Sustainable Materials and Technologies 29 (2021) e00297

Contents lists available at ScienceDirect

Sustainable Materials and Technologies

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

An advance review of solid-state battery: Challenges, progress

and prospects
Cong Li a, b, c, Zhen-yu Wang a, b, c, Zhen-jiang He a, b, c, Yun-jiao Li a, b, c, Jing Mao d, Ke-hua Dai e,
Cheng Yan f, Jun-chao Zheng a, b, c, *
a
School of Metallurgy and Environment, Central South University, Changsha, Hunan 410083, China
b
National Engineering Laboratory for High Efficiency Recovery of Refractory Nonferrous Metals, Central South University, Changsha 410083, China
c
Engineering Research Center of the Ministry of Education for Advanced Battery Materials, Central South University, Changsha 410083, China
d
School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, China
e
College of Chemistry, Tianjin Normal University, Tianjin 300387, China
f
School of Mechanical, Medical and Process Engineering, Queensland University of Technology, Brisbane, Queensland 4001, Australia

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

Keywords: The mushroom growth of portable intelligent devices and electric vehicles put forward higher requirements for
Lithium-ion batteries the energy density and safety of rechargeable secondary batteries. Lithium-ion batteries using solid-state elec­
Solid-state electrolytes trolytes are considered to be the most promising direction to achieve these goals. This review summarizes the
Ionic conductivity
foremost challenges in line with the type of solid electrolyte, provides a comprehensive overview of the advance
Interface problem
developments in optimizing the performance of solid electrolytes, and indicates the direction for the future
research direction of solid-state batteries and advancing industrialization.

1. Introduction
Given that the energy crisis has been taken seriously, global energy
consumption is gradually shifting from traditional fossil sources to other
clean and efficient sources. Efficient and clean energy storage is the key
technology for helping renewable energy break the limitation of time
and space. Lithium-ion batteries (LIBs), which have characteristics such
as high energy density, high reversible, and safety, have become one of
the great frontiers in the energy storage field [1].
The state-of-the-art LIBs are first known as rocking chair batteries [2]
because lithium ions move between two electrodes and intercalation/
deintercalation in the active materials during charge/discharge cycles.
In 1991, Sony Corporation of Japan took the lead in developing LixC6/
organic electrolyte/Li1-xCoO2 LIBs and successfully realized commer­
cialization [3]. Oxide/redox reaction on two electrodes promotes the
transport of Li+ inside the battery, and electrons go through external
circuits [4,5].
Most of LIBs are generally composed of four parts, namely, cathode,
anode, electrolyte, and separator. During the discharging process,
electrons cannot transfer by electrolyte but flow from the anode via an
external circuit to the cathode. Meanwhile, deintercalated Li+ from
anode moving via the electrolyte intercalates into the cathode and un­
dergoes a redox reaction. The charging process is the opposite. The
separator prevents direct contact between cathode and anode, whereas
the electrolyte plays a role in transporting Li+ and blocking electrons
[6,7]. Each component of a battery has its unique function and interacts
with each other to realize the mutual conversion between chemical and
electrical energy.
At present, the commercial electrolyte system usually consists of
lithium salt and carbonate-based organic solvent, whereas some
potentially serious safety threats may be caused by the liquid electrolyte
system. First, leaking organic solvent can make toxic effects on the
human body when battery packing is damaged. Furthermore, low igni­
tion point and low boiling point generate serious threats, such as ther­
mal runaway when the battery is overcharged and discharged.
Moreover, the characteristics of liquid aggravate performance deterio­
ration and the side reactions between electrode and electrolyte, which
are common reasons for electrolyte system failure [8]. Narrow working
temperature, decomposition under high voltage, and the inability to
suppress lithium dendrite make the traditional liquid electrolyte no
longer satisfied with the high-energy battery of the future [9].
For more than 200 years, scientists have devoted considerable time

* Corresponding author at: School of Metallurgy and Environment, Central South University, Changsha, Hunan 410083, China.
E-mail address: jczheng@csu.edu.cn (J.-c. Zheng).

https://doi.org/10.1016/j.susmat.2021.e00297
Received 8 March 2021; Received in revised form 20 April 2021; Accepted 22 May 2021
Available online 17 June 2021
2214-9937/© 2021 Elsevier B.V. All rights reserved.
C. Li et al.
and vigor to the study of liquid electrolytes with limited properties.
Since the 1960s, the discovery of high-temperature Na–S batteries
using a solid-state electrolyte (SSE) started a new point for research into
all-solid batteries, which has attracted a lot of scientists [10]. Replacing
liquid electrolyte and separator, while keeping other parts unchanged,
SSE avoids the use of organic solvents with good mechanical strength,
which can solve some safety problems in traditional lithium-ion batte­
ries. In parallel, solid electrolytes have fewer side effects than liquid
electrolytes, which leads to the longer life expectancy of solid-state
battery [11]. SSEs stand out of the liquid electrolytes with extraordi­
nary potential in increasing energy density. Given the trend that
portable electronic devices are becoming increasingly small and
demanding increasingly high power, solid-state batteries will become
increasingly significant.
This section is followed by an introduction, which generalized many
arduous challenges in the development process of solid-state battery.
The methods and perspectives of optimizing the performance of SSE in
recent years, which described the spacious foregrounds of solid-state
battery in the future, are summarized (Fig. 1).
2. Challenges of solid-state batteries
The common cathode materials, characterized by providing the
lithium, are listed of the layered transition metals oxides, olivine, or
spinel according to all kinds of structures [12]. With the ever-growing
renewable energy demands, many efforts have been paid for exploring
the energy storage equipment, with high capacity, high voltage and low
cost. There have been some novel cathode materials emerging to fulfill
this demands such as Co-free layered cathode material, [13] Ni-rich or
Li-rich cathodes and so on [14]. Secondary batteries with metal anodes
such as lithium, sodium and potassium provide higher storage capacity
[15,16]. Lithium metal batteries have the highest theoretical capacity
(3860 mAh g− 1) and lowest electrochemical potential (− 3.04 V versus
the standard hydrogen electrode) [17,18]. The earliest Li metal batteries
came from the finding of Moli Energy company about Li-MoS2 batteries.
But soon after, this kind of battery was been found huge safety problems
due to the dendrite growth, that Li metal anode push hard [19–21].
Different kinds of skills are available to improve the properties of Li
Fig. 1. Schematics of the main types and the direction of improvement of solid-
state electrolytes.
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Sustainable Materials and Technologies 29 (2021) e00297
metal [22]. Huang et al [23] designed properly Li metal batteries by
devoting Si from the separator to produce a protective layer (LixSi),
which can solve a series of problems from Li metal. To satisfy the
industrialization of new energy vehicles and large-scale energy storage
equipment, lithium metal batteries should attach more importance.
However, high specific capacity and energy density is double-edged,
which makes the battery life shorter and triggers frequent security
problems [24]. the unstable characteristic limits application. Interest­
ingly, SSE also shows a potential application in the next generation of
high-performance energy storage devices such as Li–S battery with
sulfur as the cathode, Li–O2 battery using O2 as the cathode, and Li-
intercalation type cathode battery [25]. At present, SSE is still under
developing and unable for the large-scale commercial application. In
other words, a series of problems need to be solved before commer­
cialization, such as ionic conductivity at room temperature, interface
stability, mechanical property, voltage window, and integrated battery
design [26]. According to the composition of SSE, which could be
roughly divided into three categories, namely, inorganic ceramic SSE,
polymer SSE, and ceramic-polymer hybrid SSE, each type has its own
unique challenges (Fig. 2-1,Table 1).
2.1. Ceramic electrolytes
The ceramic-based β-alumina (Na2O⋅11Al2O3) was first discovered in
the 1960s and is capable of rapid solid-state ion transport, which is
marked as a milestone of electrolytes. This discovery boosts the
advancement of ceramic-based SSE. Many different types of inorganic
materials have aroused wide attention in the solid-state battery system,
including LiPON-type [27], Li3N-type [28], garnet-type [29,30],
perovskite-type [31], sulfide-type [32], lithium superionic conductor-
like [33], and sodium superionic conductor-like [34–36].
The essence of fast ionic conductor ceramics is a material with tun­
nels of crystal lattice defects or glass network structures [37]. Ions can
move through these tunnels with a certain direction. Ionic goes hand in
hand with crystal structure defects (Fig. 2-2). The defects of crystal
structure affect the transport path of ion conduction. Crystal structure
defects are closely related to temperature [38,39]. Normally, the higher
the temperature is, the higher the concentration of ions or vacancies can
be made [37]. As a result, SSE performs better ionic conductivity under
high temperature [ [40]]. Furthermore, given small radius and low
valence, Li+ can exhibit high ionic conductivity even at room or lower
temperature. That is, the ionic conductivity of the inorganic SSE, espe­
cially solid sulfide electrolyte, can compare with the traditional one.
Fig. 2-1. Summarization of common electrolyte systems type and examples.
C. Li et al.
Table 1
Comparative characteristic of different types of SSEs. A: Liquid Electrolytes; B: Ceramic Electrolytes; C: Polymer-Based Electrolytes; D: Hybrid SSE.
SSEs Ionic conductivity Interfacial compatibility
A Excellent High
B High Low
C Low Excellent
D High High
Fig. 2-2. Three typical inorganic solid ion migration pathways [38].
Therefore, inorganic SSE can present a wider working temperature
range than traditional liquid electrolytes.
However, the interface problem is a formidable challenge that hin­
ders inorganic SSE from continuing the application. First, poor interface
contact not only increases the interface impedance, resulting in a serious
polarization, but also harms the electrochemical performance of the
battery, including rate capability, coulombic efficiency, cycle stability,
and low energy conversion efficiency. Simultaneously, the space charge
layers formed between the inorganic ionic conductor and the electrode
are a kind of barrier to the ion diffusion [41]. SSE is believed to be
unaffected by dendrite-induced damage because of mechanical rigidity
at the beginning. However, recent reports show that lithium metal can
penetrate solid materials [42]. Metal dendrite can grow along the lattice
defects to penetrate separator. Thus, SSE does not depend on complete
electrolyte shear modulus. Minimizing interfacial defects has been
suggested to fight against lithium metal penetration effectively. Inor­
ganic solid electrolytes are also difficult to process because of their
brittleness [43].
2.2. Polymer-based electrolytes
In 1973, Wright et al. [44] discovered a new direction for solid-state
battery research. Ionic conduction can occur between polyethylene
oxide (PEO) and alkali metal salts because PEO can be complicated with
alkali metal salts. The conductivity of the complex is mainly because of
the contribution of cation migration. Cation movement can be carried
out not only at different coordination sites in a chain but also between
coordination sites in different chains. Many descriptions of ionic con­
duction mechanism exist in complexes, among which crystal vacancy
diffusion mechanism [45] and free volume model [46] are the most
popular. The types of polymers chiefly consist of PEO-based [47] and
polysiloxane-based [48] single lithium-ion conducting polymer [49,50].
Compared with inorganic solid electrolyte and liquid electrolyte, solid
polymer electrolyte is more flexible, has more plasticity, and safer;
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Sustainable Materials and Technologies 29 (2021) e00297
Electrochemical Stability Mechanical strength Price
Medium Low Cheap
Medium Excellent Cheap
High Medium Expensive
High High Expensive
wetting property, which greatly reduces the interface impedance be­
tween electrolyte and electrode, paves the way for the integrated flex­
ible battery design [51]. For solid polymer electrolyte, first, ensuring
that the polymer base has the ability to dissolve lithium salt and
coupling with lithium ion is crucial. When the operating temperature is
lower than the polymer glass transition temperature, increasing the
resistance of decoupling makes dissociate lithium and polymer chain
becomes more difficult [52]. Furthermore, to promote the dissociation
of lithium in polymer, the selected lithium salt should have low lattice
energy with a high dielectric constant for the polymer [53,54]. The
number of free Li+ and the mobility of the chain overwhelmingly affect
the mobility of Li+, in which the quantity of free lithium ions depends on
the degree of dissociation of lithium salt in polymer electrolyte. Being
acted on by an electric field, Li+ can be transported through the
following forms. First, the ions are carried by a polymer chain and move
together. They are relatively static. Second, the ions move along the
polymer chain. Finally, Li+ jumps between different polymer chains
(Fig. 2-3) [55]. Most of the research in the influence of the ionic con­
ductivity of polymer electrolyte has been examined. As an example,
Fig. 2-3. Schematic diagram of lithium ion transport [55].
C. Li et al. Sustainable Materials and Technologies 29 (2021) e00297

PEO-based polymer electrolyte is mainly affected by the molecular
weight of the polymer, working temperature, and end group [56]. The
results of the work of the Gupta group imply that ionic conductivity is
~2.5 × 10− 5 S cm− 1 at 25 ◦ C and 2.3 × 10− 4 S cm− 1 at 40 ◦ C in ionic
liquid (IL)-based polymer electrolyte. The mobility of lithium ion in
polymer electrolyte at room temperature is proven to be much lower
than that at high temperature [57]. Moreover, the end group has a great
influence on ionic conductivity because the mobility of the end group is
higher than the middle one. That is, the smaller the molecular weight of
the polymer main chain is, the greater the effect of the end group on the
dynamic properties of the polymer chain is [58,59]. Devaux et al. [58]
constructed an equation that explained the relationship between mo­
lecular weight and end groups. When the mechanical strength of poly­
mer electrolyte is insufficient, lithium dendrite grows rapidly, which
makes the positive and negative electrodes short-circuited and leads to
battery failure (Fig. 3-1)[60]. Another weakness of polymer electrolyte
is the narrow voltage window. The most investigated polymeric hosts for
electrolyte cannot absolutely match the requirements of high voltage
LIBs. which is a great challenge for industrialization [61].
2.3. Hybrid SSEs
Hybrid SSE becomes a research hotspot to compensate for the dis­
advantages of single type material. Although inorganic ceramics mate­
rial enjoys high mechanical property, poor interface compatibility is
adverse for hybrid SSE [62–64]; polymer material can ignore interface
problem, but insufficient mechanical strength stands out [65]. Typical
ceramic/polymer composite SSE, which uses polymer material to
improve interfacial compatibility between electrodes/electrolyte and
uses inorganic fillers to regulate ion migration, reaps large fruits. As an
example, Chen et al. [66] found that GO could create a close connection
with PVDF-HFP-PEO based gel polymer electrolyte via weak hydrogen
bond interactions. The results imply that the ionic conductivity of PVDF-
HFP-PEO-GO is 2.1 × 10− 3 S cm− 1, which is up to twice as many as
PVDF-HFP-PEO. Furthermore, the 3D porous network shaped by GO
with polymers provides ample mechanical strength for gel polymer
electrolytes.
However, complementing one another is not that simple. Initially,
constructing a superior packing polymer dispersion system for the
preparation of hybrid SSE is formidable [67]. The most common concern
is the particle agglomeration effect, which may sacrifice many advan­
tages of the polymer [68,69]. Then, the compatibility of polymer and
filler has a great influence on hybrid SSE. Mendes et al. [70] pointed to
the importance of the filler size in determining the interaction with the
polymer matrix. The smaller the particle size, the larger the relative
interaction region between the ceramic filler and the polymer matrix.
The migration index of Li+ is limited by the filler size, concentration, and
morphology of filler dispersion in composite electrolyte [71,72]. A
perfect balance point is the critical key for hybrid SSE performance.
Another challenge for ceramic/polymer electrolytes is to construct
ultrathin electrolyte membranes [73]. The increase in electrolyte weight
may lead to a decrease in energy density; also, thicker electrolyte
membranes mean higher electric resistance, leading to worse perfor­
mance [74,75].
Compared with the synthesis of a single polymer or inorganic ma­
terials, the cost of materials and equipment for composite electrolyte is
higher, which brings arduous things for the commercialization of hybrid
SSE in the future. Therefore, discovering a simple synthesis technology
for hybrid SSE on the basis of considering the excellent properties of
composite electrolyte is urgent. In any case, composite electrolyte is the
trend of electrolyte research in the future, which has great research
potential in the field of all solid-state batteries.
As a conclusion, the main challenges of SSE can be concluded as the
following four points:
1) to achieve high ionic conductivity at room temperature to ensure
that it can be comparable with liquid electrolyte
2) To study the mechanism of the lithium dendrite growth of solid
electrolyte and find a way to solve thoroughly the problem of
dendrite growth of composite solid electrolyte
3) To resolve financially-challenged contact between electrodes/elec­
trolytes and reduce side effects between interfaces during the charge-
discharge cycle
4) To ensure positive thermal stability and electrochemical stability at a
wide range of temperatures and voltages
3. Progress in improving the property of SSEs
3.1. Improvement of physical properties
Compared with liquid electrolyte, SSE usually has higher mechanical
modulus, which can prevent the growth and diffusion of lithium
dendrite to a certain extent [76]. For a traditional liquid electrolyte
battery system formed by Li+ reduction reaction, lithium dendrite
continuously consumes the electrolyte, causes electrode/electrolyte
interface instability, destroys the generated SSE interface membrane,
and detaches from the electrode, leading to dead Li and resulting in low
coulomb efficiency [77]. In some extreme cases, the separator

Fig. 3-1. Schematic of the Li stripping/plating process. a). Normal Li metal electrode with perfect SEI; b). Li plating causes volume expansion, which cracks the SEI
film; c). Further plating causes Li dendrites to shoot out through the cracks; d). Li stripping produces isolated Li which becomes part of the dead Li, while volume
contraction results in further SEI fracture, meanwhile, some isolated Li redeposit; e). continuous cycling result in accumulated dead Li, thick SEI and porous Li
electrode [77].

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C. Li et al. Sustainable Materials and Technologies 29 (2021) e00297

Fig. 3-2. The morphologies of lithium with a single polymer network and double network [84].

Fig. 3-3. a). Schematic illustration of the synthesis process of the HGPE. b). Digital photo of the as-prepared GPE and HGPE. c). Schematic comparison of the Li
dendrite growth in the HGPE and GPE [102]. d). Structure and Na-ion transportation mechanism of ANs–GPE [100].

penetrated by lithium dendrite causes a series of battery failure hazards,
including internal short circuit, thermal runaway, and explosion.
Mechanical strength, the ionic conductivity of polymer and polymer
base SSE, and inorganic SSE interface compatibility are insufficient.
Their excellent potential ability deserves further investigation.
3.1.1. Polymer engineering
Various approaches are adopted to improve the semi-crystalline
nature of the polymer, such as crosslinking and blending [78,79].
Polymer crosslinking is a cost-effective method and has captured more
attention. The polymer crosslinking section includes thermal cross­
linking [80] and radiation crosslinking [81]. Cross-linking can not only
stabilize the amorphous phase and enhance ionic conductivity at room
temperature but also inhibit the mechanical property degradation
caused by the use of a low glass transition temperature chain as the
skeleton structure [82]. Crosslinking is the process of changing linear

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C. Li et al.
Fig. 3-4. a). Schematic illustration of the inhibition of dendrite growth by 2D nanoflakes [106]. b). Schematic of vertical temperature gradient freezing of VS
dispersion in a Teflon mold, which is placed on top of liquid N2 to induce the directional [110]. c). Schematic image for the preparation of MOF membrane [109].
structure polymer with reactive activity into a 3D network structure
polymer through a series of reactions [83]. A quintessential example
should be cited. Wu et al. [84] demonstrated a double polymer network
(PVDF-HFP and PEO) as the framework by UV crosslinking to enhance
mechanical strength and ion conductivity (Fig. 3-2). The PEO matrix
provides the tunnel for cation migration, whereas the PVDF-HFP matrix
supports improving mechanical properties.
The polymer blend is another way to improve the dimensional sta­
bility of the polymer matrix. The mixed polymer gives rise to the
structure change of the host polymer matrix structure change and re­
duces the crystallization tendency of the matrix [85]. The common
morphology of the blend polymer is that the polymer as a minor
component is dispersed in the continuous phase of another polymer.
Wang and Tang [86] prepared the polymer electrolytes composed of the
blend of PMAML/PVDF-HFP. On the basis of high ionic conductivity
guaranteed by PMAML, those successfully blended with PVDF-HFP can
compensate for the mechanical stability of the polymer membrane. The
particle size, uniformity of the dispersed phase particles, and dis­
persibility in the continuous phase mainly depend on the compatibility
of the components and the blending method, which has a noteworthy
impact on the properties of the composition [87].
Besides the above polymer modification methods, many other
methods improve the mechanical strength in the polymer matrix, such
as polymer grafting [88]. In the future, we need to explore and discover
more polymer modification methods.
3.1.2. Inert filler
Adding nano-inorganic materials into polymer SSE to improve me­
chanical strength has a long history [ [89–92]].Inorganic fillers can be
embedded in SSE to form self-supporting structures to improve
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Sustainable Materials and Technologies 29 (2021) e00297
mechanical properties. According to the properties of inorganic fillers
for polymers, fillers can be divided into inert and active fillers, in which
inert fillers do not participate in ion transport [93]. Poor Li-ion
conductive materials are introduced to polymer SSE to enhance their
mechanical properties. The size and morphology of inorganic filler can
significantly affect the mechanical properties [94]. In recent years, the
morphology of inorganic fillers has been expanded from nanoparticles to
1D and 2D materials and has become a research hotspot of new solid
electrolyte design [95,96].
0D nanoparticles. Since 1982, Weston and Steele [97] first found that,
when α-Al2O3 was added to the polymer system as an inert filler, α-Al2O3
could be uniformly dispersed to the polymer system as a skeleton
structure to enhance greatly the mechanical strength of SSE. A new
window has been made for strengthening SSE mechanical properties by
filling metal oxide into polymer SSE, such as TiO2 [98], Al2O3 [99], SiO2
[100], and ZrO2 [101]. Besides that, more exotic materials provided
with passive fillers are occurring [ [102]].For more than 30 years of
polymer electrolyte development, scientists found that regulating the
size and proportion of nano-particle doping can generally improve the
conductivity of the electrolyte by one to two orders of magnitude. When
the inorganic filler particles are relatively large (>40 um), no obvious
increase in ionic conductivity is observed [103]. However, as the par­
ticles become smaller (diameter ranging from submicron to a few mi­
crons), the conductivity of the ions increases [103].
Although inorganic filler can improve mechanical strength, the
uniformity and compatibility of inorganic filler are still an intractable
problem to be solved. If the dispersion of the inorganic filler in the
polymer is uneven, agglomeration may happen, and ionic conductivity
becomes affected [104]. In this perspective, Lin et al. [105] reported a
C. Li et al. Sustainable Materials and Technologies 29 (2021) e00297

Fig. 3-5. a). Schematic of Li-ion pathways within LLZO (5 wt%)–PEO (LiTFSI), LLZO (20 wt%)–PEO (LiTFSI), LLZO (50 wt%)–PEO (LITFSI), and LLZO (50 wt%)–
PEO (LiTFSI) (50 wt%)–TEGDME composite electrolytes [122]. b). Schematic of the hybrid solid-state composite electrolyte, where ceramic garnet nanofibers
function as the reinforcement and lithium-ion–conducting polymer functions as the matrix. The inter-welded garnet nanofiber network provides an constants ion-
conducting pathway in the electrolyte film [126]. c). The effects of ordered and disordered nanoparticles and nanowire on lithium ion transport in polymer matrix.

into an interlacing network, the excellent plasticity is significant to the

Fig. 3-6. Li+ ion coordination in ternary polymer electrolytes containing active
polymers (PEO) and inactive polymers (PVDF) [55].
method of in situ synthesis of inorganic fillers (SiO2) into PEO-LiClO4,
which ensures the uniformity of the particles and significantly improves
the electrochemical performance of composite electrolytes.
1D nanowire. Given that the ability of nanoparticle fillers support me­
chanical strength is relatively low and limited, high dimensional mate­
rials emerged. High specific surface and the length-to-diameter ratio of
nanowires normally provide better mechanical strength characteristics
than same material nanoparticle [106,107]. Nanowires also have
excellent mechanical flexibility and Young’s modulus. When fabricated
manufacture of micro flexible or wearable electronic components. For
instance, Zhao et al. [108] engineered a nanowire-film-reinforced
hybrid gel polymer electrolyte. The interlacing porous nanowire films
serve as the skeleton, which strengthens the mechanical structure for
SSE and ensures the coherence of Li + conduction. The free-standing
MnOOH@Al2O3 skeleton accomplishes the suppression of Li dendrites
and additionally promotes ionic conductivity (1.04 × 10− 4 S cm− 1) with
the film of a controllable thickness (Figs. 3-3a, 3-3b, and 3-3c). A larger
surface area results in a larger electrode-electrolyte contact area and
shortens charge/discharge time. Moreover, nanowires can restrict vol­
ume expansion, inhibit mechanical degradation, and extend cycle life
[109]. Outstanding performance can be observed in LIB and sodium-ion
batteries. The cross-linked β/β”-Al2O3 nanowires (ANs) coated by
PVDF–HFP composite electrolyte display excellent capacity retention of
78.8% after 1000 cycles at 1C and 60 ◦ C in sodium batteries [110].
According to Lei’s result, compared with the traditional PVDF-based
polymer electrolyte, this nanowire design suppresses sodium dendrite
formation and side reaction occurrence (Fig. 3.3d). 1D nanostructures
with easy stress release and short ion diffusion distance are important
for the fabrication of fast and long-life batteries.
2D nanosheet. Ultra-thin 2D nanomaterials are an emerging class of
nanomaterials with lamellar structures. Normally, horizontal di­
mensions are more than 100 nm but only a single or few atoms thick

7
C. Li et al.
Fig. 3-7. a). Interfacial reaction (1) redox, (2) chemical and (3) electrochemical reactions [146] [143].
Fig. 3-8. Schematic of the novel cathode-supported SSLIB in comparison with a conventional rigid SSLIB and a typical liquid LIB [162].
(typically less than 5 nm), usually including transitioning metal car­
bides, nitrides, and carbonitrides (MAX phases); layered double hy­
droxides; metal-organic frameworks (MOFs); and covalent organic
frameworks [111]. In recent years, 2D nanomaterials graphene and
graphene analogs have been widely studied and applied [112]. Shim
et al. [113] reported a simple and effective strategy to prepare highly
dendrite-suppressing gel polymer electrolytes utilizing 2D boron nitride
nanosheets as a multifunctional additive, which eventually leads to the
realization of safe, long cycle life and high-rate performance (Fig. 3.4 a).
This kind of 2D nanosheets possesses strong in-plane covalent bond and
thin atomic layer thickness and contributes excellent mechanical
strength and flexibility. This unique filler design takes the mechanical
properties to a new level. Tang et al. [114] designed vertically aligned
2D sheets (VS) as an advanced filler for solid-state lithium metal bat­
teries. VS induced directional freeze casting (Fig. 3.4b). This kind of
highly ordered inorganic filler presents ionic conductivity as high as
1.89 × 10− 4 S cm− 1 at room temperature. Even after long cycles, the
surface of lithium metal remains smooth and flat, and no observational
dendrite growth is observed under a scanning electron microscope.
Furthermore, given that the 2D material can maintain atomic thickness
while having the maximum plane size, which gives the 2D material a
large specific surface area. 2D nanomaterials for huge surface areas are
known to bring viable support capacity alongside polymer matrices
[115]. However, randomly arranged 2D nanomaterials have over­
lapping stacking areas, which determine whether the utilization of the
surface is maximized. As a result, the nanometer skeleton constructed by
directional alignment appears, which shows better mechanical
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Sustainable Materials and Technologies 29 (2021) e00297
properties. The ordered arrangement of 2D nanosheets can be induced in
many ways. Among them, vacuum filtration can be regarded as the
simplest and the lowest cost way. Tian et al. [116] assembled and ori­
ented flexible MOF membrane using the vacuum-assisted filtration
method. The self-supporting MOF membrane is strong enough to replace
the separator and prevent dendrite penetration (Fig. 3-4c). In the future,
the application of 2D materials to solid electrolytes as the filler has a lot
of potential and deserves further exploration and research.
3.2. Ionic conductivity
3.2.1. High Li+ conductive materials
Apart from the inert filler, the active filler can be used as a skeleton
structure, mainly improving the ionic conductivity and thermal stability
of the solid electrolyte. Active fillers, also known as Li+ conductive
materials, which can directly participate in ion transport and provide
lithium source, can be directly used as components of solid electrolytes,
such as Li0.33La0.557TiO3 [117], tetragonal Li7La3Zr2O12 [118], and
Li1.3Al0.3Ti1.7 (PO4)3 [119]. Adding inorganic solid electrolyte particles
with high ionic conductivity into the polymer to prepare mixed solid
electrolyte can not only reduce the degree of crystallization of polymer
but also realize the migration and conduction of lithium ion in inorganic
ions, thus greatly improving the ionic conductivity of the composite
solid electrolyte. However, in the composite electrolyte, the relation of
the proportion of the active filler and the contribution to the ionic
conductivity is positive, or the active filler is only used to inhibit
dendrite growth. Zhao et al. [120] synthesized a PEO-LITFSI solid
 C. Li et al.
Fig. 3-9. a, b). Schematics of the Li stripping/plating at high rate and high capacity in solid-state cells with a garnet-type SSE, using a pure Li-metal anode and the
Li–Mg alloy anode [164]. c). The schematic illustration for the synthetic process to produce both LAGP nano-coating and salt-based passivation [165].
Fig. 4-1. The energy density growth trend of lithium battery in the
future [168].
electrolyte membrane with the additive of Al-doped Li6.75La3Zr1.75
Ta0.25O12. This active filler has little effect on ionic conductivity but is a
rigid part to block dendrites. With the increasing proportion of active
fillers in the polymer matrix, the material is transitioning from “ce­
ramics in polymer” to “polymers in ceramics.” [121] Zheng and Hu
[122] found that with the Li7La3Zr2O12 (LLZO) phase proportion
increasing in the LLZO–poly (ethylene oxide) composite, the ion
migration path type shifted from polymer to ceramics. The active ion
9
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Sustainable Materials and Technologies 29 (2021) e00297
concentration increased (Fig. 3-5a). Compared with the ion transport
mechanism of polymer, ceramic electrolyte normally has faster ion
transportability. With the increasing load of ceramic in polymer, ionic
conductivity can be increased by approximately 10 orders of magnitude
or more [123]. Lithium ion can conduct rapidly on the interface between
active fillers and polymer electrolyte [124]. On this account, ionic
conductivity increases with the increasing filling rate. However, at a
certain packing ratio, ionic conductivity begins to decrease because of
the reduction of the interface between polymer and ceramic fillers due to
the aggregation of high concentration fillers [125].
Active fillers, which are the same as inert fillers, can be divided into
0D, 1D, 2D, and 3D inorganic fillers. The morphology of the active filler
has a great influence on ionic conductivity and can be mainly attributed
to the ion migration path difference. At present, 3D inorganic fillers
stand out because of a large aspect ratio and good migration routes that
are superior to others.
Fu et al. created a 3D lithium-ion–conducting ceramic network in
light of a garnet-type Li6.4La3Zr2Al0.2O12 (LLZO) lithium-ion conductor
to provide nonstop Li+ exchange channels in a PEO-based composite
(Fig. 3-5b). The 3D garnet nanofiber networks are prepared by an
electrospinning/calcination process. By this way, the ionic conductivity
can even reach 2.5 × 10− 4 S cm− 1 at room temperature. This kind of
continuous 3D inorganic network can optimize the ion transport per­
formance by constructing a continuous active inorganic/organic inter­
face matrix, which can provide a continuous lithium-ion transport
channel, reduce the interface stacks between the polymer and ceramic
fillers, and provide the possibility for further improving the ionic con­
ductivity of such composite solid electrolytes.
Regardless of the shape of the inorganic material, the orientation of
C. Li et al.
the fillers has a great influence on the ionic conductivity [127,128].
When the fillers are randomly arranged in the polymer matrix, the
interface between the fillers and the polymer may be zigzag and
discontinuous, which leads to the failure to maximize the ion transport
capacity. Liu et al. [129] reported a composite polymer electrolyte with
well-aligned inorganic Li+-conductive nanowires, which has one order
of magnitude higher ionic conductivity than that with a randomly
aligned one. The result shows the importance of a continuous interface
for aligned CSSEs (Fig. 3.5c). According to the above discussion, a less
tortuous, continuous network of active inorganic/organic interfaces
facilitates ion conduction, which is a higher breakthrough in ionic
conductivity.
3.2.2. Plasticizer
Compared with an active material filler, the plasticizer is another
effective way to increase electrochemical performance. Given that the
ion transport of polymer is mostly realized by the chain segment
movement in the amorphous region, high crystallinity and low salt
solubility lead low room temperature ionic conductivity. To improve
conductivity, scientists mainly focus on two points:
1. Increasing the percentage of the amorphous phase in the polymer
matrix
2. Reduce the glass transition temperature
Multiple methods have been used to reduce the crystallinity and
increase the conductivity of polymer electrolytes, including copoly­
merization [130], grafting [131], crosslinking [132], adding plasticizers
[133], and the mixing of inorganic additives [134]. The most effective
way to increase conductivity is to form gel polymer electrolytes by
adding plasticizers into solid polymer electrolytes. The reason is that
plasticizers are mostly liquid or liquid-like materials, which greatly
contribute to the improvement of ionic conductivity. The addition of
plasticizers can increase the amorphous area, promote the movement of
chain segments and the dissociation of ion pairs, and improve the ionic
conductivity of polymer electrolyte [135]. Given the different forces
between plasticizer molecules, between plasticizer molecules and
polymer molecules, and between polymer macromolecules, adding
plasticizers can generally change the forces between polymer molecular
chains. More specifically, the force between polymer molecular chains is
weakened. Thus, the mobility between polymer molecular chains is
increased, and other molecules with different structural types are
introduced between polymer molecules to make the molecules irregular
such that the crystallinity of the polymer molecular chain is also
reduced. Furthermore, SSE, combined with plasticizers, can reduce
brittleness to achieve better interface contact between solid electrolyte
and electrode in terms of physical properties. Plasticizers can be
generally divided into three categories, namely, low molecular solid
organics, organic solvents, and ILs.
Solid organics with low molecular weight normally is the cheapest
and most common plasticizer among the three categories above. Chen
et al. [136] added SN (N ≡ C-CH2-CH2-C ≡ N, abbreviated as SN) into
the PEO-LITFSI-LGPS system. SN, as a solid organic nonionic plastic
material, can dissolve lithium salt and form solution at room tempera­
ture. When the content of SN is 10%, the conductivity reaches 9.1 ×
10− 5 S cm− 1 (25 ◦ C). Meanwhile, SN possesses high-voltage tolerance,
which can widen the electrochemical window to 5.5 V [137]. This
compound shows excellent cycle rate performance in the LiFePO4/Li
battery system. The research result also pointed out that, when the
content of SN is more than 10%, excessive SN gathers and aggregates to
block ion transmission, resulting in a decrease of ionic conductivity.
ILs are organic salts that remain in the liquid state over a wide
temperature range. ILs have the advantages of stable thermal and elec­
trochemical property, negligible vapor pressure, and incombustibility
[138]. ILs also display high ionic conductivity as a result of their high
mobility and high concentration of carrier ions. As a consequence, ILs
10
Sustainable Materials and Technologies 29 (2021) e00297
are usually used as an excellent plasticizing additive to improve the ionic
conductivity of SSE [139]. Tsurumaki et al. [134] mentioned that
Pyr14TFSI can react with the PEO matrix at room temperature, forming a
turbid mixture. When the mixture is formed, ion transport occurs in both
phases and mainly in the ILs phase [140]. However, when ILs are added
to the non-interacting polymer matrix, ILs are used as “liquid solvents,”
which greatly affect the viscosity of gel electrolytes [55]. As an example,
in the PVDF-HFP/ILs system, PVDF-HFP can act as inert support to
immobilize ILs, and ILs are used to provide rapid ion transport (Fig. 3-6)
[55].
The organic solvents are widely used as plasticizers in SSE, such as
ethyl carbonate and propyl carbonate. Given that the organic solvents
mostly have high relative permittivity, they are provided with the ability
to enhance the dissociation of salt ion pairs [141,142].
Controlling the content of plasticizers to solve the problems of the
solid electrolyte is crucial. Some plasticizers have the characteristics of
liquid solvents, which affect the viscosity of solid electrolyte and thus
influence the electrochemical performance of the battery. The addition
of a liquid plasticizer can improve conductivity. Furthermore, the me­
chanical properties of the electrolyte may be damaged, which causes
degeneration performance in the cycle and safety problem of the
battery.
3.3. Interface problem
Given that electrolyte is changed from liquid to solid, the electrolyte/
electrode interface of the LIB system is transformed into the solid-solid
interface. Currently, the solid-solid interface between the electrolyte/
electrode presents a host of challenges [143]. First, in contrast to liquid
electrolytes, no wettability is between the solid-solid interface, which
makes achieving full contact difficult. The small effective interface area
between the electrolyte/electrode can form a higher contact resistance
and lead to a large barrier for charge transfer [144,145]. Second,
chemical reactions that take place at an electrolyte/electrode interface
during cycling should be considered (Fig. 3–7). The chemical reaction is
mainly divided into the oxidation-reduction electrolyte decomposition
reaction and the chemical reaction between the electrolyte/electrode
[146]. Decomposition reaction is characterized by only the insertion or
removal of electrons or carriers [143]. These two reactions can occur
independently or simultaneously, which determines the electrochemical
performance of the LIB. Finally, the electrolyte/electrode interface
forms a space charge layer, which leads to a sharp increase in the in­
ternal resistance [147]. Besides, the existence of the space charge layer
hinders the uniform deposition of lithium dendrites and induces the
growth of lithium dendrites.
The ideal interface layer should be an ionic conductor and an elec­
tronic insulator. If the interface layer is a mixed conductor of ions and
electrons or in an unstable state, the interface reaction takes place all the
time, and the reactants produced deposit into the interface layer. With
the increasing thickness of the interface layer, the electrochemical per­
formance severely deteriorates. The methods to solve the interface
problems mainly consider two angles. One is to regulate the composition
of the solid electrolyte, and the other is to design the whole solid-state
battery structure engineering.
3.3.1. Components of SSEs
Many researchers have been working on inorganic ceramic electro­
lytes since the 1960s as an inorganic material with high ionic conduc­
tivity [148]. However, inorganic ceramic electrolytes in the
development of solid-state batteries lose intense contact between the Li/
SSE interface, which leads to side reaction and poor electrochemical
stability [143,149]. After cycling, the volume of lithium metal electrode
expands and even pulverizes because of the side reaction. Furthermore,
the lack of elasticity of the interface layer further deteriorates interface
performance [150]. Adding liquid solvents to ceramic electrolytes to
form gel electrolytes (also known as semi-solid electrolytes) can
C. Li et al.
circumvent the problems caused by interfacial effects [151,152]. Poly­
mers have the advantage of better flexibility; once the polymer is
compounded with the ceramic electrolyte to form a composite electro­
lyte, it can make better interface contact and greatly alleviate interface
problems [153,154]. Moreover, the composite electrolyte composed of
inorganic ceramics with high ionic conductivity and soft polymer matrix
can provide excellent interface contact and achieve high compression
[155]. The reasonable control of the composition of the composite
electrolyte can also reduce the interface impedance and prevent the
interface reaction.
3.3.2. Structural design of solid-state batteries
Starting from the whole solid-state battery design, varieties of inte­
grated battery structure that can effectively solve various interface
problems emerged. The ideal interface engineering between solid elec­
trolyte and electrode is also key in the extension of the electrochemical
stability window. So far, the design of multilayer electrolyte is the most
popular in interface engineering. Fu et al. [156] proposed to modify the
interface between electrode and electrolyte by embedding Li–Al alloy
layer as a wetting layer. In the report, Al alloyed with the Li metal can
fully coat the garnet SSE material. Based on that comparison, the
interface impedance of garnet/Li in direct contact is 950 Ω cm2. After
surface modification, the impedance falls to 75 Ω cm2, which is better
than an order of magnitude difference. Adding a middle layer between
solid electrolyte and lithium metal is considered to be the most common
and effective way to improve mechanical compatibility and reduce the
interface resistance. To date, the reported surface treatment layers
include a thin film of Li-M alloy [157], oxides [158], or amorphous Si
[159], among others [160].
Besides, professor Wang’s team from the South China University of
Technology initiated a new method to solve the electrodes/electrolyte
interface [161]. The SSE slurry is directly coated on the surface of the
cathode electrode material. Meanwhile, the slurry can penetrate the
pores of the cathode electrode material with the solvent, which perfectly
solves the contact problem between the electrode and the electrolyte
(Fig. 3-8).
Sun’s team [163] first proposed to use molecular layer deposition
technology to deposit an organic-inorganic mixed interlayer between
the lithium metal anode and the sulfide electrolyte, which can ensure the
good contact between the lithium metal and the electrolyte and avoid
the generation of lithium dendrites. This solid-state battery design
matched with lithium anode shows a lower degree of polarization and
higher capacity.
Surface modification at the interface of electrode and electrolyte
only solves the problem of the interface. As the lithium ions are
continuously embedded and removed, voids also occur inside the elec­
trode. Thus, Yang et al. [164] designed an electron/ion dual-conductive
alloy framework, which fills the gap between the interface with volume
change (Figs. 3-9a and 3-9b). The framework can be constructed by
dealloying a Li–Mg alloy anode on a garnet electrolyte. The design
principle is when a certain amount of lithium is stripped from the alloy
anode. The alloy becomes a kind of lithium deficient material with the
porous framework but still forms seamless interface contact and keeps
low interface contact with garnet electrolytes. The main reason is that
the structure of lithium magnesium solid solution is similar to that of
lithium metal, which effectively prevents the phase transformation of
lithium metal in the process of electrochemical plating/stripping, and no
structural fracture is observed. This idea solves the poor contact of Li/
SSE interface and restrains the pores caused by lithium circulation inside
the electrode. Professor Yang Yuan’s team [165] fully mixed LCO and
LAGP through ball milling as positive electrodes, which realized higher
voltage electrodes and ensured good interface compatibility during
battery charging and discharging operation (Fig. 3-9c).
This solid electrolyte/electrode material integrated design can
effectively strengthen the solid-solid interface contact, reduce the bat­
tery impedance, and achieve the high specific energy and long life of the
11
Sustainable Materials and Technologies 29 (2021) e00297
flexible solid-state battery.
4. Conclusion and outlook
The worldwide campaign on battery application has entered a high-
speed development stage, which urgently needs energy storage tech­
nology with high specific energy, high energy density, and safety.
Commercial LIBs have restricted energy density because of flammable
liquid organic solvent electrolyte and have exposed many security
problems during the practical application process. Although many ad­
ditives [166,167] are added to improve the electrochemical perfor­
mance and safety of liquid electrolyte, they cannot completely solve the
problems caused by the liquid electrolyte. Particularly for large-scale
energy storage equipment, this improvement is not enough to fulfill
the demand. At present, solid-state batteries with high energy density
and high safety characteristics are attracting worldwide attention [168].
The solid-state lithium battery is expected to become the leading di­
rection of the next generation of automotive power battery(Fig. 4-1)
[21].
In this perspective, we identified the most critical challenges for SSE
and pointed out present solutions for these challenges. Given that these
challenges are often interrelated, compromises are often made to bal­
ance different aspects of battery properties. It is next to impossible to
make a further breakthrough in the energy density of commercialized
lithium-ion battery, unless increase nickel content or level up cut-off
voltage, which might bring low thermostability and security risk.
Widely believed that battery system solidization is the terminate solu­
tion to the safety issue.
As Darren H. S. Tan ‘s team [169] proposed, there are four major
challenges to the practicality of solid-state batteries: solid-state elec­
trolyte properties, interface characterization technology, scale-up
design and production, and sustainable development; Jennifer L. M.
Rupp group [170] critically discusses the opportunities of oxide solid
state electrolytes application. Further low-cost technology and elaborate
economical calculation are needed to ensure solid-state batteries
commercialization.
Relevant research institutions and enterprises from different coun­
tries and regions have entered the “track” one after another, opening a
“pull race” to promote the layout and speed up the research and
development of solid-state batteries. In 2011, Bolloré of France intro­
duced the first commercialize solid-state batteries for electric vehicles
with only approximate 100 Wh/kg energy density. 5 years later, another
solid-state electrolyte lithium metal battery was introduced by America
Solid Energy Company reached 300 Wh/kg. Though thin-film method
manufacture route gradual maturity brings 3 times energy density
increasing in the past several years, compared with liquid electrolyte
system, complicated manufacture process makes all solid battery large-
scale application still be a long day off [11,49].
In conclusion, the ideal solid electrolyte should have high ionic
conductivity, negligible electronic conductivity, wide working voltage
window, and good chemical compatibility with the electrode. To ach­
ieve these goals, potential research efforts are proposed as follows:
1. Improved research of the mechanism of lithium-ion transport and the
reaction between the interfaces will help us to design lithium-ion
batteries with higher energy density and safety.
2. Future research should go back to the source to study the factors of
battery failure and design a solid-state battery with high specific
capacity and long cycle.
3. More advanced characterization technology and simulation must be
developed. These methods will be more convenient and accurate in
the study of the ion transport mechanism and electrolyte/electrode
interface properties, such as synchrotron radiation-based X-ray
techniques (XAS, STXM, X-ray computed tomography), HRTEM,
Rutherford backscattering spectroscopy.
C. Li et al. Sustainable Materials and Technologies 29 (2021) e00297

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