These complexes are able to
participate in redox reactions by changing the oxidation state of
the central metal ions. The selection of organometallic mediators
is limited to metal ion couples such as Fe2+/Fe3+, Co2+/Co3+, and
Ru2+/Ru3+ because they need to have suitable redox
potentials.[82] It is worth mentioning that organometallic
mediators can not only facilitate the OER process but also
influence the ORR process by enhancing the solubility of O2 and
Li oxide compounds, which is related to their affinity for O2.[83]
Thus, organometallic mediators are classified as dual-function
catalysts. Similarly, the heme molecule (Figure 3c), a common
porphyrin cofactor in blood, is considered to be an OERM that
can increase the efficiency of O2 evolution in Li–air batteries and
Accepted Manuscript
also facilitate the ORR process.[84] Ru(II) polypyridyl complex
(RuPC) was recently demonstrated as a multifunctional soluble
catalyst to facilitate the reversible Li2O2 formation and
decomposition in Li–air batteries. RuPC can not only expand the
formation of Li2O2 in electrolyte via a solution-mediated
mechanism, but also suppress the reactivity of LiO2 intermediate
by forming RuPC(LiO2-3DMSO) intermediate during discharge,
which is effective to alleviate the cathode passivation and
parasitic reactions. In addition, a one-electron pathway can be
achieved when charging in turn; thus, the Li2O2 products can be
decomposed reversibly with a low overpotential. Consequently,
the Li–air batteries exhibited high discharge capacity, low
charge overpotential, and ultralong cycle life.[85]
Inorganic OERMs are mainly halide ions such as I− or Br−
(introduced via LiI or LiBr in solution, respectively) that can
promote decomposition of Li2O2 through redox reactions.[86-89]
These OERMs usually involve X−/X3− redox couples rather than
X3−/X2 couples because of the corrosive nature of I2 and Br2. LiI
has been used to lower the polarization of Li–air batteries,
resulting in markedly enhanced cycle performance.[90] However,
LiI can trigger side reactions between reactive O2 species, glyme
solvents, and H2O, which cause the formation of LiOH rather
than Li2O2.[91] And the Li–iodide electrochemistry was observed
at the end of the charging process(Figure 3d).[92, 93] LiBr
performed better than LiI in diglyme solution because of its fewer
side reactions.[76, 88] Interestingly, halides such as CsI and RbI
show promise as multifunctional OERMs because a low
concentration of Cs+ or Rb+ can remain in the electrolyte even
when Li+ is reduced to Li. Cs+ or Rb+ can act as an electrostatic
shield to protect the Li anode and hinder Li dendritic growth
caused by Li+ reduction.[94] Moreover, InI3 has been proposed as
a self-defense RM to raise the efficiency of Li–air batteries. In3+
can form a stable indium layer on the Li anode, which protects
the Li anode from attack by the soluble I3−. The pre-deposited
indium layer also suppresses the growth of dendrites.[95] Another
kind of inorganic OERM is LiNO3, which can serve as not only a
Li salt but also a useful OERM in Li–O2 batteries.[74, 76] LiNO3 is
also beneficial for the formation of a stable SEI on the surface of
lithium metal.[46] When combined with suitable solvent such as
tetramethylene sulfone, LiNO3-based electrolyte produced fewer
side reactions than electrolytes based on other Li salts, owing to
the low overpotential originated from the NO2−/NO2 redox
reaction.[96]
2.3.2. ORR mediators
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ORRMs mediate the electron transfer between the cathode and
O2 in the electrolyte during the discharge process. The reduction
potential of ORRMs needs to be slightly lower than the
theoretical formation potential of Li2O2 and higher than the actual
discharge plateau. As shown in Equation (17) and (18), during
the discharge process, the ORRM is reduced before the ORR
(Equation (17)); subsequently, the reduced ORRM participates in
the formation of Li2O2 by transferring two electrons to Li+ and O2,
as summarized in Equation (18).
2(ORRM) + 2e− → 2(ORRM)− (17)
2(ORRM)− + 2Li+ + O2 → 2(ORRM) + Li2 O2 (18)
The reduction of the ORRM is the only electrochemical reaction
during the discharge process, which determines the discharge
potential of Li–air batteries. Therefore, the reduction potential of
batteries can be controlled by selecting an appropriate ORRM.
Moreover, the formation of Li2O2 in weakly solvating electrolyte
solutions can be realized by adding ORRMs to electrolytes.[97]
By complexing Li+, O2 and ORRM−, the formation of LiO2
intermediate as well as related side reactions can be avoided at
the same time.
Recently, Bruce et al.[98] described a 2,5-di-tert-butyl-1,4-
benzoquinone (DBBQ) ORRM for Li–O2 batteries (Figure 3e).
On discharge, DBBQ is first reduced to DBBQ– at the cathode
and then binds to Li+ and reduces O2 to O2–, forming the
complex LiDBBQO2 in solution. This complex in turn
disproportionates to Li2O2 and reforms DBBQ. LiDBBQO2 is
more stable as an intermediate than LiO2 because it has lower
free energy, which effectively lowers the overpotential during
discharge. The conversion between DBBQ and LiDBBQO2
occurs repeatedly during discharge, endowing the batteries with
high discharge rates and high capacities. In this way, solvents
with high DN or AN or highly associated Li salts are not required
to promote solution-phase formation of Li2O2. Dual mediators
such as DBBQ and TEMPO have also been introduced to
stabilize the carbon cathode of a Li–O2 battery during both
discharge and charge processes (Figure 3f). This battery
showed lower polarization and improved rate and cycle
performance compared with those of the equivalent battery
without mediators.[99] Thereafter, Peng et al.[100] reported the
coenzyme Q10 (CoQ10) can be used as a soluble ORRM. The
CoQ10/CoQ10− couple shows a formal potential of 2.63 V and a
reduction peak at 2.54 V, indicating the ability of CoQ10− to
assist chemical reduction of O2 to Li2O2 in Li+-containing
electrolyte solution. When the current density was 0.1–0.5 mA
cm−2, the battery with CoQ10 delivered a discharge capacity
about 40–100 times that obtained for the battery without CoQ10.
2.3.3 Effect of moisture on Li–air battery performance
Water can be used as an additive in Li–air batteries. As shown in
Figure 4(a–d), the deposition of Li2O2 in an Li–air battery usually
occurs via a surface electrochemical growth process on a
nucleated film of Li2O2 through the sequential transfer of
solvated Li+ (Li+(sol)) and an electron to the intermediate species
LiO2, eventually forming Li2O2. The electron must tunnel through
the nucleated Li2O2 film, but this process is limited by the low
electronic conductivity of Li2O2. Water is a strong electron
acceptor and triggers a solution pathway with Li+(sol) and
solvated O2− (O2−(sol)), leading to the growth of toroidal-shaped
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10.1002/anie.201903459
Li2O2. O2−(sol) is adsorbed as LiO2 on the growing toroidal
particles, ultimately disproportionating to form Li2O2. Thus,
O2−(sol) acts as a redox shuttle and leads to the formation of
larger crystalline Li2O2 particles, thereby circumventing the
conductivity limitations caused by surface electrochemical
growth.[101] This is the reason why a trace amount of water in
electrolytes can catalyze the reactions on the cathode of Li–air
batteries during discharge and charge to result in increased
capacity.[86, 102] The charge overpotentials and the morphologies
of discharge products depend on the H2O concentration in the
electrolyte (Figure 4f–j).[103] If an excess amount of H2O is
present in the electrolyte, the discharge product will be disk-form
LiOH instead of the typical toroidal-shaped Li2O2. Recently, Zhou
Accepted Manuscript
and co-workers proposed a novel H2O2 additive that assists the
decomposition of either solid LiOH compounds at the cathode or
dissolved LiOH in the electrolyte in an H2O-containing Li–O2
battery.[104] The addition of H2O2 greatly decreased the charge
plateau to 3.50 V and increased the charge capacity to above
1.40 mAh. However, an excess amount of H2O will increase
parasitic electrochemistry, even if the Li anode is protected by a
LICM. They further proposed an organic peroxide compound
urea hydrogen peroxide, which avoided the need for addition of
H2O, successfully lowering the charge potential to 3.26 V with
Li2O2 as the product in a non-aqueous Li–O2 battery.
Not only water but also other additives can be used to
induce the solution pathway of Li2O2 growth. The free energy of
dissolution for LiO2* into Li+(sol) and O2−(sol) in different solvents
is shown as a function of the Gutman AN and DN in Figure 4e.
The free energy plot is normalized relative to that of pure DME.
DMF, dimethyl acetamide (DMAc), and DMSO have high DNs
and are thus capable of stabilizing Li+. In contrast, water and
methanol have high ANs and thus stabilize O2−. It is predicted
that solvents or additives that fall in the top-right quadrant of this
plot will favor solution-mediated deposition of Li2O2, which will be
essential for high-capacity Li–O2 batteries. This provides a
directional reference for further exploration of additives and
solvents for Li–air battery systems.
3. Ionic liquid electrolytes
IL electrolytes are a class of non-aqueous liquid electrolyte.
However, they are distinct from the above aprotic solvents
because of their molten salt characteristics. Considering the
limited application value of high-temperature molten salts, room-
temperature ionic liquids (RTILs) are focused on in this section.
Different from aprotic solvents, RTILs have negligible vapor
pressure, which can effectively solve the problem of electrolyte
evaporation in open systems. RTILs also ensure safety because
of their wide electrochemical window, low flammability, and high
chemical/electrochemical and thermal stabilities. In addition,
some RTILs are highly hydrophobic, which is helpful to inhibit
the corrosion of the Li anode of Li–air batteries in an open
atmosphere. In Figure 5, examples of commonly used IL cations
and anions, as well as solvate IL electrolytes are presented, their
main performance in Li–air battery compared with aprotic
electrolytes are evaluated.
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3.1. RTIL electrolytes in Li–air batteries
The O2/O2− couple has been proved to display reversible
ORR/OER behavior in RTILs.[105-107] Kuboki et al.[108] first used
the imidazolium-based RTIL 1-methyl-3-octylimidazolium
bis(trifluoromethylsulfonyl)-amide (EMITFSI) into an Li–air
battery. The battery worked for 56 days in air, and showed a
particularly high capacity of 5360 mAh g−1. After this promising
result, a variety of RTILs combined with different kinds of cations
and anions were used in Li–air batteries, as shown in Figure 5.
Perfluoroalkanes such as bis(fluorosulfonyl)imide (FSI−),
bis(trifluoromethanesulfonyl)imide (TFSI−),
(trifluoromethanesulfonyl) (nonafluorobutanesulfonyl)imide
(IM14−), and bis(pentafluoroethylsulfonyl)imide (BETI−) are the
most used anions, owing to their ability to dissolve O2. RTILs
with the IM14− anion do not crystallize because of its high
asymmetry, but instead display rather high viscosity.[109, 110] The
FSI− anion can lower the viscosity and improve the conductivity
of RTILs, but at the cost of thermal stability.[111, 112] The cations of
RTILs are mainly imidazolium, pyrrolidinium, piperidinium, and
quaternary ammonium-based tetraalkylammonium units such as
1-ethyl-3-methylimidazolium (EMI), 1-butyl-3-methylimidazolium
(BMI), N-methyl-N-butyl-pyrrolidinium (PYR14), N-methyl-N-
propylpiperidinium (PP13), N,N-diethyl-N-methyl-N-propyl-
ammonium (N1223).[108, 113-117] Notably, RTILs with ether-
functionalized cations show higher conductivity, lower viscosity,
and better thermal behavior than their analogues.[118-120] For
example, RTILs containing the N-methyl-N-
methoxyethylpyrrolidinium (PYR12O1+) cation have higher
conductivity and lower viscosity than those with the PYR14
cation. In addition, PYR12O1+ displayed high LiOx generation
activity to realize superior O2 supply capability in Li–air battery
applications.[121] Among various RTILs, pyrrolidinium and
piperidinium cations are more stable than imidazolium and
quaternary ammonium cations in Li–air batteries, as confirmed
by DEMS tests.[122] In particular, N-methyl-N-butyl-pyrrolidinium
bis(trifluoromethansulfonyl)amide (PYR14TFSI) shows better
stability and higher performance than DME as the electrolyte of
Li–air batteries. Batteries using PYR14TFSI showed a stable
electrolyte–electrode interface, improved reversibility, and low
overpotential, exceeding the performance of aprotic
electrolytes.[115] However, PYR14TFSI is still susceptible to
decomposition in the presence of reactive O2 species.[123, 124]
The development of RTILs for use in Li–air batteries is at the
initial stage, and the electrochemical process in such batteries is
still not clear. Further investigation is required to find stable
RTILs. In addition, it is essential to determine the reasons for the
different behavior of RTILs in Li–air batteries, including the
inherent influence of the type of RTIL and the extrinsic effects of
various impurities.
The RTILs developed to date possess the following
disadvantages. (1) RTILs have low salt solubility and poor Li+
mobility, which hinder the formation of an SEI layer on the
surface of the Li anode and limit the rate performance of the
battery. (2) The O2 diffusivity coefficients of RTILs are almost
one order of magnitude lower than those of DME and DMSO,
further limiting the capacity of Li–air batteries.[125] (3) It is difficult
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10.1002/anie.201903459
for RTILs to effectively infiltrate the surface of the electrode
because of their high viscosity, which leads to large mass
transfer resistance and high interface polarization voltage. (4)
The high cost of RTILs also limits their commercial application.
The operating temperature affects the Li+ mobility in RTIL-
based electrolytes. Reports have indicated that the diffusivity of
Li+ increases with temperature in RTILs because of the
suppression of Li+-limited cluster formation.[126] Atomistic
calculations revealed that transport properties, not only Li+
diffusivity but also O2 solubility, are promoted in RTIL electrolytes
at higher operating temperatures. This behavior is quite different
from that of common aprotic electrolytes, where the solubility of
O2 decreases with rising temperature.[127] This means that RTILs
Accepted Manuscript
may work better than aprotic electrolytes in Li–air batteries at
high temperature.
3.2. RTIL-based mixed solvents
RTILs are often mixed with other RTILs or aprotic solvents in Li–
air batteries to make up for their disadvantages. For example,
the 4:1 BMITFSI:PYR14TFSI mixed RTIL showed lower
resistance and lower overpotential compared with those of the
pure RTILs when used in Li–air batteries.[128] Moreover, mixing
aprotic solvents with RTILs is a promising approach to minimize
the drawbacks and combine the best features of each
solvent.[129, 130] Different imidazolium-based RTILs such as
BMITFSI, BMIPF6, and BMIBF4 were combined with DMSO to
study their ORR/OER performance with and without O2.[131] The
mixed electrolytes exhibited enhanced ORR/OER cycling ability
and higher ORR current density than those of DMSO or the RTIL
alone. This is because of the improved O2 solubility and diffusion
coefficient in the mixed electrolytes. Meanwhile, a
PYR14TFSI/TEGDME mixed electrolyte exhibited enhanced
kinetics with low overpotential compared with those of the pure
TEGDME electrolyte.[132] Interestingly, a single-electron
mechanism was observed for a mixture of PYR14TFSI and DME
during the charging process.[133] PYR14TFSI stabilized the O2−
species and promoted the single-electron reaction, which
lowered the overpotential to 0.19 V. Recently, a mixed
EMIBF4/DMSO (25%/75%) electrolyte was used in a well-
designed Li–air battery with an MoS2 cathode and protected Li
anode.[134] The components of this system operated in
conjunction to achieve a long cycle life of over 550 cycles under
simulated air conditions with a capacity of 500 mAh g−1 and a
constant current density of 500 mA g−1. The RTIL-based mixed
electrolyte accompanied with the protected Li anode was
beneficial to prevent the formation of side products in the
presence of CO2 and H2O.
3.3. Solvate ionic liquid electrolytes
Equimolar mixtures of glyme and Li salt are liquid and their
physicochemical properties are similar to those of conventional
RTILs; for example, low flammability, low volatility, wide potential
window, high Li+ conductivity, and high Li+ transference number.
Therefore, these mixtures can be regarded as a new subclass of
IL called solvate ILs.[135] Glymes such as triglyme and TEGDME
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REVIEW
tend to form one-to-one complexes with Li+, providing new
complex cations with the structure [Li(glyme)]+. The [Li(glyme)]+
complexes behave as independent cations, similar to the cations
of typical RTILs, and can be used in Li–air batteries to achieve
the combined advantages of RTILs and aprotic solvents. Solvate
ILs provide a platform for the design of advanced electrolyte
systems.[136-139]
The [Li(triglyme(G3))1][TFSI] solvate IL was used as the
electrolyte of a rechargeable Li–air battery. This battery showed
reversible ORR and OER characteristics, which was analogous
to that of batteries with aprotic electrolytes. [140] An
[Li(TEGDME(G4))1][TFSI] solvate IL showed quasi-reversible
ORR and OER behavior and high oxidative stability up to 4.5 V
vs. Li/Li+.[141] However, subsequent work revealed that the
presence of water markedly deteriorated the reversibility of the
Li–air battery. To prevent moisture intrusion from ambient air,
several hydrophobic electrolytes were designed by mixing the
solvate ILs with other hydrophobic ILs. The moisture content in
the electrolyte exposed to ambient air was greatly suppressed
and the reversibility of the Li–air battery was improved using this
design. Adams et al.[142] proposed a new lithium ether-derived
chelate using a methyl-substituted 2,3-dimethyl-2,3-
dimethoxybutane (DMDMB) complex with LiTFSI to form a
stable [(DMDMB)2Li]TFSI salt for use in Li–O2 batteries. This salt
is compatible with Li anodes and its ether-based framework is
more stable against O2−-initiated hydrogen abstraction than
simple glymes.
4. Solid-state electrolytes
There are numerous challenges associated with current Li–air
battery technology that have impeded their operation as open
systems, especially safety issues associated with the
evaporation of flammable aprotic electrolytes and Li dendrite
growth on the Li anodes. Therefore, it is important to develop
batteries with both high safety and high energy density to satisfy
industrial demands. Solid-state electrolytes are attracting
considerable interest because they are more suitable than liquid
electrolytes for use in open systems. Compared with non-
aqueous liquid electrolytes, they are not prone to volatilization or
leakage. Benefiting from the intrinsic solid characteristics (high
Young's modulus) of solid-state electrolytes, lithium dendrite
growth and internal shorting can be suppressed.[143] The problem
of lithium metal corrosion by moisture, CO2, and reactive O2
species can also be suppressed by using a solid electrolyte to
protect the Li metal from contact with air.
High-performance solid-state electrolytes for Li–air batteries
should meet the following criteria: (1) Chemical stability and
compatibility with the Li anode or cathode material. (2) Wide
electrochemical window to protect against irreversible reactions.
(3) Thermal and mechanical stability during charge and
discharge processes. (4) Low ionic area-specific resistance, high
electronic area-specific resistance, and high total (bulk + grain
boundary) Li+ conductivity (σ > 10−3 S cm−1) at room
temperature. (5) Compatible with O2•− and Li oxide species such
as LiO2 and Li2O2. (6) Simple fabrication process, low cost, easy
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10.1002/anie.201903459
device integration, and environmentally friendly.[144]
In Figure 6, the solid matrixes of solid-state electrolytes are
divided into Li+-conducting solid electrolytes and passive fillers.
Solid polymer electrolytes (SPEs) and solid inorganic
electrolytes (SIEs) are both types of solid electrolytes. However,
their low ionic conductivity and high interfacial impedance limit
the performance of Li–air batteries containing these electrolytes.
To further improve the ionic conductivity of solid electrolytes,
complex formulations have been developed. For example, two
or more solid matrixes have been hybridized to form solid
composite electrolytes. One or more solid matrix can be
composited with a non-aqueous liquid electrolyte such as an
aprotic solvent or RTIL to develop solid–liquid composite
Accepted Manuscript
electrolytes that combine the high Li+ conductivity of non-
aqueous liquid electrolytes and good mechanical properties of
solid matrixes.
4.1. Solid matrixes
Solid matrixes include solid electrolytes and passive fillers. In
solid electrolytes, Li+ are bonded with a solid matrix such as a
polymer or inorganic ceramic.
4.1.1. Solid polymer electrolytes
SPEs are composed of polymers and Li salts. Polymers such as
PEO, poly(methyl methacrylate) (PMMA), poly(vinylidene
fluoride) (PVDF), PVDF-HFP, poly(tetrafluoroethylene) (PTFE),
and PAN are widely used in Li–air batteries. SPEs are suitable
for most battery systems because of their ability to tolerate the
volume change of batteries during the charge and discharge
processes.[145] This characteristic and their additional benefits of
scalability and processability are helpful to develop flexible
batteries for consumer electronics, implantable medical devices,
and wearable electronics.[146]
SPEs face three main challenges that need to be solved for
their use in Li–air batteries. The first challenge is the crystallinity
of the polymer. Polymer crystallization is detrimental for ion
transport because the slowed polymer chain dynamics results in
low Li+ conductivity (10−8 to 10−4 S cm−1) at room temperature.
The crystallization of polymer chains can be suppressed by
synthetic approaches such as cross-linking and
copolymerization. Crystallization can also be suppressed by
raising the temperature. For example, a Li–O2 battery containing
PEO-based electrolytes operated at 80 °C showed a low
overpotential of 480 mV and a comparable discharge specific
capacity to that of glyme-based Li–air batteries. [147] The second
challenge is the lack of an active reaction zone in a thick SPE
layer and the lack of O2 gas diffusion pathways to the cathode. A
new design consisting of a three-dimensional (3D) structure that
incorporated with CNTs and PEO has been developed. [148] This
3D CNT/PEO SPE has numerous void spaces to provide active
reaction zones to promote interaction of Li+, O2, and electrons.
The third and the most fatal limitation of SPEs is the
decomposition of the polymer matrixes in Li–air batteries under
the harsh operating conditions; for example, at high voltage,
highly reactive O2 species including O2, O2−, LiO2, and Li2O2 are
produced that can degrade SPEs. The serious decomposition of
SPEs during the charge and discharge processes would result in
batteries with a high overpotential and short cycle life. The
Angewandte Chemie International Edition
REVIEW
stability of polymers against Li2O2, O2−, and Li2O have been
evaluated by spectroscopic analysis using methods such as
ultraviolet–visible (UV-vis) spectroscopy, Fourier transform
infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and X-ray
photoelectron spectroscopy (XPS).[149-151] Those analyses
revealed signs of decomposition for commonly used polymers in
contact with O2− and Li2O2 induced by nucleophilic attack and
possible surface reactions. Yang et al.[152] studied the stability of
PEO in O2 using DEMS. Their results confirmed that PEO is
prone to auto-oxidation in the presence of O2, which leads to the
instability of PEO in Li–air batteries.
Thus, the stability of SPEs in Li–air batteries still needs to be
further improved. The hydrogen atoms that are adjacent to
electron-withdrawing groups in polymers are vulnerable to attack
by reactive O2 species in Li–air batteries, leading to polymer
decomposition, which will negatively affect the chemistry and
long-term performance of Li–air batteries. Replacing some of the
labile hydrogen atoms in the polymer chains with other
functional groups or side chains is helpful to lower the number of
potential reaction pathways for nucleophilic attack during battery
operation. Antioxidants such as sterically hindered phenol or
amine stabilizers, can be added to suppress the deterioration of
polymer electrolytes.[153, 154]
4.1.2. Solid inorganic electrolytes
SIEs are promising to allow development of safe Li–air batteries
with high energy density. SIEs have higher Li+ conductivity,
better thermal, chemical, and electrochemical stability compared
with the behavior of SPEs. The Li+ conductivities of different
SIEs have been widely studied. However, their stability in
contact with Li anodes is the primary issue for large-scale
applications of Li–air batteries. Their stability against moisture
and air should also be considered to assess their potential for
use in open systems.
As presented in Figure 7, Li+ conductivity of different
inorganic solid electrolytes and their stability with Li, moisture
and air are sorted out for comparison. Among these inorganic
matrixes, oxides such as NASICON, perovskite, antiperovskite
and garnet that exhibit good Li+ conductivity and relatively high
stability are promising to develop SIEs for use in Li–air batteries.
Perovskite and antiperovskite-type solid matrixes show relatively
low total conductivity because of their high grain boundary
resistance. Thus, NASICON and garnet-type SIEs are more
applicable for Li–air battery.
NASICON-type oxides are the most promising SIE for Li–air
batteries because of their high conductivity at room temperature,
stability towards moisture and air, relatively low sintering
temperature, and easy large-scale synthesis.[155] The main
drawback of NASICON-type Li1+xAlxTi2−x(PO4)3 (LATP) solid
electrolytes is that Ti4+ is reduced when is direct contact with Li
metal.[156] Ti is not suitable as a constituent of solid electrolytes
from the aspect of thermodynamics. The degradation of solid
electrolytes in contact with Li metal and the formation of thin
reaction layers is similar to the formation of an SEI layer in liquid
electrolytes from a conceptual point of view.[157] An Li+
conducting interlayer composed of a material such as Li3N,
aprotic solvent, or polymer electrolyte should be added between
the Li electrode and LATP.[158-160] Li1+xAlyGe2−y(PO4)3 (LAGP) is
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10.1002/anie.201903459
supposed to be stable in contact with Li metal, but a Ge4+-
related reduction reaction was also reported.[156, 161] Zhou et
al.[162] coated an amorphous Ge0 thin film on an LAGP surface
by sputtering. The Ge0 thin film effectively suppressed the
reduction reaction of Ge4+ and facilitated intimate interfacial
contact between the Li metal and LAGP. A quasi-solid-state
lithium–air battery with this Ge0 film-coated LAGP SIE operated
for 30 cycles in ambient air at a current density of 200 mA g−1
and discharge capacity of 1000 mAh g−1.
Solid-state batteries contain solid–solid interfacial contacts
between the electrolyte and electrodes. Different from non-
aqueous liquid systems, in which the air electrode is fully wetted
by electrolyte, the air electrode of all-solid-state Li–air batteries
Accepted Manuscript
should be integrated with the solid electrolyte to form a spatial
network structure to allow the contact of electrons, Li+, and
O2.[163] An integrated structure of electrolyte and electrode is a
feasible strategy to solve the problem of poor interfacial
contact.[164] An integrated structure was fabricated by coating an
LATP solid electrolyte membrane on the surface of a pre-
sintered air cathode that contained LATP powder and 75%
porous carbon (Figure 8a–d).[165] The Li–O2 battery based on
this integrated structure delivered a rechargeable capacity of
16800 mA h g−1 in the first cycle at 0.1 mA cm−2. In this
integrated structure, the triple-phase boundaries were expanded
from the conventional electrolyte–cathode interface to the entire
solid-state cathode (Figure 8e). A silicone-oil film was coated on
the pores of the integrated air electrolyte to block water vapor
and CO2 from reaching reaction sites and allow a high rate of O2
transfer because of the increase of the specific surface area of
the films. This integrated structure of electrode and electrolyte
offers a route to develop solid-state Li–air batteries that can
operate in ambient air and have low O2 transfer resistance.[166]
Garnet-type oxides are the only materials that
simultaneously exhibits relatively high conductivity and appear
compatible with Li metal among high-performance solid
electrolytes.[167, 168] The fatal drawbacks of garnet-type solid
electrolytes for open Li–air batteries is that they are unstable
towards moisture and CO2, and they have high interfacial
resistance due to their poor adhesion with electrodes.[169-171]
Garnet is sensitive to moisture and CO2, which promote the
formation of a thick Li2CO3 layer and Li-Al-O glass phase on the
surface of garnet, as well as protons in the garnet framework.
These impurities induce large resistance at the interfaces
between the garnet SIE and electrodes. Generally, surface
polishing processes such as dry polishing using sandpaper, wet
polishing using an automated polisher with polishing fluid, and
heat treatment are used to remove the Li2CO3 from LLZO.[172]
Recently, Goodenough and colleagues proposed a carbon post-
treatment to remove the Li2CO3 and protons and decrease the
amount of Li-Al-O glass phase in the garnet.[173] Moreover, when
the battery was deeply discharged, the consumed Li metal left
gaps between the Li metal and solid electrolyte. The resulting
interface separation and battery deformation problems are also
particularly prominent in solid-state Li–air battery systems. An
intermediate layer is often included to enhance the adhesion
between garnet SIEs and Li electrodes. Lithiophilic materials
such as Si, Ge, ZnO, and Al2O3 or polymers such as PVDF-HFP
Angewandte Chemie International Edition
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and PEO are sandwiched at the interface to decrease the
interfacial resistance.[169, 174-176] An Li-Sn alloy layer was
demonstrated to lower the interfacial resistance by
approximately 20 times.[177] This layer facilitated fast and stable
Li transport at high current densities. Interestingly, Chen et al.[178]
enhanced the interfacial connection between garnet SIEs and Li
electrodes by simply drawing a graphite-based soft interface
with a pencil. Sun et al. reported a solid-state Li–air battery with
a garnet-type LLZTO SIE. They synthetized a composite
cathode consisting of garnet powder, Li salt (LiTFSI), active
carbon, and polypropylene carbonate binder to reduce the
interfacial resistance. This battery showed a high density (20300
mAh g−1carbon) and was cycled 50 times at 20 μA cm−2 and 80 °C
while maintaining a capacity of 1000 mAh g−1carbon (Figure 8f-
h).[179]
4.1.3. Passive fillers
Different from solid electrolytes that can contribute to
conduction, passive ceramic fillers including Al2O3, SiO2, TiO2,
ZrO2, and B2O3 are used to achieve high ionic conductivity and
improve the mechanical strength of solid-state electrolytes.[180-
182]
Passive ceramic fillers are widely used in solid composite
electrolytes and solid–liquid composite electrolytes to improve
their performance via a classical doping mechanism or space-
charge mechanism. In solid composite electrolytes, the
enhancement in ionic conductivity is attributed to the inhibition of
crystallization in the polymer phases. In solid–liquid composite
electrolytes, the functionalized passive ceramic fillers with
functional groups grafting on their surface can promote the
dissociation of lithium salts, which is beneficial to increase the
amount of free Li+ in the electrolyte.[183, 184] The ionic transport in
these electrolytes appears to occur along the surface of the
fillers or through the interfacial region. Other materials such as
CNTs, graphene, microporous molecular sieves, zeolites, and
metal–organic frameworks with specific structures and
components can also serve as passive fillers to elevate the total
conductivity of solid-state electrolytes by providing low-energy
conduction paths.[185-187]
4.2. Solid composite electrolytes
SPEs, SIEs, and passive filler can be hybridized with each other
to form solid composite electrolytes. Solid composite electrolytes
can display the advantages of their respective components and
compensate for each other’s drawbacks. Passive fillers such as
ZrO2, Al2O3, SiO2, TiO2, or anion traps have been doped with
SPEs to improve their conductivity and electrochemical stability.
Nanometer-sized ceramic powders can behave as solid
plasticizers for PEO, kinetically inhibiting the crystallization on
annealing. The conductivity of a PEO SPE was improved by an
order of magnitude to about 10−4 S cm−1 at 50 °C and 10−5 S
cm−1 at 30 °C upon the addition of TiO2 and Al2O3 passive filler
nanoparticles.[188] Cui et al.[189] introduced passive SiO2 fillers
into PEO to enhance the chemical/mechanical interactions of
this resulting electrolyte. As a result, the electrolyte displayed
good ionic conductivity (1.2 × 10−3 S cm−1 at 60 °C and 4.4 ×
10−5 S cm−1 at 30 °C) and enhanced electrochemical stability,
enduring up to 5.5 V vs. Li+/Li without marked decomposition.
SIEs can provide Li+ transport channels in SPEs to enhance
This article is protected by copyright. All rights reserved.
10.1002/anie.201903459
Li+ conductivity. Cui’s group used 15 wt% LLTO ceramic as a
filler for PAN.[190] They reported that LLTO ceramic nanofibers
were more favorable to obtain high conductivity than
nanoparticles. This is because the nanofiber shape facilitated
formation of Li+ conduction networks in the PAN-based solid
electrolyte. This electrolyte exhibited an unprecedented ionic
conductivity of 2.4 × 10−4 S cm−1 at room temperature. The
ceramic nanowires acted as a conductive network in the polymer
matrix, allowing rapid ion transport on its surfaces. Goodenough
et al.[191] developed a series of low-cost composite
ceramic/polymer solid electrolytes that ranged from ―ceramic in
polymer‖ to ―polymer in ceramic‖. They used garnet
Li6.5La3Zr1.5Ta0.5O12 (LLZTO) as the ceramic, PEO as the
Accepted Manuscript
polymer, and LiTFSI as the salt. Both kinds of solid composite
electrolytes showed promise for use in all-solid-state Li–air
batteries. As well as improved conductivity, the PEO–LLZTO
composite electrolytes showed enhanced interfacial stability
against Li electrodes and effectively suppressed Li dendrite
growth, which was attributed to the mechanically robust and
stable framework provided by PEO and stable chemical and
electrochemical performance of LLZTO. [192]
4.3. Solid–liquid composite electrolytes
Another branch of solid-state electrolyte research is solid–liquid
composite electrolytes, which are composed of at least one non-
aqueous liquid electrolyte and one or more types of solid matrix.
This kind of electrolyte combines the fluidity of non-aqueous
liquid electrolytes and high mechanical strength of solid
electrolytes.
4.3.1. Aprotic electrolytes and solid matrixes
A typical example of this kind of electrolyte is a gel polymer
electrolyte (GPE). SPEs can be swollen considerably with
aprotic electrolytes (plasticizers) to form GPEs with low
crosslinking density.[193, 194] These GPEs combine the ideal
mechanical properties of a swollen polymer network with the
high ionic conductivity and good interfacial properties of liquid
electrolytes.[195] As one of the most important polymer electrolyte
matrixes, PVDF-HFP-based GPEs have been widely applied to
Li–air batteries. PVDF-HFP-based GPEs show benefits
including high solubility, low crystallinity, and favorable
electrochemical/mechanical properties. This kind of GPE has
great application prospects in long-life Li–air batteries. A free-
standing GPE with a PVDF-HFP matrix and TEGDME plasticizer
was fabricated for use in Li–O2 batteries.[196] The GPE exhibited
a wide operating window and acceptable ionic conductivity (1.0
× 10−3 S cm−1). Li–O2 batteries containing the GPE sported a
high initial discharge capacity of 2988 mAh g−1 and long cycle
life of at least 50 cycles (compared with 20 cycles for the
reference TEGDME-based electrolyte). To further improve Li+
conductivity and stability, a GPE membrane was fabricated using
a blend of cellulose acetate and PVDF-HFP, followed by
impregnation with 1 M LiTFSI/TEGDME solution.[193] This GPE
membrane showed good electrolyte absorption capacity, high
ionic conductivity (5.49 × 10−1 S cm−1) as well as excellent
thermal and electrochemical stabilities. Moreover, it effectively
restrained the diffusion of O2 from the cathode zone to the Li
metal anode, which lengthened the cycle life of the Li–air battery
Angewandte Chemie International Edition
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with this membrane.
To meet the growing need for flexible batteries for wearable
devices, a fiber-shaped Li–air battery with a GPE and aligned
CNT sheet air electrode was developed via UV irradiation.[146]
The GPE was coated on Li wire by of a precursor solution
containing LiTF, TEGDME, PVDF-HFP, NMP, 2-hydroxy-2-
methyl-1-phenyl-1-propanone, and trimethylolpropane
ethoxylate triacrylate. The battery exhibited a discharge capacity
of 12470 m Ah g−1 and could work stably for 100 cycles in air. As
shown in Figure 9, the electrochemical performances of this
battery were well maintained after bent, twisted and even
immersed in water. [197] Because of its high electrochemical
performance and flexibility, this kind of GPE-based Li–air battery
is very promising to form wearable and flexible power textiles for
various electronic devices. Wang et al.[198] prepared a long-life
Li–air battery that operated in ambient air using a PVDF-HFP-
based GPE containing 0.05 M LiI. Li passivation induced by air
was efficiently alleviated using the hydrophobic GPE.
Furthermore, the reversible conversion of the OERM (I−/I3−)
lowered the polarization on charge and increased the
charge/discharge efficiency of the Li–air battery, which showed
reproducible voltage curves with almost no capacity fade for 400
cycles.
4.3.2. RTIL electrolytes and solid matrixes
Electrolytes consisting of a combination of RTIL electrolytes and
solid matrixes are also called ionogel electrolytes. An emerging
trend in RTIL research is to combine the fluidity of RTILs and
high mechanical strength of solid matrixes as well as give full
play of their safety.[199, 200] Ionogels are promising for use in Li–
air batteries because they can effectively prevent the formation
of dendrites due to their high mechanical modulus, regulate Li+
transport through the electroosmotic flow in nanopores, and
protect the Li electrode from reacting with reactive O2 species
and humidity.[201]
A hydrophobic RTIL 1,2-dimethyl-3-propylimidazolium
bis(trifluoromethanesufonyl)imide was used to form a composite
with LiTFSI, SiO2, and PVDF-HFP and then applied in Li–air
batteries.[202] The composite electrolyte showed long-term
durability and high ionic conductivity (1.83 × 10−3 S cm−1 at room
temperature), which were attributed to the interactions between
all the components. Another ionogel electrolyte consisting of a
PVDF-HFP-based polymer matrix, pyrrolidinium-based RTIL
(PYR14TFSI), and lithium salt (LiTFSI) was fabricated and then
used in an Li–O2 battery.[203] The battery (Figure 10a) operated
successfully with a discharge capacity of 72 mA h−1 with
reversible Li2O2 formation and decomposition at a current
density of 0.25 mA cm−2 (Figure 10 b–d). The Li–O2 battery
could be operated at a capacity of 10 mA h−1 for at least 30
cycles, but a side reaction involving the abstraction of fluorine
via dehydrofluorination was observed.
Zhou et al.[204] developed a water-resistant quasi-solid ionogel
electrolyte using a superhydrophobic SiO2 matrix combined with
an Li+-conducting RTIL (0.5 M LiTFSI dissolved in 1-methyl-3-
propylimidazolium bis(trifluoromethylsulfonyl)imide). This ionogel
electrolyte effectively suppressed H2O crossover from the
cathode to the Li anode and delivered good thermal stability,
stable mechanical strength, high ionic conductivity (0.91 × 10−3 S
This article is protected by copyright. All rights reserved.
10.1002/anie.201903459
cm−1), and wide voltage window (>5.5 V). Furthermore, the Li–air
battery with this ionogel electrolyte could be operated in a humid
atmosphere safely for a long time, which is a far better result
than that achieved using liquid electrolytes.
5. Hybrid and aqueous electrolytes
Although the theoretical energy densities of hybrid and aqueous
Li–air batteries are lower than those of non-aqueous Li–air
batteries, a higher system-level energy density can be
anticipated for batteries with hybrid and aqueous electrolytes
because of the elimination of extra components that are needed
Accepted Manuscript
to operate the batteries in a pure O2 atmosphere. To achieve
practical application of hybrid and aqueous Li–air batteries, there
are endless avenues yet to be explored.[205] In the case of
electrolytes for hybrid and aqueous electrolytes, the challenges
include maintaining the long-term stability of the Li anode
against H2O and avoiding LiOH precipitation in the cathode.
Thus, developing stable LICMs and buffer layers with high
conductivity and adjusting the pH of the acidic/alkaline aqueous
electrolyte over a reasonable range are promising research
directions.[30]
5.1. Li+-conducting membranes
The most successful LICMs in hybrid and aqueous Li–air
battery are the commercially available NASICON-type glass-
ceramic LATP/LAGP LICMs, which possess high conductivity,
good chemical and thermal stabilities, as well as good
mechanical strength.[206] Other Li+-conducting solid electrolyte
materials used in solid-state Li–air batteries such as perovskite-
type LLTO, garnet-type LLZO, and single-crystal Si wafers are
also promising as LICMs for hybrid and aqueous Li–air batteries.
However, there are several problems associated with the
chemical stability of LICMs. Most oxides tend to dissolve in
strongly acidic or alkaline solution, which narrows the acceptable
pH range of aqueous electrolytes. NASICON-type materials,
perovskite-type materials, and single-crystal Si wafers are
unstable in direct contact with Li anodes, which necessitates the
introduction of buffer layers and further increases the internal
resistance, cost, and safety issues of aqueous Li–air batteries.
Unfortunately, garnet-type materials are unstable in water
despite their stability towards Li anodes. The development of
LICMs should be aided by the knowledge base of solid-state
electrolytes, which has been summarized in Section 4.
5.2. Acidic and alkaline electrolytes
Aqueous electrolytes are composed of water, acid/base, and
supporting salts. As summarized in Equation (13) and (14), the
cell reactions of aqueous Li–air batteries are different depending
on the pH of their aqueous electrolytes. Different aqueous
electrolytes also result in various energy densities. As listed in
Table 3, assuming that all discharge products are dissolved, the
highest theoretical energy density of 1169.29 Wh kg−1 can be
achieved by using a strongly acidic solution of hydrochloric acid
(HCl).[207]
Unfortunately, strong inorganic acids could degrade LICMs.
Accordingly, weaker acids such as acetic acid (CH3COOH) and
Angewandte Chemie International Edition
REVIEW
phosphoric acid (H3PO4) are favored in hybrid and aqueous Li–
air batteries, which also lack CO2 ingression and LiOH
precipitation problems compared with the case for batteries with
alkaline electrolytes. However, CH3COOH is volatile, so it should
be stored in a closed system, and its pH is too low for LATP.
Moreover, corrosion and an increase in the bulk or grain
boundary resistances of LATP still occur when H3PO4 solution
alone is used as the aqueous electrolyte. The addition of
conjugate bases such as lithium acetate (with CH3COOH) and
Lithium dihydrogen phosphate (LiH2PO4) (with H3PO4) is helpful
to suppress the dissociation of weaker acids and increase the
pH of the aqueous electrolyte, which will eventually protect the
LICMs.[208] Other polyprotic organic acids such as malonic acid
and citric acid have also been added to aqueous electrolytes to
increase the discharge capacity (even higher than that for
hydrochloric acid), and delay the generation of insoluble
discharge products. An aqueous Li–air battery with a malonic
acid electrolyte operated for 77 cycles at an area-specific
capacity of 5 mAh cm−2 with discharge and charge rates of 1 mA
cm−2 (C/5) and 0.5 mA cm−2, respectively.[209] This converted to a
total cycle capacity of 385 mAh cm−2, which is a high cycle
capacity for reported Li–air batteries.
Another strategy is to deposit a Li+-conducting polymer on
the LICM to avoid direct contact of the solid electrolyte with the
acidic solution. In addition, strong acids can be used in hybrid
and aqueous Li–air battery electrolytes when accompanied by
imidazole, which acts as a protons reservoir in water, as
presented in Figure 11 (a–h).[210] However, imidazole-buffered
electrolytes are not stable at high voltages because the
imidazole will be oxidized prior to water splitting during the
charging process.[26]
The supporting salts of alkaline electrolytes include LiOH,
LiClO4, LiNO3, and LiCl.[211] Among them, LiOH is the most
utilized supporting salt because it can not only provide Li+ for cell
operation but also create an alkaline environment to promote the
ORR on non-noble metal catalysts.[212] A high concentration of
Li+ is preferred to increase the conductivity of alkaline
electrolytes. However, when LiOH is used alone, the alkalinity of
the alkaline electrolyte will be too high and the LICM will be
brittle with large resistance. Therefore, the addition of other
supporting salts such as LiClO4, LiCl, and LiNO3 is necessary to
provide a high concentration of Li+ and keep the low pH at the
same time. LiCl and LiNO3 are hygroscopic salts that can
scavenge H2O from the atmosphere during battery operation,
alleviating the need for quantitative addition of water for the
battery reactions. However, alkaline electrolytes with a high
concentration of LiCl suffer from several drawbacks such as Cl2
evolution, low practical energy density, and the limited solubility
of the discharge product LiOH.
The biggest problem facing alkaline electrolytes is the
precipitation of LiOH as a monohydrate (LiOH·H2O) with low
solubility and insulating character, which can clog the pores of
the cathode, similar to the accumulation of insoluble Li2O2 in
non-aqueous Li–air batteries, and block O2 diffusion. One way to
solve this problem is to develop a flow-through operating system
to keep a low concentration of LiOH in fresh alkaline electrolyte
(Figure 11i).[213-215] Another problem is the production of insoluble
This article is protected by copyright. All rights reserved.
10.1002/anie.201903459
Li2CO3 derived from the reaction of the alkaline electrolyte with
CO2 (from air), which will block the active surface of the catalyst
particles. A soda-lime filter device can be added on the cathode
side to eliminate CO2 from open air. The deposition of an anion-
conducting polymer layer between the cathode and aqueous
electrolyte can also help to solve the above two problems. A
polymer layer can prevent the CO2 in the air from entering the
aqueous electrolyte. A polymer layer can also conduct OH−
formed during the ORR process, suppressing the precipitation of
LiOH on the surface of cathode.[216]
6. Conclusions and outlook
Accepted Manuscript
In this review, we discussed recent studies and current
understanding of the electrolytes developed for different kinds of
rechargeable Li–air batteries. The electrolyte plays a critical role
in the performance of Li–air batteries. A minor change in the
electrolyte could lead to dramatic difference in the internal
mechanism and further affect the battery performance.
For non-aqueous liquid systems, different types of solvents,
lithium salts, additives have been discussed for their effects on
the performance of Li–air batteries. While single components
have limited impact on the performance improvement of lithium
air batteries, and most of them have corresponding side
reactions and decomposition issues.[217] Therefore, the design of
Li–air battery electrolyte needs to regard the electrolyte as a
whole system. For example, solvents with low DN exhibit high
stability, but result to low discharge capacity in Li–air batteries. In
that case, highly associated Li salt, ORRMs or a trace amount of
water can be used to promote the formation of large amount of
toroidal-shaped Li2O2, thereby increasing the discharge capacity
of Li–air battery. Furthermore, OERMs are very helpful to
decompose the large Li2O2 toroidal particles at a low charge
potential, thereby improving the energy efficiency and cycle
performance of the battery. Volatile electrolytes are not suitable
for use in open systems. RTILs and solvate ILs are promising
candidates to volatile aprotic solvents in open system. Mixed
solvents combine the merits of different solvents and sometimes
display synergistic effects. A large number of combinations are
possible given the enormous amount of aprotic solvents and
designable RTILs.[218] In addition, the concentrations of Li salts
and additives related to the formation of stable SEI layers
require further optimization.[219] Novel solvents, Li salts and
additives should be discovered inspired by continuous
innovation work.[220]
Solid-state electrolytes have great potential for use in Li–air
batteries to realize open systems with good safety and high
energy density. SPEs such as PVDF-HFP, PEO, and PMMA as
well as SIEs such as NASICON and garnet are considered
promising solid electrolytes for Li–air batteries. However, their
ionic conductivity and stability still need to be improved. Solid
composite electrolytes have been developed to display the
advantages and overcome the drawbacks of two or more solid
matrixes including SPEs, SIEs, and passive fillers. Because
research in this direction is still at the initial stage, all-solid-state
Li–air batteries using solid electrolytes or solid composite
Angewandte Chemie International Edition 10.1002/anie.201903459

REVIEW

electrolytes still face many challenges; for instance, limited ionic

conductivity and stability, and poor interface chemistry with the Jingning Lai is currently a Ph.D. candidate
electrodes. Solid–liquid composite electrolytes combine the supervised by Professor Renjie Chen in School of
fluidity of non-aqueous liquid electrolytes with the favorable Materials Science and Engineering, Beijing
mechanical properties of solid matrixes. GPEs, which combine Institute of Technology. She received her
swollen polymer networks with aprotic electrolytes, show Bachelor’s degree in 2015 from School of
promise for the development of flexible and wearable Li–air Materials Science and Engineering, Beijing
batteries. Ionogel electrolytes are another new trend in the Forestry University. Her research interests mainly
development of Li–air battery electrolytes. Ionogel electrolytes focus on electrolytes and additives for high-
combine the fluidity and nonvolatility of RTILs with the high performance metal-air batteries.
mechanical strength of solid matrixes to facilitate long-term
operation. To completely avoid the disadvantages of non-
Yi Xing is currently a postdoctoral fellow under
aqueous liquid electrolytes, all-solid-state Li–air batteries should

be regarded as an important approach to achieve the ultimate
goal of developing Li–air batteries with high energy density and
high safety. Realizing this goal will require a combination of
research studies on not only solid electrolytes, but also
coordinated air electrode structures, catalysts, Li electrodes, and
interface chemistry.
Hybrid and aqueous electrolytes use an aqueous solution as
the electrolyte and operate via different reaction mechanisms
compared with those of non-aqueous systems. The discharge
products have better solubility in aqueous solution compared
with that in the non-aqueous liquid systems, which corresponds
to better rate capability. Batteries with hybrid and aqueous
electrolytes can be operated in the open air with a protective film
added to protect the active Li metal and a buffer layer added to
protect the commonly used NASICON-type LICM. However,
particular attention has to be paid to this LICM, which should be
stable against acidic/alkaline solutions and able to conform to
the changes of the anode shape and size during the lithium
stripping/plating process. The development of LICMs for hybrid
Accepted Manuscript
the supervision of Prof. Shaojun Guo at Peking
University. He received his Ph.D. degree in 2017
from Beijing Institute of Technology under the
supervision of Prof. Feng Wu. His current
research focuses on catalysts, electrolytes for
rechargeable metal-air and metal-CO2 batteries.
Nan Chen is an associate professor in the School
of Materials Science and Engineering at Beijing
Institute of Technology. She was a post-doctoral
fellow in Department of Materials Science and
Engineering at Peking University. She received
her Ph.D. degree in 2016 from Beijing Institute of
Technology. Her current research focuses on
electrochemical energy storage, solid-state
electrolytes for rechargeable batteries.
Li Li is a professor in the School of Materials

and aqueous Li–air batteries can be inspired by recent research Science and Engineering at Beijing Institute of

on solid-state electrolytes. At present, the energy densities of
hybrid and aqueous systems are still far lower than those of non-
aqueous liquid systems, and the ORR/OER process in aqueous
solution restricts their performance.
Overall, conventional aprotic electrolyte is used in the basic
research of Li–O2 batteries, but cannot meet all the
requirements. IL electrolytes, solid-state electrolytes, aqueous
electrolytes, and their composites with aprotic solvents are
candidate materials to realize safe, long life and practical Li–air
battery. Especially, IL electrolytes and solid-state electrolyte offer
possibilities to realize high energy density and high safety in Li–
air batteries. More experimental, computational, and practical
investigations are still needed to advance the field of Li–air
batteries. Although it needs to take a distance to get a truly Li–
air battery, the RTIL-based liquid and solid-state electrolytes
meet the requirements of operating in the open air, which is a
peek of things in the future.
Technology. Her research interests are
electrochemical energy storage & conversion
technology and recycling technique & life-cycle
analysis for spent secondary batteries. As the
principal investigator, Pro. Li successfully hosted
the National Key Program for Basic Research of
China, National High Tech 863 project, National
Natural Science Foundation, etc.
Feng Wu is the director of the Professor
Commission of the School of Materials Science
and Engineering at Beijing Institute of
Technology, the director of the Green Energy
Research Institute, and the vice president of the
China Battery Industry Association. As the chief
scientist, he has hosted the National Key Program
for Basic Research of China (973 projects), Basic
Research on New Rechargeable Batteries and
Related Materials. In 2012, he was awarded the
IBA Research Award for outstanding research of battery material and
systems for electric vehicles.

This article is protected by copyright. All rights reserved.

Angewandte Chemie International Edition 10.1002/anie.201903459

REVIEW

[16] W. J. Kwak, J. B. Park, H. G. Jung, Y. K. Sun, ACS Energy Lett. 2017, 2

Renjie Chen is a Professor in the School of 2756-2760.
Materials Science and Engineering at Beijing [17] Y. Zhang, X. Zhang, J. Wang, W. C. McKee, Y. Xu, Z. Peng, J. Phys.
Institute of Technology. His research focuses on Chem. C 2016, 120, 3690-3698.
[18] H. D. Lim, B. Lee, Y. Bae, H. Park, Y. Ko, H. Kim, J. Kim, K. Kang,
electrochemical energy storage and conversion
Chem. Soc. Rev. 2017, 46, 2873-2888.
technology. He was a post-doctoral fellow in
[19] Y. Liu, L. Wang, L. Cao, C. Shang, Z. Wang, H. Wang, L. He, J. Yang,
Department of Chemistry at Tsinghua University
H. Cheng, J. Li, Z. Lu, Mater. Chem. Front. 2017, 1, 2495-2510.
and a visiting professor in Department of Materials [20] S. Ganapathy, B. D. Adams, G. Stenou, M. S. Anastasaki, K. Goubitz, X.
Science and Metallurgy at University of F. Miao, L. F. Nazar, M. Wagemaker, J. Am. Chem. Soc. 2014, 136,
Cambridge. As the principal investigator, Prof. 16335-16344.
Chen successfully hosted the National Key Research and Development [21] B. Lee, J. Kim, G. Yoon, H. D. Lim, I. S. Choi, K. Kang, Chem. Mater.
Program of China, National Natural Science Foundation of China, and 2015, 27, 8406-8413.
National High Tech. 863 project etc. [22] Y. Wang, Z. J. Liang, Q. L. Zou, G. T. Gong, Y. C. Lu, J. Phys. Chem. C
2016, 120, 6459-6466.

Accepted Manuscript
[23] H. Kitaura, H. Zhou, Chem. Commun. 2015, 51, 17560-17563.
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Development Program of China ―New Energy Project for [27] P. Tan, H. R. Jiang, X. B. Zhu, L. An, C. Y. Jung, M. C. Wu, L. Shi, W.
Electric Vehicle‖ (2016YFB0100204), the National Natural Shyy, T. S. Zhao, Appl. Energy 2017, 204, 780-806.
Science Foundation of China (51772030), the Joint Funds [28] Y. Li, X. Wang, S. Dong, X. Chen, G. Cui, Adv. Energy Mater. 2016, 6,
of the National Natural Science Foundation of China 1600751.
[29] A. Khetan, A. Luntz, V. Viswanathan, J. Phys. Chem. Lett. 2015, 6,
(U1564206), Major achievements Transformation Project
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Entry for the Table of Contents

Layout 1:

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Li–air battery electrolytes include Jingning Lai, Yi Xing, Nan Chen, Li Li,
non-aqueous liquid electrolytes, Wu Feng, Renjie Chen *
solid-state electrolytes, aqueous
electrolytes and hybrid electrolytes. Page No. – Page No.

Accepted Manuscript
This review reveals the importance A comprehensive insight into the
of electrolytes to the mechanisms electrolytes for rechargeable
and performance of lithium-air lithium–air batteries
batteries, and provides a basis of
selecting suitable electrolytes. This
review also puts forward the existing
challenges, corresponding solutions,
as well as the guidance for the future
direction of this field.

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Figure 1. Mechanisms of Li–air battery with different electrolytes

Table 1. Some physical properties, electrochemical properties and calculated values of various solvents for reference to select suitable solvents

Solvent Commonly Melting point Vapor pressure Viscosity ΔGr ΔGact pKa in AN/DN
researched (°C) [28] (bar) 20°C [32] (mPa s−1) (kcal mol-1) (kcal mol-1) DMSO [29, 50]

[28] [47, 48] [47, 48] [29, 50]

25°C
EC (40°C) 36.4 10−5 ~10−2 0.1825 -6.94 14.22 — —/16.4
Carbonate PC -49 10−5 ~10−2 2.513 -5.64 15.47 — 18.3/15.1
DMC 4.6 10−5 ~10−2 0.5805 -11.39 12.42 — —/17.2
Acetonitrile CH3CN -48.8 10−1 0.341 18.96 24.92 31.3 18.9/14.1
DMF -60.4 10−3 0.802 — — — 16.0/26.6
Amide DMA -20 10−3 0.927 19.45 37.36 34.4 13.6/27.8
NMP -24.4 10−3 1.663 — — — 13.3/27.3
Dimethyl
DMSO 18.0 10−3 1.996 3.8 21.6 35.1 19.3/29.8
sulfoxide
Ether DME -58 10−5 0.455 19.88 31.56 51.8 10.2/20.0
TEGDME -30 — — — — — 11.7/16.6

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Table 2. Five decomposition pathways of the solvents and related reactive O2 species

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Figure 2. (a) C1s, O1s, F1s, and Cl2p XPS data collected on the discharge products of Li–air batteries using different Li salt. Reprinted with permission.[58]
Copyright 2012, American Chemical Society; (b) Ionic association strength of several kinds of anions in Li salt, and discharge curves (3 μA cm-2) of 1 M LiX in
diglyme using sputtered gold cathodes. Reprinted with permission.[61] Copyright 2016, American Chemical Society; (c) Discharge performance and SEM images of
the discharge electrode with 10-3 to 5 M LiTFSI in electrolytes under 25 mA gcarbon-1. (d) Illustration of the discharge capacities and morphologies influenced by Li+
concentrations. Reprinted with permission.[64] Copyright 2016, Royal Society of Chemistry.

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Figure 3. (a) Schematic illustration of the reaction mechanism of RM for Li–air batteries. (b) Molecular orbital energies of RMs and TEGDME. Reprinted with
permission.[75] Copyright 2016, Nature Publishing Group; (c) Structure of heme molecule and schematic illustration of O2 electrode charged in the heme-
containing Li–O2 cell. Reprinted with permission.[84] Copyright 2016, Nature Publishing Group; (d) The effect of LiI and H2O on the Li–O2 chemistry. Reprinted with
permission.[92] Copyright 2016, American Chemical Society; (e) Schematics of reactions on discharge with DBBQ. Reprinted with permission.[98] Copyright 2016,
Nature Publishing Group; (f) Schematics of positive electrode reactions on discharge and charge in the presence of DBBQ and TEMPO. Reprinted with
permission.[99] Copyright 2017, Nature Publishing Group.

Figure 4. (a and b) The two pathways for Li2O2 formation. Discharge LSVs performed at 0.05mV s−1 with a Vulcan XC72 carbon cathode and Li anode using 1M
LiTFSI based electrolyte solutions in nominally anhydrous DME (a) and DME with 4,000 ppm water (b). (c) Theoretically predicted discharge LSV curves for the
two independent mechanisms using the developed electrochemical model. (d) Proposed mechanism for the growth of Li2O2 toroids in the presence of water. (e)
Quantitative basis for solvent selection for high-capacity Li–O2 batteries. Reprinted with permission.[101] Copyright 2015, Nature Publishing Group; (f, g, h and i)
SEM images of the EMD/Ru/SP cathodes after the first discharge of the Li–O2 batteries with varied concentrations of H2O in TEGDME electrolyte: (f) dry
electrolyte, (g) 78 ppm, (h) 1700 ppm and (i) 4600 ppm. (j) Morphology evolution of the discharge products in different H2O containing electrolytes. Reprinted with
permission.[103] Copyright 2015, Royal Society of Chemistry.

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Figure 5. Examples of commonly used RTIL cations and anions, aprotic solvents and solvate IL electrolytes, as well as main performance evaluations of different
non-aqueous liquid electrolytes in Li–air battery.

Figure 6. Components, classifications, Li+ ions transport mechanism, as well as main performance evaluations of different solid-state electrolytes in Li–air battery.

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Figure 7. Li+ conductivity of different inorganic solid electrolytes and their stability with Li, moisture and air

Figure 8. The SEM images for (a) and (b) integrated structure, (c) one pore in the porous cathode support before carbon loading, and (d) one pore in the porous
cathode support after carbon coating. The inset shows the thickness of the carbon layer on the LATP scaffold prepared by an impregnation and pyrolysis process.
(e) Schematic diagram for product formation inside the monolayer carbon coated solid-state cathode during the discharge process. Reprinted with permission.[165]
Copyright 2015, Royal Society of Chemistry; (f) Schematic image and (g) cross-section image of a typical SSLAB. (h) The PPC:LiTFSI cell operated at 80 °C in
real air with a cutoff discharge capacity of 1000 mAh g−1 carbon at 20 µ A cm−2. Reprinted with permission.[179] Copyright 2017, Nature Publishing Group.

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Figure 9. Cable-type flexible Li–O2 battery powered a commercial red light-emitting diode display screen at (a) various bended and twisted conditions, (b) the
corresponding discharge curves. (c) Charge–discharge curves of cable-type flexible Li–O2 battery after bended thousands of times. (d) Cable-type flexible Li–O2
battery powered a commercial red light-emitting diode immersed in water. Reprinted with permission.[197] Copyright 2016, Wiley-VCH.

Figure 10. (a) Schematic diagram and (b) discharge–charge profile of the Li–O2 battery with the ionogel electrolyte. (c) SEM micrographs, (d) XRD patterns and
(e) Raman spectra of the pristine, discharged and charged cathodes. Reprinted with permission.[203] Copyright 2014, The Royal Society of Chemistry.

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Table 3. Summary of specific capacities and energy densities for aqueous Li–air batteries using different electrolyte solutions, and weight ratios of active materials
in batteries.207
Aqueous Discharge solubility Minimum amount Specific capacity Energy density Mass ratio
electrolyte product (g/100g H2O) H2O for 1mol of (mAh g-1) at OCV=3.69V Li/Salt/Water
-1
solution product(mol) (Wh kg )
LiOH LiOH 12.5 11.14 129.19 476.70 3.35/0/96.65
CH3COOH CH3COOLi 45 8.15 130.97 483,28 3.39/29.35/67.26
HClO3 LiClO3 459 1.09 262.51 968,68 6.80/82.73/10.47
HClO4 LiClO4 58.7 10.07 95.83 353.63 2.48/35.92/61.60
HCOOH HCOOLi 39.3 7.35 152.10 561.24 3.94/26.12/69.94
HNO3 LiNO3 102 3.76 208.49 769.33 5.40/49.02/45.58

Accepted Manuscript
H2SO4 Li2SO4 34.2 17.86 72.73 268.37 1.88/13.31/84.81
HBr LiBr 181 2.67 211.31 779.74 5.47/63.79/30.74
HCl LiCl 84.5 2.79 316.88 1169.29 8.20/43.11/48.69
HSCN LiSCN 120 3.01 240.97 889.19 6.24/53.13/40.63

Figure 11. (a) Schematic representation of how imidazole stores protons to keep the catholytes near neutral pH. (b) Calculation of the pH values of HCl +
imidazole buffer with different amounts of imidazole additives. SEM images of (c) pristine LTAP and (d) after immersing in 0.1MHCl for 1month, and (e) after
immersing in 0.1MHCl +1.01Mimidazole for 2.5 months, and (f) after immersing in 6M HCl + 6.06 M imidazole for 2.5 months. (g) CV of Pt/C in 1M HCl+1.01 M
imidazole with saturated O2 or N2, (h) the schematic representation of recycled imidazole buffer catholyte for hybrid Li–air batteries. Reprinted with permission.[210]
Copyright 2014, Elsevier; (i) A schematic representation of the developed Li–air fuel cell system with energy conversion unit and product recycle unit. Reprinted
with permission.[214] Copyright 2010, Elsevier.

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