Materials Chemistry and Physics 313 (2024) 128796

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Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Electrolytes in Lithium-Ion Batteries: Advancements in the Era of

Twenties (2020’s)
Sana Kainat a, b, *, Junaid Anwer b, Abdul Hamid b, Nafisa Gull a, Shahzad Maqsood Khan a, **
a
Institute of Polymer and Textile Engineering, University of the Punjab, Quaid-e-Azam Campus, Lahore, 54590, Pakistan
b
Department of Chemistry, University of Okara, Okara, 56300, Pakistan

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Lithium-ion batteries are viable due to

their high energy density and cyclic
properties.
• Different electrolytes (water-in-salt,
polymer based, ionic liquid based)
improve efficiency of lithium ion
batteries.
• Among all other electrolytes, gel poly­
mer electrolyte has high stability and
conductivity.

A R T I C L E I N F O A B S T R A C T

Keywords: Lithium-ion battery technology is viable due to its high energy density and cyclic abilities. Different electrolytes
Electrolyte are used in lithium-ion batteries for enhancing their efficiency. These electrolytes have been divided into liquid,
Lithium-ion batteries solid, and polymer electrolytes and explained on the basis of different solvent-electrolytes. Aqueous electrolytes
Solid electrolyte interphase
are preferable due to their preference over organic electrolytes having properties like non-flammability, low cost,
Aqueous Lithium-ion batteries
and safety. However, many other factors like pH, corrosion process, oxidation-reduction side reactions, and
Gel polymer electrolyte
Solid polymer electrolyte hydrogen gas evolution created limitations in their performance. Later, solid-state lithium-ion batteries are
preferred over both aqueous lithium-ion batteries and organic-based lithium-ion batteries due to their
outstanding electrochemical competencies. The electrochemical cycles of batteries can be increased by the
creation of a solid electrolyte interface. Solid-state batteries exhibited considerable efficiency in the presence of
composite polymer electrolytes with the advantage of suppressed dendrite growth. In advanced polymer-based
solid-state lithium-ion batteries, gel polymer electrolytes have been used, which is a combination of both solid
and polymeric electrolytes. The use of these electrolytes enhanced the battery performance and generated

* Corresponding author. Institute of Polymer and Textile Engineering, University of the Punjab, Quaid-e-Azam Campus, Lahore, 54590, Pakistan.
** Corresponding author.
E-mail addresses: sanakainat2k17@gmail.com (S. Kainat), shahzad.ipte@pu.edu.pk (S.M. Khan).

https://doi.org/10.1016/j.matchemphys.2023.128796
Received 29 August 2023; Received in revised form 29 November 2023; Accepted 5 December 2023
Available online 8 December 2023
0254-0584/© 2023 Elsevier B.V. All rights reserved.
S. Kainat et al. Materials Chemistry and Physics 313 (2024) 128796

potential up to 5 V. This review provides a comprehensive analysis of synthesis aspects, chemistry, mode of
installations, and application of electrolytes used for the production of lithium-ion batteries. This gives an insight
into the previous materials used for electrolytes, their issues, and challenges, and also provide a concrete study
about the future directions for use of electrolytes for lithium-ion batteries production.

1. Introduction
Electrolytes are categorized into weak and strong electrolytes based
on conductivity. Conductivity depends on the concentration of ions in an
electrolyte. Strong electrolytes dissociate completely into ions on
dissolution. Acids, bases, and salts fall into the category of strong elec­
trolytes. Materials that partially dissociate into their ions; like
CH3COOH, alkyl amine, etc. are placed in the category of weak elec­
trolytes. Electricity discovery has led to the invention of various storage
devices, like batteries capacitors, etc. Energy storage in batteries is
considered an efficient and reliable form of storage. During the charging
process, electrical energy is stored at the anode, and chemical energy is
stored at the cathode while during discharge, the energy is released in
the form of electricity. Electrolytes act as a transport medium for the
movement of ions between electrodes and are also responsible for the
enhanced performance and cell stability of batteries. Cell voltage and
capacity represent energy density, while coulombic efficiency and cyclic
stability indicate energy efficiency. These parameters are very important
for investigating the battery performance [1–6]. High energy density
and excellent performance make lithium-ion batteries (LIBs) an active
candidate in this field of energy storage devices. John B. Goodenough,
M. Stanley Whittingham and Akira Yoshino were awarded the Nobel
prize in 2019 in chemistry for their contribution to LIBs. Their theories
regarding LIBs are now commonly applicable around the world [7–10].
Rechargeable LIBs are promisingly used in aerospace, electrical vehicles,
and many other advanced technologies due to their high energy den­
sities. LIBs are now mostly used in electrical and hybrid automobiles.
Several factors affect the performance of LIBs, among which tempera­
ture is an important factor that influences the life cycle, cost, and energy
density of LIBs. Another important aspect of LIBs is electrolytes, which
are one of the core sections responsible for defining the efficiency of LIBs
[11–15]. Over the years, change in cell designs have necessitated the
need for more efficient electrolytes to enhance the performance of LIBs,
resulting in the innovation of various electrolytes (liquid, solid, aqueous,
organic, polymer, etc.). Some of the most commonly used electrolytes
are discussed below:
and cyclic carbonates (like ethylene carbonate (EC) and propylene car­
bonate (PC)) (Fig. 1). These carbonates have low viscosities, thereby
ensuring suitable ionic conductivity by reducing the overall mixture
viscosity. These two types of carbonates differ significantly in terms of
their interfacial characteristics, chemical, thermal, and electrochemical
stability, as well as their dielectric constant and viscosity [17]. Due to its
extremely high thermal stability, high dielectric constant, low volatility,
and, most importantly, its special film forming ability, EC is unques­
tionably the most significant compound in terms of LIB applications. A
protective layer known as the solid electrolyte interface (SEI) forms on
the surface of low-potential anode materials when EC electrochemically
breaks down at 0.8 V [18]. Graphitic carbon can be used as a material for
the lithium-ion (Li-ion) anode because of EC film-forming ability.
Initially, the Li-ion solvation shell co-intercalation and electrolyte
decomposition at the graphite surface at low potentials are inhibited by
the generated SEI, preventing graphite exfoliation [19–21].
It has been reported that EC is stable with a platinum working
electrode up to potentials of approximately 4.8 V concerning the cath­
ode side, or the electrochemical stability against oxidation [22]. This
indicates that it is a good solvent for common Li-ion cathode materials,
which (de-)insert lithium between 3.4 and 4.5 V. However, due to its
relatively high viscosity, it cannot be used as an electrolyte solvent at
room temperature. As a result, it has a low ionic conductivity and a
well-stabilized crystalline lattice due to its relatively high melting point
(≈36 ◦ C), which results from high molecular symmetry. Even though 1
M lithium hexafluorophosphate (LiPF6) in EC is a liquid at ambient
temperature, its ionic conductivity is fairly low due to its comparatively
high viscosity. Due to its far lower melting point and similar dielectric
constant, PC, the other well-researched cyclic organic carbonate, would
be a better electrolyte solvent. Unfortunately, its incapacity to generate

2. Organic electrolyte

As conductive media that facilitate the movement of ions between

the cathode and anode, organic electrolytes are essential to LIBs. Owing
to their capacity to dissolve lithium salts and promote ion flow, these
electrolytes frequently include organic carbonates like ethylene car­
bonate and dimethyl carbonate. Reversible electrochemical reactions
are made possible by the organic electrolyte, improving the overall
performance and efficiency of the battery. To address safety problems
related to flammable organic electrolytes, researchers are investigating
alternative electrolytes, like solid-state electrolytes or ionic liquids. The
electrochemical characteristics of the battery are also greatly influenced
by the selection of lithium salts in the electrolyte; several salt combi­
nations are being researched to maximize battery longevity and per­
formance [16]. In the section below, the detailed analysis of organic
electrolytes is discussed.

2.1. Organic carbonate based electrolytes solvents

Typically, an electrolyte solvent is composed of two different types of

aliphatic carbonates: linear carbonates (like dimethylene carbonate
(DMC), diethylene carbonate (DEC), and ethyl methyl carbonate (EMC)) Fig. 1. Chemical structure of carbonates [16].

2
S. Kainat et al.
a proper SEI makes it incompatible with graphite anodes, hindering its
broad use in LIBs, at least in substantial concentrations [23,24].
In general, linear organic carbonates have lower dielectric constants,
boiling temperatures, and viscosities. Additionally, it is undesirable that
linear carbonates are more volatile than cyclic carbonates and have
relatively low flashpoints [25]. Furthermore, the SEI layer created by
linear carbonates lacks the necessary characteristics, particularly sta­
bility, and as a result, it is unable to effectively stop co-intercalation of
the Li-ion solvation shell and continuous electrolyte breakdown at the
anode surface [18]. With a platinum working electrode, the electro­
chemical stability against oxidation is similar to that of cyclic carbon­
ates, which do not significantly decompose at potentials higher than
roughly 5 V. Nonetheless, there is a significant variation in the experi­
mental oxidation potential values stated in the literature, and sometimes
conflicting inferences are made. There is an overall agreement that
electrolyte decomposition is a surface-catalyzed process, meaning that
elemental makeup and morphological properties of the electrode ma­
terial, including surface area and porosity, influence the onset potential
of the decomposition process. It has also been noted that combining
cyclic and linear carbonates can help to reduce the release of harmful
gaseous breakdown products during a fire, especially when there is a
lack of oxygen [26,27]. In general, cyclic carbonates decompose more
slowly than linear ones, releasing fewer gaseous chemicals such as CO,
CH4 or CH2O; this is probably because of slower decomposition kinetics.
It is evident that the inclusion of cyclic carbonates greatly benefits the
resultant combinations. The presence of more volatile linear carbonates,
however, appears to have a significant impact on the flammability of
these mixtures in terms of kinetics of heat release, flashpoint, and mass
loss, effective and neat heat of combustion. For example, these mixtures
have flash points (Tf) of roughly 23 ◦ C, which is more in the range of
pure DMC (Tf ≈ 16 ◦ C) than pure EC (Tf ≈ 160 ◦ C). In terms of features
like ionic conductivity, film-forming abilities, and electrochemical sta­
bility, organic carbonate mixtures are unquestionably excellent
ion-conducting media; however, they offer inadequate safety qualities in
terms of flammability and thermal stability, for example [28–30].
2.2. Alternative organic electrolyte solvent
Significant research efforts have been and continue to be made to
replace organic carbonates, at least partially, with alternative solvents
that offer reduced flammability, improved thermal stability, and,
ideally, a wider electrochemical stability window (ESWs), to enhance
the safety of LIBs. A technique based on the addition of electronegative
substituents, or electron-withdrawing groups, such as cyano, sulfone, or
fluorine, to organic solvent molecules is often used or researched. When
compared to unsubstituted compounds, these derivatives are frequently
characterized by lower HOMO/LUMO levels [31], reflecting a change in
electrochemical stability towards higher potentials-greater stability
against oxidation but less stability towards reduction. Such fluorinated,
sulfonated, or cyanated solvents are advantageous, especially in relation
to cell overcharge, due to their enhanced stability against oxidation.
Furthermore, the decreased stability towards reduction can be advan­
tageous for the production of SEIs and, consequently, for safety [32,33].
Fluorinated ethylene carbonate (FEC), first proposed as a Li-ion
electrolyte by McMillan et al. [34] in 1999, is one of the most
researched substances. The initial goal was to enhance the SEI compo­
sition and coulombic efficiency in relation to the reversible (de-) lith­
iation of the graphite anode. Indeed, the incorporation of FEC into the
electrolyte based on organic carbonate led to a reduction in first cycle of
irreversibility, primarily ascribed to the production of SEI on the
graphite anode. On the cathode side, the addition of FEC to the elec­
trolyte mixture seems to be advantageous as well. Im et al. studied FEC
and methyl (2,2,2-trifluoromethyl) carbonate (FEMC) as an electrolyte
for a high-voltage LiNi0.5Mn0.3Co0.2O2/graphite system and operating at
a high electric potential. Fluorinated electrolytes (FEC, FEMC) showed
better results than non-fluorinated electrolytes such as EC and EMC with
3
Materials Chemistry and Physics 313 (2024) 128796
the same volume ratio of 1:9. FEC and FEMC exhibited low ionic con­
ductivity and higher viscosity than EC and EMC at different tempera­
tures. Despite their high viscosity, these fluorinated electrolytes showed
better result at 4.5–4.7 V than non-fluorinated conditions. The electro­
lyte demonstrated resistance to flammability as it did not contain any
additives. The super-concentrated electrolyte in the absence of ethylene
carbonate was compatible with the graphite anode [35]. Furthermore,
due to the strong carbon–fluorine link, fluorinated carbonates have
higher thermal stabilities and less flammability compared to
non-fluorinated carbonates, contributing to improved safety features.
Their higher viscosities, which resulting in decreased ionic conductiv­
ities, are undoubtedly a prevalent disadvantage. However, FEC is now
commonly found in commercial LIBs as an electrolyte. According to
recent reports, linear fluorinated carbonates, such as ethyl
(1-fluoroethyl) carbonate, may also be crucial in enhancing the safety
of LIBs [36,37].
2.3. Lithium salts based organic electrolyte
An appropriate lithium salt is dissolved in the organic solvent
mixture to permit ion movement in the electrolyte of LIBs. When such a
salt is added, the system becomes more complicated, and the physical
and electrochemical characteristics of pure solvents and their mixtures
are altered. For example, at ambient temperature, 1 M LiPF6 in EC is
liquid, but pure EC is solid. Additionally, it was noted that electrolyte
combinations containing additional linear carbonates, like DEC, dis­
played lower decomposition temperatures than electrolyte mixtures
containing LiPF6 as a conducting salt and DMC as a co-solvent (in
conjunction with EC). Depending on the linear carbonate alkyl chain
length, distinct intermolecular interactions and solvent reactivity were
suggested as the causes of this early disintegration [38–40].
Almost the sole conducting salt utilized in commercially available,
cutting-edge LIBs is LiPF6. The capacity to passivate the aluminum
current collector and possess qualities such as a wide ESW, chemical
inertness, strong ionic conductivity, and passivation are the reasons for
its extensive use. Due to its low cost and weight, aluminum is frequently
used as the cathodic current collector; therefore, the last fac­
tor—avoiding anodic aluminum dissolution—is the most crucial for
practical applications. Because of its relatively low oxidation potential,
metallic aluminum and the naturally occurring aluminum oxide
passivation layer are not suitable for use in high-voltage LIBs. However,
their use in these devices is made possible by the development of a
shielding layer of aluminum (oxy-)fluoride, where LiPF6 provides the
fluoride ions. This surface layer inhibits anodic aluminum breakdown,
often known as “corrosion”, by offering increased stability against
oxidation. LiPF6 has serious safety problems despite of these advanta­
geous qualities [41–43].
Handel et al. studied the hydrolysis sensitivity of LiPF6 in thermal
degradation products of LIBs (Fig. 2) [44]. Thermal instability and
elevated temperature were the major drawbacks faced due to the use of
LiPF6. During decomposition, LiPF6 decomposed into PF5 and LiF, and
through hydrolysis, HF formation takes place. The production of LiF was
dependent on the structure and concentration of HF. To determine the
amount of HF and H2O in LiPF6, many methods were used. The Karl
Fischer titration method was used to determine the amount of H2O. To
find the amount of HF, an ion selection method was used. In it, the HF
samples were injected into the total ion strength adjustment buffer,
which tells about the number of fluoride ions. The water molecule yields
two molecules of HF. While for controlling the amount of HF, the water
transformation into HF should be controlled [45–53].
Additives also caused a decrease in the concentration of LiF on the
anode surface and inhibited the decomposition of LiPF6. The change in
the surface of the structure was related to improvement in cyclic per­
formance [54]. Han et al. reported that the detrimental effect of LiPF6
was also overcame through the use of (trimethylsilyl)isothiocyanate
(TMSNCS) as an additive based on amino silane [55]. This additive
S. Kainat et al.
Fig. 2. Pathway of decomposition of lithium hexafluorophosphate in ethylene carbonate: diethylene carbonate at 60 ◦ C [44].
deactivates the HF and PF5 production, forms an interfacial layer be­
tween the anode and electrolyte, and increased stability. The TMSCNS
form a complex with PF5 and stop the further generation of the acidic
product (Fig. 3). Du et al. observed the effect of Li-ion depletion on
fast-charging electric current vehicles. By using different salts as an
electrolyte, it was found that lithium bis (fluorosulfonyl) imide (LiFSI)
was the best choice to enhance the ionic effect in LIB compared to LiPF6
[56].
In conclusion, organic electrolyte—made of organic salts immered in
organic solvent are essential to LIBs because they make it easier for ions
to move between electrodes. The battery total energy density and per­
formance are enhanced by the organic electrolytes. However, problems
with organic electrolytes include flammability, volatility, and safety
concerns.
3. Aqueous electrolyte
The cyclic and powerful ability of electric vehicles was increased by
the use of LIBs based on aqueous electrolytes. They can deliver high
energy and power density and are widely used in watches, LED screens,
and many other applications. In aqueous lithium-ion batteries (ALIBs),
the concentrated saline solution acts as an electrolyte that aids the
transfer of Li-ions among electrodes and produces electric current
[57–62]. In contrast to organic electrolytes (which consists of an organic
solvent and a lithium salt) [63] and non-aqueous electrolytes (organic or
inorganic solvent) [64], ALIBs are cost-effective, non-flammable, and do
not have the risk of an explosion. However, the electrochemical stability
window of ALIBs is limited to 1.23 V, along with a much smaller energy
Fig. 3. Mechanism of PF5 stabilization through the TMSNCS additive [55].
4
Materials Chemistry and Physics 313 (2024) 128796
density compared to non-aqueous LIBs. So, there was a need to develop
an electrolyte that not only enhances the electrochemical performance
but also solves the safety issues related to the operation of batteries. The
aqueous electrolyte can be classified into water-in-salt (WIS) electro­
lytes. The WIS electrolyte shows the stable electrochemical window and
low chemical activity of water, and suppressing hydrolysis side re­
actions. WIS electrolytes improve the electrochemical stability of the
battery up to 3 V. The performance of WIS electrolytes can also be
enhanced through an increase in electrolyte concentration up to satu­
ration. This electrolyte saturation result in the formation of a solid SEI.
The use of the SEI-forming additive (sulfone, carbonate, cyclic sulfate)
helps in the stabilization of electrolytes even at high-energy cathode
surfaces [65–69].
Various researches has been conducted on the salt solution,
providing deep knowledge on the effects of various salts on current
density and pH that ultimately decrease the electrolyte stability.
Columbic efficiency measurement proves useful for analyzing the ad­
ditive, electrode coating, impurities, and salt electrolyte impact on the
Li-ion cell cycle by using a half-cell experiment. Electrochemical prop­
erties can be enhanced by increasing electrical conductivity, reducing
charge transfer resistance, and improving the diffusion of Li-ions. The
diffusion of Li-ion can be accelerated by the nanopores, and a large pore
size results in more diffusion. The Li-ion diffusion path was shortened
due to the smaller particle size of carbon material, improving electrical
conductivity [70–72].
S. Kainat et al. Materials Chemistry and Physics 313 (2024) 128796

3.1. Water-in-salt electrolytes

Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) was most

commonly used in ALIBs as a source of lithium salt in WIS electrolytes.
The highly concentrated LiTFSI improved the reversible capacity and
cyclic stability compared to any other electrolyte. The titanium sulfide
(TiS2) anode showed high electrochemical reversibility in the presence
of LiTFSI electrolyte [73–76]. LiTFSI electrolyte possesses a wide elec­
trochemical stability window, and the TFSI anion will also remain stable
even during hydrolysis and at elevated temperature. Zhang et al.
analyzed the structural dynamics of LiTFSI along with the concentration
of water molecule and thiocyanate in LiTFSI aqueous solution. It has
been reported that the increase in concentration of LiTFSI resulted in the
fast decay of thiocyanate (SCN− ) anion (Fig. 4). WIS showed partial
crystallization at room temperature and resulted in battery failure [77].
Lithium (pentafluoroethanesulfonyl)-(trifluoromethanesulfonyl)imide
(LiPTFSI) has been reported as an excellent WIS electrolyte by Becker
et al. This electrolyte possesses a large electrochemical stability window.
Fig. 5. Carbon cloth coating on PVA-LiNO3; (a) carbon cloth, (b) LMO plate, (c)
It was thermodynamically stable at a low temperature of − 10 ◦ C. This
PVA-LiNO3, (d) LVO paste, (e) carbon cloth [85].
electrolyte was enabled to show stability even at low temperatures in the
presence of a graphitic anode [78,79].
Highly concentrated lithium nitrate (LiNO3) electrolyte resulted in effective Li-ion diffusion [87–96]. Similarly, vanadium oxide showed
an increase in the stability window from 1.2 V to 2.3 V and showed an improved electrochemical performance when Li2SO4 aqueous electro­
increase in charge and discharge potential window. In a 5 M LiNO3 so­ lyte was present. Under the same electrolyte conditions, expanded
lution, various anodes and cathodes showed excellent electrochemical graphite in combination with titanium pyrophosphate (TiP2O7) showed
stability [80–84]. Liu et al. reported the use of poly (vinyl to be a highly effective anode. Improved Li-ion diffusion kinetics and a
alcohol)-lithium nitrate (PVA-LiNO3) gel polymer electrolyte coated wetted electrode surface were made possible by TiP2O7 nanoparticles.
with a carbon cloth substrate (Fig. 5). It showed an excellent electro­ Applying a carbon layer to the surface of TiP2O7 allowed for even greater
chemical cyclic performance and retention capacity of 98.7 % after 100 improvement in electrochemical performance. After 600 cycles, a
cycles in the presence of LiV3O8 and LiMn2O4 anode and cathode, remarkable 97.3 % retention capacity was kept up in the presence of
respectively [85]. Duan et al. reported that the LiNO3 electrolyte in a 1 Li2SO4 aqueous electrolyte [97–101]. One-pot solid technique was used
M ZnSO4 aqueous solution showed an excellent electrochemical stability in a work by Bin et al. to produce an oxygen-vacancy-rich TiP2O7-y
window and exhibited a 130 mAhg− 1 discharge capacity after 50 cycles. anode. The cyclic performance of Li2SO4 electrolytes was positively
It was also reported that a pH value of 6 was suitable for the working of impacted by the tiny particle size and enhanced electron content. During
LiNO3/1 M ZnSO4 aqueous solution [86]. 800 cycles, the TiP2O7-y anode showed an 85 % discharge capacity when
When lithium sulfate (Li2SO4) aqueous electrolyte was utilized with coupled with a LiMn2O4 cathode [102]. Dong et al. reported the coating
sodium super ion-conducting (NASICON) type materials, high electro­ of the lithium polyacrylate (LiPAA) layer on the surface of LiMn2O4 as
chemical performance was observed. The absence of hydrogen and ox­ artificial SEI using in-situ polymerization hydrothermal technique. This
ygen evolution was mostly due to the NASICON-type electrode coating, coating suppresses the Jahn-Teller effect and prevent overcharge dam­
which decreased the possibility of interactions between the electrode age in presence of Li2SO4 aqueous electrolyte. LiPAA@LiMn2O4 pro­
and electrolyte. Wider channels for Li-ion intercalation and dein­ vides an 85.5 % retention capacity after 100 cycles. Water-in-ionomer
tercalation were produced by the lattice volume expansion. The material type electrolytes overcame many issues that occur due to the use of
nanostructure allowed for a wide contact between the electrode and organic electrolytes. In this electrolyte, the organic solvent was replaced
electrolyte, which slowed the evolution of hydrogen and allowed for by water while the fluorinated components were replaced through

Fig. 4. Concentration vs vibrational lifetime of LiTFSI [77].

5
S. Kainat et al. Materials Chemistry and Physics 313 (2024) 128796

inexpensive, non-fluorinated lithium polyacrylate. The electrochemical performance. The coating of the cathode also increased the battery
stability window was also enhanced by the use of ionomer [103–105]. performance and discharge rate [119]. Yubuchi et al. prepared the
The retention capacities of different aqueous electrolyte materials Li6PS5Cl SE from an ethanol solution. At room temperature, this elec­
are summarized in Table 1. trolyte displayed a conduction capacity of 1.4 × 10− 5 Scm− 1. The
LiCoO2-coated electrolyte as a cathode showed a 45 mAhg− 1 discharge
capacity. The huge conduction of the ion of the SE was prepared by the
3.2. Capacity fading in ALIBs
liquid phase method, which showed excellent performance in all cells.
The coating of nitrile-based material also improved battery performance
Researchers studied the electrochemical reaction through three
[120]. Zhou et al. prepared a hierarchical all-solid-state electrolyte,
different methods, and it was found that the oxidation reaction was
which was based on nitrile materials by using the in-situ synthesis
responsible for the capacity fading of a battery. In the presence of
method. The nitrate-based SE was coated with cross-linked cyanoethyl
reactive oxygen, the electrolyte reacts with the cathode, and the surface
polyvinyl alcohol (PVA-CN) polymer, which was uniformly scattered on
reactivity was damaged. Oxygen, which reacted with the electrode,
it even over the melting point, and the mechanical strength was
resulted in side reactions like electrode material dissolution in water, as
increased. PVA-CN showed a high Li-ion transference number and
the reaction involved H2/O2. The reaction of LIBs with water and oxygen
excellent thermal stability. This polymer prevents electrolyte leakage at
at any pH of electrolyte resulted in capacity fading [106,107]. Increased
high temperatures in succinonitrile-based solid electrolytes and reduced
pH values affected the material coating and resulted in a corrosive effect
SEN film thickness. It was most commonly used in chemical energy
on the aluminum current collector. A higher alkaline pH value resulted
sources [121]. Lamellar garnet ceramic electrolytes for the improvement
in more corrosion. The structure of the crystal and electrolyte pH was
of solid-state LIBs were studied by Du et al. Solid-state LIB was con­
affected by the proton intercalation. The aluminum corrosion process
structed by using Li7La3Zr2O12 (LLZTO) as a SE, which was active as a
also occurs in the presence of aqueous slurries due to the removal of the
positive electrode with a coating of composite PVDF, Li(CF3SO2)2N
native passivation layer from the aluminum [108]. The corrosion on
(LiTFSI), Ketjen Black, LiFePO4, and a coating of carbon in Li anode on
cathode coating was removed by using aluminum foil, and the slurry of
the alternative side. The medium temperature was used for the working
neutral pH. The pH was reduced by acid addition, but acid will also
of solid-state LIB [51].
result in negative effects. Removal of oxygen and maintenance of the pH
value resulted in an increased capacity of the battery operation. The
4.1. Effect of solid electrolyte interface
aluminum oxide (Al2O3) coating also suppressed the hydrogen evolution
reaction on the anode surface of lithium titanium oxide (Li4Ti5O12). The
SEI plays a major role in the energy, power density, stability, and life
lithium manganese oxide (LiMn2O4) cathode with Al2O3 coated anode
cycle of the whole battery. The SEI layer prevents the reaction between
enableed 2.4 V LIBs for 200 cycles. Observation showed that the elec­
electrode and electrolyte and increased the number of cycles of LIBs [19,
trolytic range of salt solution was higher than pure water [109–111].
122–126]. Therefore, Zampardi et al. observed SEI as an electronically
In conclusion, because of their low cost and strong ionic conductiv­
protecting film, which was formed by the decomposition of natural
ity, aqueous electrolytes are crucial in a variety of electrochemical
electrolytes at the cathode in LIB. The in-situ investigation of LIBs was
systems. However, they have shortcomings, including electrode corro­
conducted in a glove box in which the level of oxygen and water was
sion and limited voltage stability.
typically below the 1 ppm [127]. The shorter linear alkyl chain of cyclic
carbonates, when intercalated with the graphene layer, caused graphite
4. Solid electrolyte
exfoliation. To overcome this problem, Zhao et al. prepared a homolo­
gous series of propylene carbonate (PC) solvents by creating a
The largest ionic conductivity, highest electrochemical window, and
large-sized linear chain of alkyl, which was used as a solvent for graphite
best electrochemical properties were necessary for solid-state LIBs. Be­
Li-ion half-cells. The positive electrode used was made of graphite with
sides ionic conductivity, there were some other factors that must be
longer alkyl chains and avoids graphite molting during its use as a sol­
examined for the construction of electrolytes for solid-state LIBs. These
vent with PC. Single-electron reduction of graphite results in the for­
factors include the stability of the metal lithium anode and electro­
mation of a stable SEI. The graphite provides volume change during the
chemical window against the cathode, transference number of Li-ion,
cycle and produces SEI [128,129].
and dendrite growth destruction. A 90 % retention capacity was
gained by the use of solid-state high-voltage LIBs without destroying the
4.2. Electrolytes for dendrite suppression
electrochemical window. Solid electrolytes (SE) are better and safer than
aqueous electrolytes because aqueous electrolytes lead to some leakage
Lithium was significantly used as an anode in all-solid-state LIBs, but
and stability issues. In addition, the use of SE will minimize the side
its use may cause some issues when it encounters electrolytes. The rigid,
reaction that occurred due to high voltage cathode, and Li anode. SE
tiny structure formed in LIBs is termed as dendrite. Dendrite formation is
helped in the development of micro LIBs in which energy density and
a major issue that results in a decrease in energy density, storage ca­
power capacity were improved [112–118].
pacity, and battery failure. Polymer-based electrolytes have gained
Li et al. used solid-state electrolytes on LiNi1/3Co1/3Mn1/3O2 (NMC),
significant importance in the field of solid-state lithium metal batteries
which was active as a positive electrode in LIB. The atomic layer
due to their ionic conductivity, easy assembling, and flexibility. How­
deposition technique was used for the coating of lithium tantalum oxide
ever, the major target to achieve the best cyclic performance is dendrite
(LiTaO3) on NMC with varying thicknesses. NMC electrode degradation
growth in the anode. Dendrites growing between the electrolyte and Li
was decreased in NMC-10 at 3.0–4.8 V cutoff potential. Specific coating
anode resulted in battery failure [130–133]. These problem can be
thickness was significant for the improvement of cathode and battery
solved either through the coating of the anode or by the introduction of
some materials that result in the formation of an interface layer between
Table 1 the anode and electrolyte. Dendrite formation can be reduced with an
Retention capacities of different aqueous electrolyte materials.
increase in electrolyte conductivity. Sulfite-based electrolytes showed
Sr. No. Aqueous Electrolyte Retention Capacity (%) Cycles References high electrochemical performance, enhanced energy density, and sup­
1 PVA-LiNO3 98.7 100 [85] pressed dendrite formation [134–139].
2 LiNO3 95.7 250 [86] Wang et al. reported that a Li anode coated with Li phosphorous
3 Li2SO4 97.3 600 [101] oxynitride (LiPON) thin-film showed excellent cyclic stability, sup­
4 LiFSI 87.7 500 [56]
pressed dendrite formation, and resulted in the formation of the

6
S. Kainat et al.
interphase between anode and electrolyte [140]. Li1.5Al0.5Ge1.5(­
PO4)3-poly (ethylene oxide) (LAGP-PEO) was used as an electrolyte,
which also enhances the electrochemical performance. Through the
coating of the anode, the reaction with Li1.5Al0.5Ge1.5(PO4)3 (LAGP) was
prevented [141]. Hu et al. reported the preparation of Lithium bis (tri­
fluoromethyl sulfonyl) imide/poly (vinylene carbonate)
(LiTFSI/PVCA)–SiO2 interlayer for solid-state lithium metal batteries
based on LAGP. This interlayer possesses high ionic conductivity, me­
chanical strength, and better electrochemical performance [142]. Niu
et al. studied ionic solid electrolytes, which reduced dendrite formation
and increased the cyclic capacity of the cells. Ion-regulated solid poly­
mer electrolyte (SPE) was prepared based on polyethylene glycol ether
acrylate. This whole procedure was based on ion space theory. Gener­
ally, these batteries were used for the power supply of a light-emitting
diode (LED). The poly (ethylene glycol ether acrylate) (PEGEA) based
SPE (PSPE) was prepared by forming the solution of LiTFSI, SiO2, and 2,
2′-azobis-(2,4-dimethylvaeronitrile) into ethylene glycol ether acrylate
by 6 h stirring. This solution was poured into the lithium metal. Further
polymerization resulted in the formation of PSPE [143]. To reduce
dendrite formation, Zhang et al. studied the FEC and LiNO3 in the
electrolyte. The solvation sheath was changed and resulted in the for­
mation of SEI, which contains LiF and LiNxOy with Li metal anodes and
results in Li deposition, which was dendrite free. It increased the life of a
battery up to 1000 cycles and the coulombic efficiency by up to 99.96 %
[144]. All this happened due to a uniform SEI interphase, which makes
LIBs more useful. The Li-ions were solvated with the help of solvent and
anions. These make a solvation sheath, which diffuses and touches the
lithium surface, increasing the uniformity of SEI sheath. It reduced
resistance to electrolytes by using other salts. Dendrite formation most
commonly occurred in the naked Li7La3Zr2O12 (LLZO) electrolyte.
Through the coating of electrolytes, the performance of the battery was
enhanced. The doping of LLZO ceramic in the Li conductor results in the
formation of 10 μm thin layers. These helped a lot to eliminate the
dendrites, increase mechanical strength and surface area of SEI. The
tape-casting process was used to prepare the trilayer. This method was
cheap and easy to handle. LLZO was formed by the solid-state reaction
mechanism. This LLZO was mixed with the binders practices and other
compounds to prepare the tape slurry. This tape slurry was poured on
the layers one by one and then dried to get the flexible plates. This
tri-layer helped to increase the support and mechanical strength of the
battery. Moreover, it enhanced the braking force, provided a large sur­
face area, and was easy to handle [145–149].
In conclusion, solid electrolytes for LiBs are a desirable alternative
due to their potential for increased safety and energy density. By
providing a stable substrate for ion transport, they mitigate the risk of
short circuits and alleviate concerns regarding dendritic development.
However, barriers like labor-intensive production procedures and high
cost of production keep them from being broadly adopted. Electrolytes
designed for dendritic separation are vital for preventing dendritic
structure growth and enhancing battery safety and overall performance.
However, there are a few significant obstacles, such as issues with poor
ion conductivity and scalability. SEI suffer obstacles to stability and
compatibility, which lessens their usefulness in real-world applications.
5. Solid polymer electrolyte (SPE)
High room temperature ionic conductivity, rate capability, and
excellent cyclic performance make SPE suitable for LIBs. SPE is flexible,
provides a large transmission of ions, better charge and discharge ca­
pacity, and a wide temperature range for LIBs. This SPE with Li/LiFePO4
showed a brilliant life cycle at a wide temperature range. SPE consisting
of polymeric polyhedral oligomeric silsesquioxane ionic liquid shows an
electrochemical stability window of 5 V and the largest room tempera­
ture ion conductivity [150–153]. Yin et al. used a new three-step route
for the preparation of imidazolium-based polymerized ionic liquid.
LiTFSI salt and polymer ionic liquid (PIL) were used to synthesize Poly
7
Materials Chemistry and Physics 313 (2024) 128796
(1-ethyl-3-vinyl imidazolium bis (trifluoromethane-sulfonyl imide)) (P
(EtVIm-TFSI) electrolytes (Fig. 6). By using a new synthetic process,
capacity, and cyclic performance became better [154].
For detecting the thermal properties and ionic conductivity of
polymer electrolytes, Sun et al. used a cyclic monomer of trimethylene
carbonate which undergoes bulk ring-opening polymerization and forms
high molecular weight poly (trimethylene carbonate) (PTMC) (Fig. 7).
LiTFSI was also combined with PTMC and resulted in flexible SPE films
in which Li-ions ranged from 2 to 21. Differential scanning calorimetry
and thermogravimetric analysis techniques were used to analyze the
thermal properties. This PTMC proved to be an efficient candidate for 3D
micro-batteries. This polymer electrolyte showed an electrochemical
stability of up to 5.0 V [155].
Deng et al. studied single-ion conducting polymer electrolytes
(SIPEs) based on sp3 boron. Lithium bis(allylmalonato)borate (LiBAMB)
and pentaerythritol tetrakis (2-mercapto acetate) combined through a
single-step photoinitiated in-situ thiolene reaction and resulted in the
formation of SIPEs. It showed high ionic conductivity, Li-ion trans­
ference number of about 0.89, and higher capacity at 1 ◦ C after 500
cycles. The electrochemical stability window was about 5.2 V [156,
157]. The electrochemical stability was further increased through SIPE
lithium oxalate polyacrylic acid borate (LiPAAOB) reported by Zhu et al.
This polymer electrolyte consisted of polyacrylic acid, boric acid,
lithium hydroxide, and oxalic acid in different ratios. This polymer
electrolyte showed a single-ion conductive behavior. This electrolyte
was suitable for 5 V LIBs with electrochemical stability of up to 7 V and
ionic conductivity of 2.3 × 10− 6 Scm− 1 [158]. The discharge capacities
of different solid electrolyte materials are summarized in Table 2.
6. Gel polymer electrolyte
Gel polymer electrolytes (GPEs) are a combination of both liquid
electrolytes and SPEs. This electrolyte possesses high ionic conductivity
and safety. The liquid electrolyte used for GPE should possessed high
ionic conductivity, absorption capacity, and be fire-resistant. GPE shows
high conduction of ions, thermal stability, and better cyclic performance
[159–165]. The excellent polymerization ability of acrylate and the
non-flammable property of phosphates were obtained in acryloylox­
yethyl dialkyl phosphates, which were prepared through an in-situ
radical thermal polymerization technique. This acryloyloxyethyl dia­
lkyl phosphates gel copolymer electrolyte has great thermal stability and
excellent electrochemical stability of up to 4.5 V [166–169]. Carol et al.
reported the preparation of the GPE for LIB, the electro-spun membrane
of large-weighed poly(acrylonitrile) (PAN) was used as a host matrix.
They synthesized a fiber-like membrane of PAN that was bead-free, and
a diameter ranged from 880 to 1260 nm. At 20 ◦ C, GPE showed ionic
conductivity of 0.000017 Scm− 1. If the anode was made of graphite and
the cathode was made of LiCoO2, then high performance at low capacity
fading was possible. GPE was also prepared by using polyethylene oxide
(PEO), LiTFSI, and different ionic liquids (IL) such as 1-ethyl-3-methyli­
midazolium bis(trifluoromethyl sulfonyl)imide (EMIMTFSI) [170].
The composite polymer electrolyte (CPE) enhanced battery perfor­
mance and helped in achieving dendrite-free, safe, and stable solid-state
LIBs. The garnet-type composite polymer electrolyte also enhanced
battery performance. CPE was normally prepared by combining the
pyrrolidinium-based polymeric IL with succinonitrile and LiTFSI in
different ratios. These composite polymers showed high conduction of
ions at room temperature and high physical strength. Therefore, the
discharge capacity was also high. CPE shows excellent ionic conduction
and mechanical properties. It increased the cyclic efficiency of lithium
powdered ion cells by the use of single lithium sources as ionic con­
ductors and core-shell structures with SiO2 (Li+) nanoparticles. They
acted as functional fillers in composite gel electrolytes. These amend­
ments caused an increase in the discharge capacity of powdered LIB up
to 264 mAhg− 1 and showed excellent retention capacity at even high
current rates. The morphological analysis further confirms that the GPE
S. Kainat et al. Materials Chemistry and Physics 313 (2024) 128796

Fig. 6. Synthetic route of P(EtVIm-TFSI) [154].

Fig. 7. Preparation of poly(trimethylene) carbonate by ring-opening polymer­

ization [155].

Table 2
Discharge capacities of different solid electrolyte materials.
Sr. Solid Electrolyte Discharge Capacity Temperature Reference
No. (mAhg− 1) (◦ C)

1 Li6PS5Cl 45 25 [120]
2 Li7La3Zr2O12 150 60 [51]
3 LAGP-PEO 152.4 50 [140]
(LiTFSI)
4 LAGP-PEO 160.8 50 [141]
5 PTMC 153 60 [155]

suppresses the dendrites that form during cycling [171–178]. Zhou et al.
reported the used of polymer/ceramic membrane/polymer sandwich
electrolyte (PCPSE) to improve the coulombic efficiency of the battery.
Polymer covers the ceramic membrane anode, resulting in the sup­
pression of dendrite formation, and improved the electrochemical sta­
bility of the solid-state battery. The PCPSE with a solid-state LiFePO4 cell Fig. 8. Polymer/ceramic membrane/polymer sandwich electrolyte; (a) anode
delivered a coulombic efficiency of about 99.8–100 % (Fig. 8) [179]. shell, (b) anode, (c) polymer electrolyte, (d) ceramic electrolyte, (e) polymer
Hydroxyethylcellulose (HEC) was a renewable, cheap, and electrolyte, (f) cathode, (g) cathode shell [179].
environment-friendly polymer, which was used as a host for GPEs. The
HEC membrane was stable up to 280 ◦ C. At room temperature, this cheap, efficient, non-toxic. For high energy LIBs, ionic conductivity, and
electrolyte showed excellent electrochemical performance with high cycle performance were improved [180–183].
conductivity and transference number. Polypropylene (PP) separators
showed low ionic conductivity. Therefore, to increase the ionic con­ 7. PVDF (Polyvinylidene fluoride) based electrolyte
ductivity, PP separators coated with aerogel were developed, which
were made of cellulose and based on HEC. These PP separators were PVDF is most commonly used due to its high chemical inertness, and

8
S. Kainat et al. Materials Chemistry and Physics 313 (2024) 128796

it does not react with electrolytes or Li-ion. PVDF work in a high-

temperature range and provide excellent conductivity. Micro-porous
polymer electrolytes based on PVDF/Polyethylene oxide (PEO) star
polymer were prepared using the phase inversion method. With the use
of star polymer, pore formation occurred, and absorption of electrolytes
increased. At 25 ◦ C, the ion conduction was improved. By using this
method, the electrochemical stability window was improved up to 5.0 V
(vs. Li/Li+). Electrospun fibrous membranes of PVDF and PEO was re­
ported in literature. The bead-free membrane was prepared by con­
trolling spinning parameters. This membrane possessed high porosity,
sufficient mechanical strength, and uniform fiber distribution. At room
temperature, the PVDF/PEO membrane showed high conductivity
[184–187]. The coating of PVDF also proved sufficient and showed
excellent performance. Xiao et al. prepared a composite polymer
membrane by coating PVDF on the surface of the methylcellulose
membrane. The porous PVDF layer showed high electrolyte usage and a
large transference number than methylcellulose. High safety and low
cost made this composite membrane useful for LIBs. A simple and
scalable phase inversion method was used for the preparation of the
porous PIL with polyvinylidene fluoride-hexafluoropropylene composite
membrane. This composite membrane had enhanced mechanical per­
formance and thermal stability. Liquid electrolyte was absorbed into the
composite membrane to form GPE [188–191].
The fluorine composite also increased the performance of LIB;
therefore, Xiao et al. studied the CPE, which was based on P(VDF-HFP),
increased the conduction of ions and mechanical strength. These elec­
trolytes were prepared by doping them into methyl methacrylate. The
nanoparticles of ZrO2 were synthesized by the invasion phase method.
These are grafted into the methyl methacrylate (MMA) to prepare Fig. 9. Preparation of P(VDF-HFP)-based CPEs doped with the nano­
PMMA. CPE membrane, along with ZrO2 nanoparticles, not only particles [192].
enhanced the conduction of the ions but also maintained its shape
during exposure to high temperature. These cells also showed excellent of organic solvents. The high content of IL containing mixtures was
performance. The nano ZrO2 particles were prepared by the hydrolysis difficult to burn, but if it ignites, then it caused burning. PYR14FSI shows
of ZrO2-butoxide in a mixture of butanol in deionized water. A 60 ◦ C high ionic conductivity and showed more than 5.5 V of the electro­
temperature was required for this process, and the time required was chemical stability window. This battery showed 140 mAhg− 1 stability
about 6 h. The grafting of ZrO2 nanoparticles into MMA resulted in the capacity. The metallic current collector recovers by the dissolution of
formation of PMMA (Fig. 9) [192]. Further drying at 80 ◦ C resulted the H2O of the binder [200,201].
desired product. The next step was the formation of CPE. For this pur­ Fang et al. [202] investigated different properties like
pose, the casting of nanoparticles and P(VDF-HFP) was formed in charge-discharge character for IL electrolytes. The cathode limiting the
powdered form. This powdered was mixed into N, N-Diethylamide to potential of IL was 0.7 V vs Li/Li cation. At a 0.2 current rate, Li/LiCoO2
form a homogenous mixture. The time required for this purpose was cells with IL showed good competency when LiTFSI concentration was
about 2 h at 40 ◦ C temperature. The solution was poured onto the higher than 0.3 mol kg-1, and conductivity reduced. IL from C4H10N and
cleaned glass substrate and dipped into deionized water for 12 h. This C5H12N were also synthesized. At 25 ◦ C, these electrolytes showed liquid
electrolyte proved to be the most promising electrolyte for LIBs with behavior. These IL electrolytes were stable and show better capacity
high efficiency and excellent conductivity [193]. without using any additive. LIB shows excellent ionic conductivity and
electrochemical stability at room temperature and good cyclic perfor­
8. Ionic liquid electrolyte mance. The methyl carbonate-terminated perfluoropolyether electro­
lytes showed good conductivity and an enhanced lifetime of
IL possesses chemical and thermal stability, flame retardancy, very rechargeable LIBs. Protic IL showed all properties of IL and it was cost
low volatility, and is safe to use, making it a green solvent that has effective. It also enhanced the cyclic stability of LIBs [203–206].
gained a lot of attention. Super concentrated electrolyte obtained was
helpful for LIBs that operate at high voltage. Super concentrated elec­ 9. Conclusion and future direction
trolyte require low viscosity solvents than many other electrolytes and
showed an excellent stability at high-temperature [194–198]. R.S.Kuh­ There is an extensive need for LIBs in electric vehicles and hybrid
nel et al. investigated the properties of N-butyl-N-methylpyrrolidinium electric vehicles worldwide due to their excellent charged density and
bis (trifluoromethanesulfonyl) imide (PYR14TFSI), LiTFSI, and PC as an cyclic ability. This requirement has led to the study of electrolytes and
electrolyte. The mixture of PYR14TFSI and PC showed a stability window other factors that affect the performance of LIBs. Therefore, this review
up to 5 V, low viscosities, and high conductivities. It also suppressed the mainly focuses on electrolytes used in LIBs, including both aqueous and
corrosion process of the Al current collector. The mixture of LiTFSI with solid-state electrolytes. ALIBs are involved in different applications and
PYR14TFSI and PC showed specific capacity and stability at 25 and are preferred over organic electrolytes due to non-flammability and
60 ◦ C. This mixture also significantly increased the retention capacity electrochemical stability, although ALIBs still carry a risk of explosion
[199]. The safety of large-size LIBs and the thermal stability of elec­ and corrosion phenomena. A lot of work has been done to overcome this
trolytes was an important factor. The ionic liquid PYR14TFSI with a problem through the coating of the electrodes. Electrode coating en­
mixture of dimethyl carbonate-ethylene carbonate (DMC-EC) and 1 M hances the Li-ion intercalation and de-intercalation phenomena, sup­
LiPF6 was less volatile. If the amount of PYR14TFSI was reduced, then presses hydrogen evolution, and increased the electrochemical stability.
flame inhibition occurred and ignites properties rescued in the presence

9
S. Kainat et al.
Carbon coating has proven to be the most favorable due to the formation
of small pores, which increases the movement of ions.
Although ALIB offer excellent stability, they provide an electro­
chemical window of less than 3 V. To increase the electrochemical
window solid-state electrolytes have been suggested as effective. Solid-
state LIBs, providing more stability than any other type of LIBs, offers an
electrochemical window of greater than 3 V and enhances battery per­
formance. The major drawback of solid-state lithium batteries is the
growth of dendrite on the lithium anode. In recent years, studies have
aimed to control the growth of dendrites by using CPE and anode
coating. The latest studies in solid-state LIBs focus on SEI for better
battery stability. This interphase is formed between electrodes and
electrolyte to prevent the decomposition of the electrodes. GPE are a
combination of both, solid electrolytes and polymer electrolytes, having
high stability and conductivity. Gel polymer electrolytes increased the
electrochemical stability window potential value up to 5 V.
Although many other studies for improvement in LIBs performance
are underway worldwide, there is still a very specific need for more
stable and more efficient electrolyte and electrode combinations to
achieve the high voltage and deep cyclic abilities in batteries. In the
coming years, the findings we need to inquire about are: Do we need to
make improvements in working principles? Or is creating more effective
charge-conducting solid electrolytes and electrodes enough to improve
the performance of LIBs?
This work has important ramifications for future research. The re­
sults highlight the critical necessity for an extensive review of the
guiding principles driving LIB operation. Additionally, a crucial area for
investigation is the search for even more effective charge-conducting
solid electrolytes and cutting-edge electrode materials. This research
opens the road for an energy storage technology future that is more
sustainable and revolutionary by addressing these issues and investi­
gating areas for improvement. The efforts of researchers worldwide will
definitely undoubtedly be motivated and guided by this literature,
creating a collaborative and dynamic environment that will enable the
full potential of LIBs for a variety of applications outside of electric
vehicles.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
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