Energy Storage Materials 45 (2022) 969–1001

Contents lists available at ScienceDirect

Energy Storage Materials

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

Interfaces in all solid state Li-metal batteries: A review on instabilities,

stabilization strategies, and scalability
Partha P. Paul a, Bor-Rong Chen b, Spencer A. Langevin c, Eric J. Dufek b, Johanna Nelson Weker a,
Jesse S. Ko c,∗
a
SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA 94025, USA
b
Energy Storage and Electric Transportation Department, Energy and Environmental Science and Technology, Idaho National Laboratory, Idaho Falls, ID 83415, USA
c
Research and Exploratory Development Department, Johns Hopkins University Applied Physics Laboratory, 11100 Johns Hopkins Road, Laurel, MD 20723, USA

a r t i c l e i n f o a b s t r a c t

Keywords: With technological advancements in electrochemical energy storage systems increasing at a spectacular rate,
Lithium metal battery batteries equipped with a lithium anode hold the key towards unlocking high energy densities. While lithium-ion
All solid-state battery batteries with layered anodes (e.g. graphite) and liquid organic electrolytes have been ubiquitous in portable
Interfaces
electronics, electric vehicles, and grid applications, all solid-state batteries that use the combination of a lithium
Solid-state electrolyte
anode and a solid-state electrolyte (SSE) will further advance the present technology. The underlying challenge
that limits the successful development of all solid-state batteries (ASSBs) is dictated largely by the highly reactive
interfaces at the anode/SSE and the cathode/SSE interface. In this comprehensive review, we present an overview
of the following: (i) characterization of the electrode/SSE interface via multimodal characterization, which include
X-ray-, electron-, neutron-, optical-, and computation-based methods: (ii) parasitic reactions that occur from
chemical, mechanical or electrochemical instabilities and interfacial engineering strategies for improving the
stability of these interfaces classified by the class of inorganic SSEs (sulfide-, NASICON-, and garnet-type SSEs);
(iii) laboratory-to-industry scale processing perspectives of SSEs; (iv) scalability and manufacturing aspects of
current interfacial strategies; and (v) the prospects of all ASSBs within the context of extreme fast charging
capability. This review seeks to highlight key efforts in the field of ASSBs, by focusing particularly on stabilizing
the electrode/SSE interfaces, which will help to bridge fundamental studies to technological relevance.

1. Introduction to the success of reversible Li-ion intercalation, by means of the forma-

Li-ion batteries have dominated the energy storage landscape over
the past several decades, with widespread use ranging from the automo-
tive industry, to portable electronics, and even to grid-scale applications
[1]. They are being considered as a longer term and more sustainable
replacement for traditional sources of energy, such as gasoline and coal.
The underlying attributes behind this alarming growth is owed to the
highly desirable gravimetric and volumetric energy densities, enabled
by the reversible intercalation of Li-ions. Traditional Li-ion batteries
(LIBs) consist of layered active materials, which act as the positive and
negative electrodes, into which Li-ions can reversibly intercalate in a
liquid electrolyte medium [2].
However, as Li-ion technology continues to gain increased commer-
cial applicability, there is an urgent need to improve these systems,
in terms of both safety and performance [3]. Conventional liquid elec-
trolytes used in current LIBs hold safety concerns due to the fire hazards
associated with flammable organic solvents, which are the cornerstone
tion of a stable solid electrolyte interphase. In terms of performance,
the main thrusts are geared towards developing batteries that exhibit
higher capacities and faster recharging capability, particularly in the
automotive sector, where recharging times are significantly longer than
refueling times in gasoline-powered vehicles [4]. One way higher en-
ergy densities can be unlocked is by the use of alternate cations, such
as Na+ , Zn2+ , and Mg2+ , rather than Li+ [5,6]. Another major recent
thrust for batteries with improved energy densities has been to use Li
metal itself as the anode, instead of the conventional host electrode ma-
terial, such as graphite, which can theoretically result in a ten-fold in-
crease in the available energy density, owing to a more negative redox
potential and a low density [7,8]. However, Li metal is highly reactive
to environmental conditions and prone to dendrite formation at the an-
ode/electrolyte interface in liquid electrolytes. This reactivity drastically
reduces the available Li over cycling and will result in shorts between
the electrodes, eventually causing catastrophic battery failure [9]. To
fully exploit the higher theoretical energy density of the Li metal an-

∗
Corresponding author.
E-mail address: jesse.ko@jhuapl.edu (J.S. Ko).

https://doi.org/10.1016/j.ensm.2021.12.021
Received 31 August 2021; Received in revised form 7 December 2021; Accepted 15 December 2021
Available online 22 December 2021
2405-8297/© 2021 Elsevier B.V. All rights reserved.
P.P. Paul, B.-R. Chen, S.A. Langevin et al.
ode (3860 mAh g−1 ), a promising solution is to substitute the liquid
electrolyte for a solid-state electrolyte (SSE) in an all solid-state battery
(ASSB) configuration.
In an ASSB, the major function of a SSE is to physically separate the
cathode and the anode to prevent an internal short circuit, while provid-
ing a pathway for the movement of ions during charging and discharging
of the battery [10]. The SSE is multifunctional, acting as both a structure
that conducts Li-ions and as a separator between the anode and cathode.
By removing the flammable organic electrolyte, further development of
ASSBs can dramatically improve the safety aspect of this form of energy
storage [11]. Moreover, the replacement of the liquid electrolyte with a
more energy-dense SSE has advantages for the automotive sector, owing
to a potential reduction in size and weight of the battery cell.
Despite these advantages, several key challenges remain that ham-
per the successful development of ASSBs [12]. Challenges innate to
ASSBs include the following: (i) lower ionic conductivity of SSEs com-
pared to their liquid counterparts; (ii) loss of physical contact and lat-
tice mismatch at the interface of the electrode with the SSE during cy-
cling; (iii) propensity for lithium dendrite growth through grain bound-
aries of the SSE originating from the anode/SSE interface; (iv) chemi-
cal/electrochemical dissolution of the interface between the anode or
cathode and the SSE, which leads to high interfacial impedance and
loss of active Li inventory available for cycling; and lastly, (v) chal-
lenges toward manufacturing, pertaining to scalability concerns of the
numerous strategies developed at the lab-scale aiming to improve the
electrode/SSE interface.
A majority of these challenges are intricately tied to the solid/solid
interface between the SSE and the respective electrodes. While the spe-
cific challenges at the interface are dependent on the specific cathode
material and SSE employed in the ASSB, the interfacial instabilities can
broadly be classified into three overarching categories: (i) mechanical
instabilities; (ii) chemical instabilities; and (iii) electrochemical insta-
bilities. These interfacial instabilities have resulted in ASSBs that have
significantly lower current density, rate, and capacity retention over cy-
cling than current LIBs, which need to be improved significantly for
realizing widespread adoption of ASSBs. By addressing these aforemen-
tioned interfacial challenges, the prospects of developing ASSBs can be
accomplished and has the potential impact to provide next generation
safe, energy-dense electrochemical energy storage solutions for a myriad
of applications [13].
In this review, we focus on the interfaces inherent to ASSBs. We aim
to provide an overview of the various interfacial instabilities encoun-
tered in ASSBs, as well as the strategies to minimize such instabilities,
to improve ASSB performance. First, we provide a broad overview of
the various characterization methods (experimental and computational)
employed to interrogate interfaces in ASSBs. Characterization of inter-
faces in ASSBs, in particular operando studies, holds the key to under-
standing the various instabilities, which can serve as a critical feed-
back loop to inform the rational design of strategies to mitigate such
instabilities through interface engineering. The interfaces in ASSBs are
subsequently discussed from a materials perspective. The various inor-
ganic SSEs are categorized into sulfide-, NASICON- and garnet-type elec-
trolytes, and each individual interface (cathode/SSE and anode/SSE) is
sequentially discussed for each class of electrolytes. We note that we do
not cover organic, polymer-based SSEs in this review, and refer readers
to other excellent reviews on this topic [14,15]. We focus on the me-
chanical, chemical and electrochemical stability of these classes of SSEs
against the electrodes, as well as the interfacial engineering strategies
employed to mitigate these instabilities. Subsequently, we provide an
outlook on the future of ASSBs through the lens of commercialization
and batch manufacturing methods for the various interfacial strategies
discussed in the previous section. We also provide a brief overview of
the key challenges in realizing fast charging in ASSBs, without com-
promising the safety and capacity retention, which is a key to wider
commercial deployment of ASSBs in electric vehicles. Fig. 1 provides
a broad overview of the topics covered in this review. This compre-
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Energy Storage Materials 45 (2022) 969–1001
hensive review serves as a solid footprint for the future direction of re-
search aimed at interfacial strategies to stabilize solid/solid interfaces
in ASSBS.
2. Characterization of interfaces in ASSBs
Characterization of ASSBs is challenging due to the chemically com-
plex, multi-scale and time-sensitive nature of various phenomena of in-
terest in such systems. The following section provides a succinct outline
and specific examples of some of the local characterization techniques
that have been used to understand interfaces in ASSBs, in particular X-
ray–, electron–, and neutron–based techniques, apart from other imag-
ing techniques such as optical imaging and scanning probe microscopy.
We will focus on popular surface-sensitive techniques, which have been
used to study interfaces within the context of chemical, electrochemical,
and mechanical alterations, primarily on laboratory-scale cells. We also
overview the use of electrochemical impedance spectroscopy (EIS) as a
way to connect the direct observation of the interface to the impedance
at the interface, and in turn the performance of ASSBs. The outcomes
from these techniques can also be used with numerical-based modeling
techniques, either to shed further light on various interfacial mecha-
nisms in the system or to inform the design of improved interfaces with
optimized chemistries and geometries. For a more detailed overview
on characterization on ASSBs in general, we refer the reader to sev-
eral recent outstanding review articles focusing on ASSB characteriza-
tion [10,16–19]. We finally summarize our perspective on the need for
combination of complementary experimental, numerical and modeling
techniques: multimodal characterization, which holds the key towards the
a comprehensive understanding of interfacial behavior in ASSBs. Such
synergistic studies drive forward the shift from niche lab-based cells to
commercially relevant ASSBs, and their wider deployment as energy
storage devices.
2.1. X-ray–based methods
X-ray–based methods have been the popular method to study ASSBs
presently, in large part due to requiring minimal sample preparation
and the ability to conduct operando characterization across multiple
length scales, from nanometers to millimeters [20]. X-ray–based tech-
niques broadly span across spectroscopy (chemical information), imag-
ing (morphological information), and diffraction/scattering (structural
information) [21]. As an example, Vardar et al. used a suite of X-ray–
based characterization techniques including X-ray photoelectron spec-
troscopy (XPS), X-ray diffraction (XRD), and X-ray absorption spec-
troscopy (XAS) on an ASSB with garnet-type SSE (e.g. lithium lanthanum
zirconium oxide, or LLZO), to study the optimal annealing conditions
(time/temperature) for improved transport through the interface and
targeting higher capacity from the ASSB [22]. The X-ray techniques can
be either synchrotron-based or laboratory-based techniques. The for-
mer have a significantly higher flux and tunability of X-rays resulting
in reduction in data collection times making operando characterization
feasible on realistic cells; while the latter have a significantly higher ac-
cessibility, with more limited characterization capabilities and longer
acquisition times [23].
X-ray photoelectron spectroscopy: XPS is primarily a laboratory-
based technique, used to obtain information on the composition (chem-
ical) and electronic states of species at interfaces in ASSBs. Wenzel et al.
used XPS to observe the formation of reduced titanium ions (Ti3+ and
Ti2+ ), as well as metallic Ti, at the Li anode/LLTO (Li0.35 La0.55 TiO3 )
SSE interface [24]. Wood et al. used operando XPS to study the evolu-
tion of the SEI at the anode/SSE interface, as well as the local overpo-
tentials caused thereof, in sulfide SSEs [25], as shown in Fig. 2(a). Wu
et al. used XPS to gain insight into the LTO electrode/LPS SSE inter-
face, to focus on the impact of interfacial reactivity on cell performance
[26]. Park et al. used XPS to study the effect of processing temperature
on the performance of the LCO cathode/garnet SSE interface, showing
P.P. Paul, B.-R. Chen, S.A. Langevin et al.
that while elevated processing temperatures lead to improved physical
bonding, it can come at the cost of chemical instability at the inter-
face [27]. Due to XPS being relatively inexpensive and accessible, it is
a popular method to use in combination with other techniques to study
interfacial reactions in ASSBs. Koerver et al. used XPS coupled with EIS
to study the role of the formation of interfacial species and the corre-
sponding changes in key impedance parameters at the interfaces of both
the anode/SSE and the cathode/SSE to the cell performance in a sulfide
SSE system [28]. Another example of correlating EIS to XPS data was
performed by Okumura et al., where they employed depth-resolved X-
ray absorption spectroscopy to observe the effect of different nanoscale
metal oxide coating layers on the change in LCO cathode/glass ceramic
LATP SSE interfacial impedance in ASSBs [29]. Wenzel et al. conducted
a comparable study to interrogate the Li metal anode/SSE (Li7 P3 S11 )
interface and found that the interfacial reaction zone consists of species
such as Li2 S and Li3 P, and is limited to a few nanometers in thickness
[30]. The primary limitation with XPS is that carrying out time-sensitive
experiments (particularly to study metastable interfacial reactions) can
be challenging.
X-ray absorption fine structure: (XAFS) spectroscopy is a versatile
and popular method to study the electronic structure of materials at the
atomic scale, primarily at synchrotron sources, due to the highly tunable
X-rays and high X-ray flux. Various studies have conducted XAFS-based
characterization, under ex situ, in situ, as well as operando conditions.
XAFS is usually used in one of two modes depending on the extension
from the absorption edge of the energy range used: X-ray absorption
near edge structure (XANES) and extended X-ray absorption fine struc-
ture (EXAFS). While XANES is used primarily to obtain the oxidation
state and coordination environment of certain species, EXAFS furnishes
the local structure; namely, the coordination number and bond length
of the nearest neighbors to the atom absorbing the X-ray. Li et al. em-
ployed operando XANES to study parasitic interfacial reactions between
an NMC cathode and a sulfide-based SSE, resulting in the formation
of an interphase layer with various reaction by-products [31]. Wang
et al. employed operando XANES to elucidate the reactions occurring
between the LCO cathode particles and the sulfide-based Li10 GeP2 S12
SSE at the nanoscale [32]. Chen et al. used a combination of EXAFS and
XANES to study the interfacial reactions between the same LCO cathode
and Li2 S.20P2 S5 sulfide-based SSE [33]. They then validate the effect of
an Li3 PO4 interlayer in suppressing such parasitic side reactions at the
cathode/SSE interface. In general, in situ XAFS analysis of full cells is a
challenge, since it furnishes an averaged measurement on atomic infor-
mation which can render separating out phenomena from different cell
parts being probed challenging. Thus, an optimized full cell in situ scan
would require a specialized cell design.
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Energy Storage Materials 45 (2022) 969–1001
Fig. 1. Schematic of the key focus of this review: understand-
ing interfacial instabilities, and the strategies to mitigate such
instabilities in ASSBs. This schematic is not to scale.
X-ray micro-computed tomography: (XCT) is a popular imaging
tool for characterizing the morphology of the interface in ASSBs, in-
cluding under operando cell conditions [16]. In particular, they can be
effective to visualize the nucleation and growth of Li dendrites in voids
present at the anode/SSE interface [34,35], as well as the propagation
of cracks and dendritic Li into the SSE [36,37]. Tippens et al. character-
ized the growth of the anode/SSE interphase layer, leading to the frac-
ture of the Li1+x Alx Ge2-x (PO4 )3 (LAGP) SSE using XCT [38], as shown
in Fig. 2(b). Li et al. used 3D XCT at the sub-micron length scale to ob-
serve the effect of poor contact between cathode (NMC) and SSE (LATP)
single particles on the reduced Li kinetics in the ASSB [39]. XCT can also
be used to provide morphological/microstructural inputs for modeling
to shed light on interfacial issues inherent to ASSBs at solid/solid inter-
faces. Neumann et al. used XCT–based inputs to understand the under-
lying mechanisms behind lower cathode utilization in ASSBs, compared
to traditional liquid electrolytes [40]. They found that the topology of
the interface and the microstructure of the cathode/SSE interface pre-
dominantly determine the performance of ASSBs. Traditionally, imaging
Li (a very light element) and distinguishing it from voids and cracks at
the interface using XCT has been challenging. Recent advances in phase
contrast tomography, along with superior machine learning based seg-
mentation algorithms have been able to better address these challenges
[41].
2.2. Electron microscopy-based methods
Electron microscopy (EM) based techniques are yet another widely-
used imaging method for characterizing interfaces in ASSBs. EM fur-
nishes spatial information from the micron to the Ålength scales. Al-
though most commonly used for ex situ/post-mortem characterizations,
there has been a huge push towards in situ/operando characterization
of interfaces using electron microscopy, using custom-built cells. While
such custom-built nanocells may not always be representative of com-
mercial type cells, the wealth of nanoscale interfacial information that
can be accessed through such studies is invaluable. Additionally, dam-
age to the surface being imaged from the electrons as well as main-
taining an inert atmosphere for sample integrity are key concerns in
EM-based studies. In light of these challenges, cryo-EM has emerged
as a popular method for operando and in situ EM, where characteriza-
tion is conducted under cryogenic temperatures to preserve sensitive
battery elements and reduce electron beam induced damage to the cell
[42,43]. Finally, while electron microscopy is an excellent tool for imag-
ing surfaces or very thin samples, obtaining sub-surface (3D spatial) in-
formation is challenging. While serial sectioning and imaging through
P.P. Paul, B.-R. Chen, S.A. Langevin et al. Energy Storage Materials 45 (2022) 969–1001

Fig. 2. Characterization of interphases and interphasial phenomena in ASSBs: (a) XPS, showing the Li 1s spectra [25], © 2018 Springer Nature. (b) X-ray micro-
computed tomography, showing the reconstructed 3D volume (left) and a 2D snapshot of the cracked surface (right) [38], © 2019 American Chemical Society. (c)
Electron microscopy showing the uneven dissolution of Li with an LAGP SSE using TEM and cracked surface of the SSE post cycling using SEM [50], © 2019 American
Chemical Society. (d) Neutron depth profiling showing the concentration of Li as a function of depth from the metal Li anode/SSE (Li3 PS4 SSE interface [61], © 2019
Springer Nature. (e) Optical microscopy showing the growth and propagation of a crack in a garnet SSE [66], © 2018 Elsevier, and (f) EIS, showing the impedance
spectra for an Li3 YCl6 (LYC) SSE with an LCO cathode (on the left) and the correlation between the cathode/SSE interfacial resistance and the capacity fade in the
cell for two SSEs (Li3 YCl6 and Li3 YIn6 (LIC)) on the right panel [83], © 2021 Springer Nature.

focused-ion beam can address this issue, the sample preparation is often
cumbersome and the data collection is destructive.
Scanning electron microscopy: (SEM) is a ubiquitous imag-
ing technique used to image interfaces at the microscale. Krauskopf
et al. used a combination of in situ and ex situ SEM to study
the interrelationships between surface and bulk defects at the an-
ode/SSE interface, and their link to the morphology of Li deposits
(whiskers/mossy/dendritic) in Li/LLZO/Li symmetric cell [44]. Sagane
et al. used SEM to tie current densities at the anode to the morphol-
ogy of Li deposits and the stripping efficiency of such deposits (and in
turn the Coulombic efficiency over cycling) [45]. Motoyama et al. used
a custom-built SEM cell to observe the growth of Li dendrites towards
the cathode from an anode/LiPON SSE interface, and how they are af-
fected by grain boundaries on the SSE [46]. Due to their popularity as
a characterization technique, EM is often used with other techniques,
to provide complementary structural and chemical information to the
morphological information obtained from EM.
Transmission electron microscopy: (TEM) has been a popular
means to characterize the interfacial surfaces in ASSBs at the nanometer
to Åscale. Brazier et al. used ex situ TEM to observe the degradation of
a custom nano-battery (amorphous Li2 O-V2 O5 -SiO2 ) over cycling, due
to the deterioration of the cathode/SSE interface stemming from migra-

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P.P. Paul, B.-R. Chen, S.A. Langevin et al.
tion of chemical species across the interface [47]. Mori et al. employed
in situ TEM on glassy Li2 SP2 S5 (LPS) SSE, to observe the difference in
crystallization behavior of the SSE and active material dissolution due to
interfacial contact with a metal oxide cathode compared to the pristine
LPS material [48]. Ruzmetov et al. employed in situ TEM to study the
effect of thickness of the LiPON SSE layer on the cell performance, show-
ing that ultrathin film SSE layers (<100 nm) can result in a conformal
solid/solid contact at the interface, but cannot prevent self-discharge
of the cell [49]. Lewis et al. used in situ TEM, along with ex situ SEM
to find evidence of amorphization-induced cracking at the anode (Li
metal)/SSE (LAGP) interface, which can in turn lead to cell failure [50],
as illustrated in Fig. 2(c).
Scanning mode TEM can be combined with electron energy loss spec-
troscopy (EELS) to study Li-ion transport dynamics at the nanoscale. No-
mura et al. employed operando TEM with EELS on an ASSB with an LCO
cathode and Li1+x+y Alx Ti,Ge2-x Siy P3-y O12 SSE [51,52]. In the former,
they directly observed the formation of an inactive nanometer-thick in-
terphase layer at the cathode/SSE interface, leading to a significant rise
in the interfacial impedance, while in the latter they were able to ob-
serve the movement of Li-ions across as well as along the cathode/SSE
interface. Santhanagopalan et al. used a combination of in situ TEM and
EELS to observe the accumulation of lithium at the cathode/SSE (LiPON)
as well as the anode/current collector interfaces, leading to a loss in cell
capacity over cycling in custom-built nanobatteries [53]. Han et al. em-
ployed a combination of cryo-TEM and ex situ SEM to observe the effects
of interfacial coating on the increased stability of the Li metal anode and
a thin film garnet-type SSE [54]. Recently, Luo et al. used EELS along
with XPS and MD-based modeling to study the differences in dendrite
morphology for a Li versus Li-In anode at its interface with a sulfide SSE
(Li6 PS5 Cl) over long term cycling [55].
2.3. Neutron-based methods
Neutron-based methods have been used to study interfaces in ASSBs
due to their sensitivity towards Li [56]. The particular advantage of
neutron-based methods, compared to X-ray and electron-based meth-
ods is in terms of their scattering and absorption with lighter elements
(such as Li and C which are often used in batteries). Like X-ray based
methods, neutron-based characterization is non-destructive and, there-
fore, can be conducted under in situ and operando conditions [16,19,23].
The main challenges in using neutron-based methods compared to X-
ray-based methods is the ability to obtain a high degree of spatial and
temporal resolution simultaneously.
Neutron depth profiling: (NDP) can used to obtain micrometer res-
olution depth profiles of the concentration of various species, up to
depths of tens of micrometers [57]. In ASSBs, they are mostly used to
obtain Li concentration profiles across the Li metal anode/SSE interface
[58]. Wang et al. employed in situ NDP to observe the plating and strip-
ping process at the interface of the Li anode and garnet SSE, towards
developing a predictive short circuit diagnostic [59]. Ping et al. made a
similar observation on a garnet-based SSE, showing the formation and
dissolution of Li dendrites during cycling [60]. Han et al. used operando
neutron depth profiling to study the effect of conductivity on Li dendrite
formation at the anode/SSE interface with three popular SSEs: LiPON,
LLZO and amorphous Li3 PS4 [61], as shown in Fig. 2(d). They found
that a lower ionic conductivity in the LiPON SSE had a lower propensity
for Li dendrite formation than a higher conductivity (LLZO and Li3 PS4 )
SSE.
Neutron reflectometry: Neutron reflectometry is a way to obtain
2D spatial maps of different species, at a slightly lower spatial resolution
compared to NDP. Seidlhofer et al. used operando neutron reflectometry
to observe the lithiation and delithiation of a Si anode [62], as did Jerliu
et al. using a combination of operando neutron reflectometry with cyclic
voltammetry [63].
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Energy Storage Materials 45 (2022) 969–1001
2.4. Other experimental characterization techniques
This sub-section covers brief overviews of some other popular char-
acterization techniques used to understand interfaces in ASSBs, viz. op-
tical imaging/microscopy, cantilever surface probe type scanning probe
microscopy techniques and nuclear magnetic resonance (as well as its
combination with imaging). We also briefly discuss on electrochemical
impedance spectroscopy (EIS), which is a numerical tool for estimating
the impedance of the material/volume of interest, using global electro-
chemical cycling data. The various characterization methods presented
for multi-length scales in this section are summerized in Table 1.
Optical imaging and microscopy: Optical-based methods are a
popular method for visualizing the morphology of various interfaces
in ASSBs, usually in the millimeter to sub-micrometer range [64,65].
Optical-based imaging methods generally involve less complicated con-
ditions than electron-microscopy, and can provide information at a
given spatial resolution ranging from millimeters to micrometers. Op-
tical microscopy is often combined with SEM, in order to complement
OM with the finer resolution afforded by SEM. Manalastas et al. used
OM combined with electron microscopy to link the failure of a garnet
SSE containing ASSB to Li dendrite formation at the anode/SSE inter-
face [66], as illustrated in Fig. 2(e). Kazyak et al. used a similar com-
bination of operando OM and SEM on a garnet-based SSE to observe
the propagation of Li filaments in the SSE via a crack-opening mecha-
nism [67], while Sagane et al. used it on a LiPON SSE cell to establish a
link between the current density to the morphology of Li deposits [68].
Davis et al. used Auger electron spectroscopy with OM to visualize the
spatial heterogeneity of Li plating, and linked it to the degradation of
the anode/SSE interface in a sulfide-based ASSB [69]. While optical mi-
croscopy is a very useful tool to observe the failure in ASSBs, it can
only be carried out under carefully curated conditions, such as having
an optically transparent cell.
Scanning probe microscopy: (SPM) encompasses a suite of surface-
sensitive techniques that provides nanometer resolution surface maps
of the mechanical relief, microstructure or electrochemical properties
on a surface [70–72]. The key advantages are high spatial resolution
(nanometers) and in situ characterization. SPM has been used to spa-
tially map out the Li-ion conductivity as well as the microstructure of
a NMC thin film cathode [73], as well as TiO2 [74] and Si [75] thin
film anodes, all conducted in LiPON SSE-based nanobatteries. Kumar
et al. explored a similar link between Li-ion kinetics and the microstruc-
ture in the SSE itself, using the commercially-available Li-ion conducting
glass ceramic SSE [76]. Wang et al. similarly studied the link between
Li-ion conductivity and microstructure for the NASICON-based LAGP
(Li1.5 Al0.5 Ge1.5 (PO4 )3 ) SSE [77]. Through such complementary electro-
chemical and microstructure surface maps, they were able to correlate
the regions of high Li-ion conductivity with the presence of surface de-
fects and grain boundaries. To maintain the integrity of the surface,
methods for maintaining sample transfer in an inert atmosphere is a
necessity for ex situ SPM—characterizations.
Nuclear magnetic resonance: (NMR) is a non-destructive, quanti-
tative way to track Li concentrations, usually done by monitoring the
6 Li or 7 Li signals. NMR can provide a wealth of chemical and structural
information in ASSBs, due to its high chemical specificity and ability
to characterize crystalline and amorphous species [78]. Tsai et al. used
ex situ NMR, with TEM to understand the role of improper interfacial
contact leading to Li dendrite formation at the anode (Li metal)/SSE
(garnet-based) interface, in turn inducing short circuits in the ASSB,
by confirming the presence of dendritic Li by tracking the 7 Li signal
[79]. Since it is non-destructive, NMR is readily adaptable towards in
situ and operando characterizations. Yu et al. used NMR to show that the
Li transport through the SSE (Li6 PS5 Cl)/cathode (Li2 S) interface was or-
ders of magnitude smaller than the bulk conductivity of the SSE itself,
thus making the interface the limiting factor in ASSB performance [80].
Additionally, NMR spectroscopy can be readily combined with imaging.
Nakayama et al. employed NMR-based imaging to study the dependence
P.P. Paul, B.-R. Chen, S.A. Langevin et al.
Table 1
Summary of experimental techniques commonly used for characterizing interfaces in ASSBs.
Characterization Technique Length Resolution
X-ray photoelectron spectroscopy (XPS) nanometer
X-ray absorption fine structure (XAFS) sub-nanometer
X-ray micro computed tomography (micro-CT) sub-micrometer
Scanning electron microscopy (SEM) sub-micrometer
Transmission electron microscopy (TEM) sub-nanometer
Neutron depth profiling (NDP) millimeter
Neutron reflectometry millimeter
Optical microscopy (OM) micrometer
Scanning probe microscopy (SPM) nanometer
Nuclear magnetic resonance (NMR) nanometer
of cyclic stability of an organic PEO-based SSE on the formation of a sta-
ble solid electrolyte interphase layer at the cathode/SSE interface [81].
The in situ NMR imaging was also able to elucidate the degradation
mechanisms through cathode (e.g. LiFePO4 ) pulverization and subse-
quent SSE breakdown at the cathode/SSE interface. A challenge with
NMR imaging is the limited spatial resolution. Obtaining information
at the sub-micrometer range is extremely challenging, thus limiting the
study of interfacial phenomena to length scales above the microscale
[78].
Electrochemical impedance spectroscopy: (EIS) is a popular elec-
trochemical method to estimate the impedance of a given system within
the context of multiple interfaces present in an ASSB [82]. Therefore,
using EIS with the many characterization techniques outlined above is
an extremely popular way of correlating structural, morphological and
chemical measurements of the interface to the electrochemical perfor-
mance of the interface, through measuring its impedance. Moreover, EIS
is a relatively fast technique, in which the frequency range studied can
allude to time-sensitive interfacial processes (e.g. electrolyte resistivity,
charge-transfer resistance, and diffusion coefficients). By providing a
link between the experimental characterizations and the electrochemi-
cal performance of the interface, the local degradation mechanisms at
the interface can be tied to the global cell performance using EIS. Za-
hiri et al. exploited this philosophy to elucidate the role of the cath-
ode/SSE interface in the cell performance across various SSE systems
[83], as shown in Fig. 2(f). They also employed DFT-based atomic cal-
culations to devise strategies for optimizing hybrid electrodes for the
best ASSB performance. Sharafi et al. used EIS along with XPS to sys-
tematically study the effect of temperature, pressure and current density
on the impedance, and thus the kinetics across the anode (Li metal)/SSE
(LLZO) interface [84]. We note that caution must be exercised to decon-
volute the various reactions happening across various interfaces in the
cell during its operation to the overall impedance rise observed by EIS.
A three-electrode cell configuration (with a reference electrode in ad-
dition to a working and counter electrode) is often employed to enable
such decoupling of deleterious reactions happening at the positive and
negative electrode interface, in the overall impedance spectrum of the
cell.
2.5. Computation-guided efforts to understand and improve interfaces
For this part of the review, we dive into the impact computational
efforts have had on our understanding and discovery of novel SSEs. Re-
cent computational efforts have accelerated our understanding of the
development of ASSBs, and will be further advanced by leveraging com-
putational techniques, which have recently been conducted in regards to
understanding and advancing materials and interfaces [85,86]. In par-
ticular, ab initio molecular dynamics simulations have been conducted
in studying fast ion conductors, thermodynamic calculations have been
conducted by materials databases to identify the chemical and elec-
trochemical stability of SSE materials and interfaces therein, and first-
principles calculations for the design of novel SSEs [85]. For this review,
we focus our attention on computation-guided evaluation of the elec-
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Energy Storage Materials 45 (2022) 969–1001
ASSB phenomena observed Examples
Chemical composition, electronic states [24,25,28]
oxidation state, coordination number, bond lengths [31–33]
Volumetric morphology of interface/interfacial species [34,35,38]
Surface morphology of interface/interfacial species [44–46]
Surface morphology of interface/interfacial species [50,52,54]
Li 1D spatial maps [58,60,61]
Li 2D spatial maps [62,63]
Surface morphology of interface/interfacial species [38,66,67,69]
Surface Li-ion conductivity/microstructure [73,76,77]
Li concentration across interfaces [80,81]
trochemical stability of SSEs and interface stability and compatibility in
ASSBs.
With early design principles for solid-state lithium superionic con-
ductors being validated via density functional theory (DFT) calculations
[87–89], it has become evident that the chemical and electrochemical
stability of these frameworks underscored the realization that redox re-
actions occur, which induces a change in composition at the interface
(Fig. 3a) [90]. For LGPS, first-principles calculations yielded that the
intrinsic electrochemical window is only 1.7–2.4 V [91], compared to
the wide 0–5 V window measured from cyclic voltammetry [92]. This
discrepancy is owed to the small surface area contact between the SSE
and the semi-blocking electrodes, which limits the kinetics of decompo-
sition reactions [85,93]. The intrinsic electrochemical window was vali-
dated through experimentation using XPS, where the reduction of Ge4+
and P5+ at low potential and the oxidation of S2- at high potential oc-
curred [91,93,94]. To further extend the importance of computational
efforts, the air stability of sulfide-based SSEs has also been studied by
focusing on hydrolysis reactions that generate H2 S [95]. First-principles
calculations were performed within a broad range of cations, anions,
and compositions, where general trends of moisture stability showed
that sodium-based SSEs exhibit improved suppression towards the gen-
eration of H2 S gas [95]. These efforts exemplify the advantages of per-
forming computational calculations to not only identify electrochemical
stability windows, but even towards understanding undesirable decom-
position products via moisture.
Based on thermodynamic calculations, the intrinsic electrochem-
ical stability window has been further evaluated for a number of
other SSEs, such as NASICON-type and oxide-based systems (Fig. 3b)
[85,90,96]. Akin to the aforementioned LGPS system, both NASICON-
type and oxide-based (e.g., garnets) SSEs exhibit varying stability win-
dows. Oxide-based SSEs, such as LLZO, have a wider electrochemical
stability window than sulfides, and are more stable at lower poten-
tials (0.05 V vs. Li/Li+ , as indicated by thermodynamic calculations
[90,96]. As mentioned above in the section on garnets, though the stabil-
ity against lithium metal is exemplary, the wetting issues at the surface
of the SSEs poses one of the underlying challenges for this material [97–
100]. For NASICON-type systems, the electrochemical stability window
shows high oxidative stability up to 4.5 V vs. Li/Li+ , and the reductive
instability arises from reduction of Ti4+ at 2.2 and 1.8 V, respectively
[90,96], consistent with experimental validation [101,102].
As an extension to the thermodynamic calculations performed to as-
sess the electrochemical stability window of SSEs, additional computa-
tional studies can be performed to understand the chemical stability in
ASSBs. In particular, when SSEs come in contact with lithium metal,
exothermic lithiation and reduction reactions occur spontaneously that
lead to the formation of interphases. For instance, LiPON, a standard
electrolyte for thin-film LIBs, can achieve a long cycle life of ≈10,000
cycles [103]. Zhu et al. were able to show from thermodynamic calcula-
tions that the standard lithium reduction products derived from LiPON
favors desirable phase equilibria comprising Li3 N, Li3 P, and Li2 O at the
interface [90]. As a result, compatibility can be assessed by analyzing
via thermodynamic calculations, the formation of a stable passivating
P.P. Paul, B.-R. Chen, S.A. Langevin et al. Energy Storage Materials 45 (2022) 969–1001

Fig. 3. (a) Schematic diagram regarding the electrochemical window and lithium chemical potential profile in all-solid-state lithium metal batteries. Reprinted with
permission from Ref. [90] © 2015 American Chemical Society. (b) Thermodynamic intrinsic electrochemical stability windows of lithium binary compounds, selected
solid electrolytes, and corresponding phase equilibria of the solid electrolytes at 0 V and 5 V. The dashed boxes mark the potential at which the compound is fully
delithiated. Reprinted with permission from Ref. [85] © 2018 Elsevier. (c) Illustration of different types of lithium metal/SSE interfaces. Reprinted with permission
from Ref. [85] © 2018 Elsevier.

interphase layer. Another key advantage to performing computations
lies in understanding phase stability at the cathode/SSE interface. A
key constituent to the limitation of stable cycle life in ASSBs originates
from the formation of mixed ionic and electronic conducting (MIEC)
interphase layers (Fig. 3c) [85]. For instance, LPS and LiCoO2 react to
form a combination of Co9 S8 , Li2 S, Li2 SO4 , and Li3 PO4 , which has an
exothermic enthalpy of reaction of -0.41 eV atom−1 [96]. The fidelity
of these calculations were further verified by Sakuda et al. [104]. The
presence of cobalt sulfides, which are electronically conductive, forms
an MIEC interphase layer that leads to interfacial degradation and Li-ion
transport across the interface continues to be obstructed. Further studies
have been performed with which to provide guidelines for stable cath-
ode/SSE interfaces, where Nolan et al. affirmed that lithium phosphates
and lithium ternary fluorides support high oxidation limits [105]. To ex-
pand the library of stable SSEs, the use of computational efforts have also
led to the discovery of new compounds, such as chlorides, bromides, and
nitrides, which may provide even more desirable attributes for the devel-
opment of ASSBs [106,107]. The power of computational calculations
cannot be overlooked, and provides a unique advantage in correlating
theoretical understanding with experimental observations. As progress
in the development of SSEs continue, we find that computation-guided
efforts will be further advanced to bring forth deeper insight into the
correlation between mechanical and electrochemical degradation pro-
cesses.
2.6. Multimodal characterization
We see the three major considerations for characterizing ASSBs as:
(i) the need for superior spatial resolution, (ii) temporal resolution, and
(iii) chemical sensitivity. A finer spatial resolution is required to charac-
terize surface/interfacial properties and mechanisms, and deconvolute
them from bulk phenomena. Secondly, superior temporal resolution of
techniques is desired, to perform operando characterization. This chal-
lenge is exaggerated in ASSBs, due to the metastable nature of many
interfacial species and the short timescales associated with chemical
and structural changes at the SSE/electrode interface upon electrochem-
ical bias. Finally, due to the wide variety of chemical species formed in
ASSBs, techniques that are sensitive to distinct chemical speciation are
desirable.
Through this section, we have highlighted some of the most com-
monly used experimental and computation–based characterization tech-
niques to understand ASSBs in general, and their interfacial phenom-
ena in particular. We see a variety of techniques, each with their
unique advantages and challenges, that yield structural, microstruc-
tural, chemical, electrochemical, morphological and mechanical infor-
mation. In order to gain a more holistic view of ASSBs, and the interfa-
cial phenomena, we stress the need for combining techniques to yield
complementary information. We have focused on highlighting exam-
ples of such multimodal analyses throughout this section. For exam-
ple, Ning et al. used a combination of in situ 2D X-ray diffraction and
3D XCT, to correlate the location of Li dendrites to cracks present in a
Li/Li6 PS5 Cl/Li ASSB [34]. The 3D XCT data was also used to calculate
the evolution of strain fields in the SSE over cycling using digital vol-
ume correlation. The in situ X-ray methods were complemented by ex
situ SEM imaging to obtain higher resolution images of the cracks, by
finite element modeling to simulate heterogeneous current distributions
around voids formed at the Li/SSE interface, and by EIS measurements
to link the formation of cracks in the SSE and their subsequent filling

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P.P. Paul, B.-R. Chen, S.A. Langevin et al.
with Li metal to the decrease in impedance of the ASSB. Thus, multi-
modal analyses can involve combinations of experimental techniques,
or the combination of one or more experimental techniques with nu-
merical analyses, as well as modeling-based studies. They hold the key
to obtaining a more holistic view, that spans from the cell-scale to the
atomic scale along with temporal information from metastable interfa-
cial species, to the life cycle of the ASSB. Such a holistic understanding
becomes essential when transitioning from custom-made cells that are
optimized for a particular characterization technique to commercially
relevant cell sizes and designs and realistic charging conditions. In such
a transition, versatile experimental techniques that are easily accessible
along with numerical/modeling predictor-based approaches will hold
the key. Therefore, the synergy between characterization through ex-
periments, modeling, and numerical analyses hold the key towards un-
derstanding the current limitations of ASSBs, in the push for their greater
commercial viability.
3. Interfacial instabilities and solutions for inorganic solid state
electrolytes
In this section, we outline the interfacial challenges and strategies
towards addressing underlying instabilities in inorganic SSEs. Inorganic
SSEs can be broadly classified into sulfide-based and oxide-based solid-
state electrolytes (SSEs). Among oxide-based SSEs, the two major sub-
categories are sodium superionic conductors (NASICON), and garnets.
These electrolyte classes comprise the majority of the subsequent discus-
sion in this review. Each sub-section contains a high-level introduction
to that particular class of SSEs viz. sulfide-, NASICON-, and garnet-based
SSEs, with their salient features as well as characteristic advantages and
limitations. Next, the interfacial issues for that electrolyte class are dis-
cussed, in terms of interfacial challenges at the cathode/SSE interface,
followed by the anode/SSE interface. Broadly speaking, the interfacial
challenges can be due to instabilities that arise from a chemical, electro-
chemical or mechanical origin. Despite sharing some common features,
the cathode/SSE and anode/SSE interfaces face slightly different chal-
lenges, within the broad framework of the origin of the instabilities.
At the anode/SSE interface, the primary concern is of a mechani-
cal nature and involves the formation of Li dendrites at the interface,
which cause several detrimental effects, such as loss in active material
through cracking/pulverization and loss of interfacial contact that re-
sults in a loss of cell capacity over cycling, and in some severe cases,
potential shorting between the electrodes once the Li dendrites pierce
through the SSE [108]. The precise mechanisms for Li dendrite growth
in ASSBs are still under investigation. Usually, voids can formed at the
interface of the Li/SSE interface during stripping of Li+ ions from the
anode during cell discharge, which creates vacancies at the anode/SSE
interface. When the rate of migration of Li+ is larger than the diffusion
of the associated vacancies from the interface into the bulk of the an-
ode, or the creep flow of Li metal into the vacancies, voids occur at the
anode/SSE interface [109]. These voids subsequently nucleate cracks,
which grow out from the anode/SSE interface into the interior of the
SSE over cycling and are filled with metallic Li eventually leading to
short circuit of the cell [110]. Other concerns at the anode/SSE inter-
face include accommodating the volume change of the anode between
charge and discharge, the electrochemical stability window of the SSE,
and reaction of the metal anode with the SSE, forming undesirable re-
action products.
The primary concerns at the cathode/SSE interface include the vol-
ume changes in the cathode between the charged and discharged states
(’breathing effect’) [111] which induce mechanical stresses and can
lead to particle cracking over repeated cycling. Additionally, the elec-
trochemical stability window, and chemical reactions between species
present in the SSE and the cathode can result in interfacial instabilities,
causing deterioration of the SSE and consumption of active cathode par-
ticles. Fig. 4 schematically summarizes the various interfacial issues in
ASSBs, at the cathode/SSE and anode/SSE interface.
976
Energy Storage Materials 45 (2022) 969–1001
The strategies for improved interfaces and more stable ASSBs are nu-
merous, reflective of the many interfacial instabilities. Each electrolyte
system and the electrode materials (particularly cathode) dictate the
nature of the interface and thus inform the strategies to optimize the
interfaces. However, broadly speaking, interface stabilization involves
achieving the following: (i) Mechanically, the interface should be suffi-
ciently flexible to maintain good contact between the SSE and the elec-
trode over charge and discharge by accommodating the volume changes
of the electrode associated with (de)lithiation. Additionally, the inter-
face should also minimize the formation of voids/Li dendrites at the
anode/SSE interface; (ii) ehemically, the interface should be such that
chemical side reactions that consume active Li inventory are minimized;
and (iii) electrochemically, the interface should be such that the polar-
ization/potential drop should be minimized and redox stability maxi-
mized.
In general, the commonly employed strategies for interfacial engi-
neering in ASSBs are:
1. Optimization of the processing methods employed to fabricate
SSEs for ASSBs, both thin-film and bulk type is a popular way of
tailoring the interfacial properties for mitigating interfacial instabil-
ities [112]. This strategy is commonly employed to obtain desired
mechanical and microstructural properties (such as high shear mod-
ulus, low grain size/boundaries) to mitigate mechanical instabilities
at the interface, and higher conductivities to maintain efficient con-
ducting channels through the interface and the bulk of the SSE [113].
2. Surface conditioning of the chemistry of the SSE by using strate-
gies, such as doping, is a popular method for achieving higher
conductivity at the interface between the SSE and the electrode.
The doping can be substitutional [114], interstitial [115] or mixed
[116] type doping, on either the cathode or the anode side.
3. Interfacial coatings [117,118] and buffer layers [119] can act as
an intermediate at the interface of either electrode and the SSE, for
enhanced mechanical, chemical and electrochemical stability. Me-
chanically, such coatings/layers should promote better interfacial
contact and reduce Li dendrite formation. Chemically, they serve to
mitigate deleterious side reactions that consume the electrode/SSE;
and electrochemically, they widen the stability window between the
bare SSE and the electrode.
4. Composite electrodes are also employed to reduce transportation
and reaction heterogeneity between the electrode and the SSE, for
improved conducting pathways across the interface, as well as im-
proved interfacial contact. They can be in the form of alloyed Li
metal on the anode side [120] or SSE-cathode composites on the
cathode side [121]. Such composites can provide added mechani-
cal stability at the interface by including materials that can better
absorb interfacial stress due to the breathing effect over repeated
charge/discharge.
3.1. Interfaces for sulfide-based solid state electrolytes (S-SSEs)
Sulfide-based SSEs are among the most popular solid electrolytes
used in batteries [122,123] and are the most promising for room temper-
ature ASSBs, due to their relatively higher ionic conductivity compared
to other SSEs. This high conductivity arises from the superionic conduc-
tor structures, such as Li10 GeP2 S12 [92] and Li9.54 Si1.74 P1.44 S11.7 Cl0.3
[124], owing to their open framework that ensures large channels for
Li-ion transport, which is often due to the large size of S2- . Liquid sulfide-
based electrolytes, despite several advantages, have the main bottleneck
of the formation of various metastable polysulfide species, which are
deleterious to cell performance and stability over cycling, through a
’shuttle effect’ [125]. Sulfide-based SSEs can mitigate the shuttling ef-
fect as compared to liquid sulfide-based electrolytes [126]. The other
main advantage of sulfide-based SSEs are that the S-Li bond is weak,
so Li can, in theory, be reversibly cycled efficiently. Additionally, they
exhibit good ductility compared to other SSEs, which can result in bet-
P.P. Paul, B.-R. Chen, S.A. Langevin et al.
ter interfacial contact and accommodate volume expansion of the anode
or cathode. Finally, S-SSEs are usually relatively easy to manufacture,
including using conventional cold pressing type methods, due to their
good ductility.
Sulfide-based SSEs are typically thio-LISICON compounds (pre-
pared by replacing O2- with S2- in LISICON compounds). thio-LISICON
SSEs can be broadly sub-divided into binary ((100-x)Li2 S-(x)P2 S5 ) and
ternary (Li2 S-Mx Oy -P2 S5 ) electrolytes, based on composition. Binary
thio-LISICON SSEs typically have good physical properties [127]. The
most common stoichiometries are Li3 PS4 and Li7 P3 S11 . Ternary systems
typically exhibit the highest ionic conductivity [128], with the most
common system being Li2 S-GeS2 -P2 S5 . The Ge4+ can also be replaced
with other +4 cations, such as Si [129,130] or +3 cations, such as Al
[131], which have exhibited.
Based on crystalline state, they can be divided into glass, glass-
ceramic and crystalline. Glassy sulfide SSEs have isotropic conductivity,
low cost and have negligible grain boundaries [132]. Glass-ceramic SSEs
are crystallized from glassy electrolytes and have a relatively higher con-
ductivity [133]. However, they tend to have a low chemical stability
(reactivity with moisture and oxygen), high cost for processing and low
compatibility with the positive electrode. Crystalline S-SSEs typically
exhibit the highest conductivity (at par with liquid electrolytes) due to
well defined conduction pathways.
One of the main challenges associated with S-SSEs include their high
reactivity to moisture. So proper control of environmental conditions
during processing and cell operation is required. Additionally, their nar-
row electrochemical stability window can render their interfaces with
electrodes susceptible to deleterious side reactions. Zhu et al. show this
relatively narrow stability window of S-SSEs compared to other SSE
classes against Li metal (Fig. 2 in [90]), as well as commonly used coat-
ing materials for the cathode (Fig. 3 in [90]).
3.1.1. Interfacial challenges: Sulfide-based SSEs
The most common source of chemical challenges at the interface
arise from reaction between the S-SSEs and the electrode, creating by-
products which can be toxic (such as H2 S produces in Li-S systems in
the presence of moisture [134]), or other polysulfide species, which can
result in an increased interfacial impedance [89]. Apart from causing
an increase in the interfacial impedance limiting the motion of Li-ions
through it, side reactions at the interface can also often result in con-
sumption of the active electrode/SSE material [135]. The mechanical
977
Energy Storage Materials 45 (2022) 969–1001
Fig. 4. Interfacial instabilities in ASSBs. At the anode/SSE inter-
face, the primary instabilities are Li dendrite growth, which is co-
located with cracks in the SSE, and can lead to formation of dead
Li or short circuit between the electrodes. On the other hand, the
breathing effect for the cathode/SSE interface can lead to parti-
cle pulverization in the cathode. The formation of a reactive inter-
phase layer, as well as reaction products (mix of chemical reactions
and redox reactions) are common to both interfaces.
nature of interfacial instability primarily arises from the ’breathing’ ef-
fect, where the cathode expands and contracts during charge/discharge,
which induces mechanical stresses at the interface, and can result in
loss of interfacial contact. On the anode side, the expansion and con-
traction of Li dendrites that nucleate preferentially at the interface can
lead to cracking. Finally, the electrochemical stability window for the
electrode/S-SSE can determine the interfacial stability [136]. Previous
studies indicated that the difference in the chemical potential of Li in
the electrode and the S-SSE can also cause the formation of a ’space
charge layer’, which significantly increases the interfacial impedance,
and causes a deterioration in cell performance over cycling [137]. How-
ever, recent studies have shown that the space charge layer has a neg-
ligible effect, if any, on the interfacial impedance and performance of
the ASSB [138]. Now, we sequentially discuss these specific instabilities
between the S-SSE/cathode and S-SSE/anode interfaces.
Sulfide-SSE/cathode interface:
Oxide-based cathodes: These class of cathodes primarily include
LTO (Li4 Ti5 O12 ), LCO (LiCoO2 ), NMC (Li Nix Mny Coz O2 ) and LMO
(LiMn2 O2 − ), and comprise the most commonly used class of cathodes
used in S-SSE ASSBs. In these systems, the chemical reactions at the
interface can result in sulfides being converted to sulfur, formation
of metastable polysulfides and oxygen release, which all contribute to
the chemical interfacial instability [139,140]. Additionally, the carbon-
binder material used as an electrically conductive additive in the cath-
ode reacts with the S-SSE to form reaction byproducts that consume
the S-SSE, as well as decrease the ionic conductivity at the interface
[141,142]. Zuo et al. systematically demonstrated the different degrada-
tive reactions at the interface of LGPS SSE and NMC cathode, as a func-
tion of the SOC of the ASSB [143]. While the lower voltage degradation
was dominated by the formation of polysulfide species and LGPS decom-
position; the formation of phosphate and sulphate species dominated in
the high voltage range. Kitaura et al. saw such an increased impedance
for the transfer of Li-ions from an 80Li2 S.20P2 S5 S-SSE to the LTO cath-
ode during the discharge process [144]. Yoon et al. also showed that
the addition of carbon conductive additives into a Li10 GeP2 S12 SSE re-
sults in slower kinetics, even though the conductivity of the SSE itself is
enhanced [145]. This slowdown is primarily due to the formation and
growth of a passivation layer at the carbon/SSE interface, which eventu-
ally results in capacity loss over cycling. Mechanically, oxide materials
can exhibit a change in volume of 8%, and is usually higher in high Ni
content NMC-type cathodes. Compared to the metal oxide cathodes, the
P.P. Paul, B.-R. Chen, S.A. Langevin et al.
S-SSEs usually have a significantly lower elastic modulus, which means
that they cannot accommodate the stresses induced through the vol-
ume changes in the cathode elastically [146]. Therefore, these interfa-
cial stresses during charge/discharge often result in plastic deformation
or cracking of the S-SSE, which further hinders the motion of Li-ions
through the interface, apart from consuming active electrolyte material
[147].
Sulfur-based cathodes: Finally, in Li-S batteries, interfacial issues play
a major role in limiting their performance, and therefore their commer-
cial applicability [148]. Li-S batteries generally have chemical interfa-
cial issues stemming from the poor ionic and electronic conductivity of
S and Li2 S, which can be formed by the reaction of the Li2 S cathode
and the S-SSE. An additional chemical interfacial instability that arises
due to side reactions at the interface is the formation of H2 S gas as a
reaction product. Not only does this result in the deterioration of cell
performance over cycling, the gas is also toxic. Chemistry-based strate-
gies have been used to suppress this H2 S formation. Mechanically, the
large volume change between the lithiated and delithiated states of the
cathode (Li2 S and S, can cause a loss of contact and build up of me-
chanical stresses, causing particle pulverization at the interface. Saccone
et al. used emulsion stereolithography-based 3D printing to create a con-
formal interface between the SSE and cathode, to mitigate mechanical
interfacial instabilities in a Li-S battery [149].
Sulfide-SSE/ Li anode interface:
Similar to the interface between the S-SSE and the cathode, there
are a number of key issues affecting the anode/S-SSE interface [9]. Pri-
marily, the growth of Li dendrites into cracks in the SSE compromise
the interfacial stability, and cause capacity loss over cycling, as well as
potential shorting between the electrodes. These cracks typically grow
along grain boundaries or defects near the interface [150], due to the
relatively higher conductivity of the grain boundary compared to the
grain interior, resulting in preferential Li deposition along grain bound-
aries, which in turn can lead to Li dendrite growth [151]. However,
Li dendrite growth at the interface has also been observed in glassy S-
SSEs, without grain boundaries [152], where low compaction density in
S-SSEs can result in defects, which also act as potential sites for voids/Li
dendrite growth.
Additionally, the shear modulus of the SSE compared to Li metal has
been hypothesized to play an important role in dendrite formation [84].
An SSE with a lower shear modulus is less effective in suppressing inter-
facial roughening over cycling, in turn increasing the propensity to form
Li dendrites [153]. Finally, poor solid/solid contact can result in holes
or spaces forming at the anode/S-SSE interface, which provide space
for the deposition of Li into such voids, in turn leading to potential Li
dendrite growth. The other major cause of mechanical instability facing
the interface between the anode (usually Li metal) and the S-SSE in-
clude accommodating the large volume changes associated with Li plat-
ing/stripping at the anode, which can result in deteriorating solid/solid
contact over repeated plate/strip cycles.
Apart from the mechanical instabilities, maintaining the chemical
and electrochemical stability of the anode/S-SSE interface is also a chal-
lenging issue. The chemical stability of the interface is often gauged in
terms of the reactions occurring at the anode/S-SSE interface, which
can result in various reaction byproducts that can consume the active
material in the cell, resulting in a loss of cell capacity, or evolution of
species such as oxygen that can compromise the safety of the ASSB due
to potential thermal runway [154]. The processing techniques employed
for fabricating the SSEs can also contribute to the chemical interfacial
instability. For example, Ito et al. showed that residual impurities are
often preferentially segregated towards the interface, which can am-
plify chemical instability at the interface [155]. On the other hand, the
electrochemical stability window for Li metal against S-SSEs is narrow
to begin with and can be further compromised due to the presence of
chemical side reactions at the interface, resulting in a build up of interfa-
cial impedance [123]. A stable interface is preferentially ionically con-
ducting and electronically insulating. However, the interface between
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Energy Storage Materials 45 (2022) 969–1001
S-SSEs and a Li-metal anode can often have some electronic conduc-
tivity, thus acting as a mixed ionic electronic conductor. The resultant
electron transfer across the interface then causes a continuous consump-
tion of the active SSE material, while also leads to commensurate vol-
ume growth of the unstable interfacial layer, increasing the interfacial
impedance and decreasing the cell performance [156]. Finally, there is
a push towards understanding if the choice of cathode material for the
ASSB can also affect the interfacial stability of the anode/SSE interface
[157].
3.1.2. Interfacial strategies: Sulfide-based SSEs
In light of the various interfacial instabilities outlined in the earlier
sub-section, there are several strategies that have been implemented to
improve interfacial stability in ASSBs [158]. Irrespective of the partic-
ular interfacial strategy or combination of strategies employed, the pri-
mary objectives of such interfacial strategies remain broadly similar, in
terms of mitigating the various mechanical, chemical and electrochem-
ical instabilities discussed above. Finally, the interface between the S-
SSE and either electrode should be thin, so as to maintain high specific
energies.
Chemical doping: Doping-based strategies can be broadly classi-
fied into substitutional, interstitial and mixed-type doping. In substitu-
tion doping, the sulfur is replaced with either Se or O [114,159]. While
substituting Se induces point defects in the SSE, O doping makes it a
3D structure from a 2D structure, both of which can result in better in-
terface conductivity [160,161]. On the other hand, interstitial doping is
usually done on the anode, primarily with halides [115,162]. Li doped
with In is the most commonly implemented interstitial anode doping
strategy. Such doping of the Li metal anode with halides results in a
suppression of dendrite formation at the anode/SSE interface [163], as
illustrated in Fig. 5 (a). Finally, dual doping is a combination of both dop-
ing types, often involving substituting a metal for P, as well as a halide
for S), as shown in [116,164,165]. While ternary S-SSEs have the high-
est conductivity, they contain Ge, which is considered to be high cost.
So substitution doping in ternary SSEs can also be geared towards finding
suitable cost-effective replacements for Ge, without compromising the
high conductivity of the SSE. Towards achieving this objective, Whiteley
et al. substituted Si [166], Ong et al. substituted Sn [167], while Ooura
et al. explored substitution of Ge with Al [131]. Ong et al. demonstrated
via simulations that making such cationic substitutions for Ge should not
have any noticeable effect on the interfacial stability of the SSE against
a Li metal anode [167], while Whiteley et al. experimentally demon-
strated a slightly more stable anode/SSE interface with Li10 SiP2 S12 com-
pared to Li10 GeP2 S12 [130], resulting in better cyclic capacity retention
over 70 cycles.
In Li-S batteries, the formation of toxic H2 S as a reaction byproduct is
a major challenge, as discussed in Section 3.1.1. Addition of oxides to the
Li3 PS4 SSE has been a popular method to suppress H2 S formation. Hood
et al. explored the addition of Li6 ZnNb4 O14 , Al2 O3 , and SiO2 [168];
Hayashi et al. conducted a similar study with Fe2 O3 , ZnO and Bi2 O3
as the oxide fillers [169] and Ohtomo et al. explored the addition of
Li2 O, [170]. However, these additives came at a cost of lower ionic
conductivity of the SSEs. Hayashi et al. added ZnO, which did not show a
similar reduction in SSE conductivity as compared to other metal oxides
[171].
Optimizing processing methods: With mechanical ball milling, the
chief strategy is to control grain size/boundaries. Reducing the particle
size of the cathode materials is helpful to form sufficient contact between
the electrolytes and cathode, as demonstrated by Peng et al. [172] and
Xu et al. [173]. Additionally, controlling the grain size of the SSE can
also be used to mitigate Li dendrite growth, as well as obtaining SSEs
with homogeneous properties. For example, Sakuda et al. claimed that
the largest particle should be less than half the thickness of the SSE
layer [174] for achieving a relatively homogeneous SSE layer between
the electrodes. Seino et al. used a novel hot press method (a type of
melt processing technique) to reduce grain boundaries, which helped
P.P. Paul, B.-R. Chen, S.A. Langevin et al. Energy Storage Materials 45 (2022) 969–1001

Fig. 5. Various strategies employed for stabilizing interfaces in sulfide-based SSEs. (a) Co-doping an agrodyte-type SSE with ZnO, to stabilize the anode/SSE and
cathode/SSE interfaces. Adapted with permission from Ref [163]. © 2019 American Chemical Society. (b) Coating on the cathode surface. The left panel shows an
interfacial region between the LCO cathode and Li2 S - P2 S5 SSE, while the right panel shows the sharp interface with an Li2 SiO3 coated LCO cathode. to increasing
the cathode/SSE interfacial stability. Adapted with permission from Ref. [184] © 2010 American Chemical Society. (c) Use of I as a buffer layer between the SSE and
Li- metal anode, resulting in a suppression of Li dendrite formation. Adapted with permission from Ref [188]. © 2018 Elsevier. (d) Composite SSE-cathodes. The top
example shows the stable cyclability for Li3 PS4 coated Li2 S cathode nanoparticles [194], while the bottom example shows an LCO cathode - LGPS SSE composite and
the corresponding cyclic behavior [121]. Adapted with permission from Ref [194]. © 2013 American Chemical Society. Adapted with permission from Ref [121].
© 2017 American Chemical Society.

to mitigate Li dendrite formation at the anode/SSE interface for S-SSEs
[113].
To obtain conformal interfaces, laser deposition techniques have
proven to be a popular fabrication method. These techniques, while
popular in a laboratory type setting, have challenges with scalability,
and thus need to be suitably modified for commercial applications. Oh
et al. demonstrated a scalable single-step wet-chemical fabrication pro-
tocol for bendable sheet-type composite electrodes [175]. They used a
wet chemical process, consisting of a one pot slurry using SSE materials
(Li2 S and P2 S5 ), active electrode materials (NMC/graphite) and poly-
meric binders to fabricate a sheet-type ASSB [175]. Park et al. similarly
demonstrated a scalable solution coating technique to fabricate a 0.4LiI
0.6Li4 SnS4 ASSB [176]. The enhanced contact at the interface resulted
in significant improvements in capacity retention of the cell over cy-
cling, coupled with enhanced air-stability during processing.
Interfacial coatings and buffer layers: Coatings are among the
most common strategies for mitigating electrochemical and chemical
instabilities. In particular, coatings can play a major role in decreasing
the oxidative degeneration of the S-SSE at the cathode/SSE interface
leading to an increase in interfacial impedance and eventually a loss of
cell capacity over cycling [117]. Cathode coatings can serve to isolate
reactive species; thus, improving the chemical interfacial instability. Me-
chanically, coatings are also expected to mitigate the loss of interfacial
contact due to the breathing effect [177].
An ideal coating material is Li-ion conducting and electron insulat-
ing, has oxidative stability against the SSE and the electrode, and is me-
chanically deformable, to accommodate the volume changes of the cath-
ode during cycling. Kitsche et al. recently demonstrated the markedly
superior cyclability (over 60 cycles) and rate capability (up to 1C) of a
lithium thiophosphate SSE based ASSB, by using an HfO2 coating, de-
posited by atomic layer deposition on to a Ni-rich NMC cathode [178].
In general, using a coating material with Li and large cations with high
oxidation states (such as Nb5+ or Ta5+ ) is a common strategy, due to
their low mobility and low likelihood to oxidation. LiNbO3 is the most

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P.P. Paul, B.-R. Chen, S.A. Langevin et al. Energy Storage Materials 45 (2022) 969–1001

commonly studied coating material employed in S-SSEs. Several previ- lenge, limiting their capacity retention, safety and rate capability. While
ous studies have investigated the effect of spray coating LiNbO3 on LCO several promising strategies, such as doping and coatings have been ex-
cathodes, seeing an improvement in cell performance [179–181], while plored to mitigate these instabilities, there is still plenty of work to be
Takada et al. saw a similar effect with LMO cathodes [182]. Takada done to truly realize the transition from commercial LIBs to ASSBs. Some
et al. also studied the effect of spray coating Li4 Ti5 O12 , and LiTaO3 , of these avenues are discussed subsequently in Section 4.2.
apart from LiNbO3 , for an LCO cathode and S-SSE system [183]. They
showed that LiNbO3 and LiTaO3 coatings are more effective for higher
3.2. NASICON-type polyanionic frameworks
power density operation, due to their higher ionic conductivity. Other
Li-metal based oxide coatings that have been studied include Li2 SiO3
The sodium superionic conductor (NASICON) structures were first
[184], LiTaO3 [185], LiAlO2 [186] and Li2 ZrO3 [187]. Fig. 5 (b) illus-
discovered in the early 1970s, referred to as a family of solids with
trates the use of Li2 SiO3 coating on an LCO cathode in creating a sharp
the chemical formula Na1+x Zr2 P3-x Six O12 [195–197], and have since
cathode/SSE interface (Li2 S - P2 S5 ), resulting in a lower impedance and
continued to stimulate intense interest in their use as SSEs. NASICON-
improved cyclability of the cell [184]. While coatings have been shown
type skeletal structures, conducive towards Li-ion transport, yield sev-
to markedly increase ASSB performance, the underlying mechanisms
eral such advantages as high electrochemical stability, chemical sta-
are not yet fully comprehended; thus, leaving lingering questions for
bility in ambient atmosphere, mass production, and potentially low
the future design of optimal coatings.
cost. NASICON-type Li-ion conducting electrolytes with the formula
Conversely, buffer layers have been implemented for S-SSEs primar-
LiM2 (PO4 )3 , where M, in the +4 oxidation state, can be replaced par-
ily at the anode/SSE interface. Kato et al. showed that by using a thin
tially by trivalent ions, (Al3+ , Sc3+ ) to generate the most commonly
gold film between the Li metal anode and 75Li2 S.25P2 S5 S-SSE, the mor-
studied electrolytes, Li1+x Alx Ge2-x (PO4 )3 and Li1+x Alx Ti2-x (PO4 )3 .
phology of Li on the anode could be better controlled for improved uni-
These NASICON-type electrolytes exhibit high Li-ion conductivities up
formity, resulting in better cycling performance of the symmetric Li/S-
to 10−3 S cm−1 at room temperature.
SSE/Li ASSB [120]. Having a Li-halide layer in between the Li metal
Although NASICON-type electrolytes offer high oxidative stability
anode and the S-SSE has also been used to suppress dendrite forma-
[85,90,96], their instability at the anode/SSE interface hampers their
tion at the anode interface. Xu et al. demonstrated the superior stabil-
implementation for ASSBs [101,102,198]. Moreover, for electric vehi-
ity of the anode/S-SSE interface with LiF and LiI layers coated on to
cle (EV) applications, where fast charging is of utmost priority, the lower
the Li7 P3 S11 SSE, resulted in dendrite formation suppression [188], as
ionic conductivity compared to other electrolytes (e.g. sulfides, oxides),
shown in Fig. 5(c). In particular, an LiF interlayer achieved superior den-
further exacerbates the feasibility for this particular application; how-
drite suppression, compared to LiI. Han et al. also saw a significant im-
ever, for scenarios that do not require fast charging (e.g. primarily for
provement in the critical current density over cycling with an LiI buffer
military applications, and large-scale energy storage), the coupled ad-
between the Li anode and Li2 S-P2 S5 SSE, which they attributed to the
vantages between high voltage stability and air inertness, offers a com-
suppression of Li dendrite formation due to improved mobility of Li-ions
pelling system for an energy-dense, safe, system.
at the anode/SSE interface [189]. This improvement in cell performance
Several such strategies have been employed to improve the stabil-
for a LiI anode compared to a Li anode was consistent over a wide tem-
ity of NASICON-type electrolytes when in contact with reactive lithium
perature range (from 25 °C to 100 °C), for galvanostatic cycling at 1C
metal. The first method has focused on the incorporation of an inorganic
charging and discharging up to 100 cycles.
buffer layer, such as (e.g. alumina, Al2 O3 [199]; germanium, Ge [200];
Another particularly popular buffer layer is the bi-layer configu-
bismuth, Bi [201]). The second strategy has involved polymer compos-
ration in which a binary S-SSE is used as an intermediate buffer be-
ites that combine the benefits of liquid electrolytes (or Li+ -containing
tween the Li anode and the ternary S-SSE, due to poor stability of Li
salts) and NASICON-type powders [202–206]. This method has gar-
metal against ternary S-SSEs. Trevey et al. showed that in an ASSB
nered the most interest for leveraging prior knowledge in polymer elec-
with a Li metal anode, which has an unstable interface with the ternary
trolytes, and adapting protocols to incorporate SSE materials. Although
Li2 SGeS2 P2 S5 SSE, an intermediate binary SSE (Li2 SP2 S5 ) greatly im-
not as ubiquitous as inorganic and organic coating strategies, leveraging
proved the interfacial stability at the interface [190]. Shin et al. simi-
the NASICON skeleton structure with analogous NASICON anode and
larly had LPS (Li3 PS4 ) as an intermediate buffer between the Li anode
cathode materials (e.g. lithium titanium phosphate, Li3 Ti2 (PO4 )3 ; and
(alloyed with In) and the ternary LGPS (Li10 GeP2 S12 ) SSE, and observed
lithium vanadium phosphate, Li3 Ti2 (PO4 )3 , respectively) has shown to
a similar decrease in the interfacial instability [191]. Xie et al. doped
improve lattice matching of the respective NASICON-type SSE [207].
Li3 PS4 with SbO2 to generate a bi-layer /Li3 P0.98 Sb0.02 S3.95 O0.05 /
Below, we first detail the challenges at the cathode/SSE interface, then
Li10 GeP2 S12 SSE configuration, showing a greatly enhanced stability
identify the underlying challenges at the anode/SSE interface, and will
against the Li anode, resulting in enhanced capacities [192].
provide a review of the numerous strategies that have been employed
Cathode–SSE composite electrodes: Another strategy to mitigate
to address these critical interfacial challenges.
interfacial instabilities, particularly with oxide-based cathodes and S-
SSEs is to create composites of the cathode material and the respec-
tive SSE. Sakuda et al. used a pulsed laser deposition technique to coat 3.2.1. Interfacial challenges: NASICON-based SSEs
Li2 SP2 S5 SSE onto LCO cathode particles, to obtain a nearly 50% in- The challenges in understanding and improving the interfaces be-
crease in the cell capacity of the ASSB [193]. Lin et al. similarly coated tween the anode/ and cathode/SSE interface underpins the stability of
Li3 PS4 onto a core shell of the Li2 S cathode particles in a Li-S ASSB, ASSBs. The combination of chemical and mechanical instabilities at the
to achieve a markedly improved cycling performance and rate capa- interface leads to a number of such issues as capacity fade, mechan-
bility due to small particle size and improved ionic conductivity [194]. ical failure, and even thermal failures [38,50,208–211]. Much of the
Zhang et al. systematically studied the effect of different compositions of instability of NASICON-type electrolytes involve contact of the Li-ion
Li10 GeP2 S12 S-SSE on composite electrodes with an LCO cathode [121]. conducting electrolytes with the formula LiM2 (PO4 )3 electrolyte with
They found that on one hand, a low fraction of S-SSE is better suited for bare lithium metal. The spontaneous reduction of the metal (e.g. Ti or
high energy applications, while on the other hand, a higher fraction of Ge) from M4+ /M3+ leads to the formation of an unstable solid elec-
SSE in the composite is more suitable towards high power applications. trolyte interphase. The sensitivity of this spontaneous reduction can be
Fig. 5 (d) illustrates the stable cycling behavior of cathode nanoparticles attributed to the highly-reducing lithium metal anode; thus, it is imper-
coated with nanofilms of the SSE, as shown in [194] and [121]. ative that interfacial strategies must be implemented to either form a
Therefore, while S-SSEs are the most popular class of SSEs due to stable spontaneous interphase, or directly apply a stable interphase that
their higher ionic conductivity, interfacial instabilities remain a chal- minimizes this metal reduction process. ASSBs without interfacial layers

980
P.P. Paul, B.-R. Chen, S.A. Langevin et al.
have a limited cycle life up to 50 cycles, which underscores the impor-
tance of these forthcoming strategies [212]. In essence, this chemical in-
stability further exacerbates the mechanical instability of the NASICON-
type SSE under lithium plating/stripping operation that leads to the
formation of cracks and lithium dendrite penetration [38,50]. Through
theoretical models, NASICON-type electrolytes are expected to provide
high oxidative stability[85,90,96]; yet, other factors, such as increas-
ing interfacial resistance and the growth of a lithium depletion layer,
promotes other areas of challenges for interfacial strategies.
NASICON/cathode interface: Much of the focus on stabilizing the
interfaces at the cathode have gathered around sulfide- and oxide-based
solid state electrolytes [213]. The contact between the SSE and the cath-
ode presents a charge-transfer resistance that arises from poor contact,
thermal expansion mismatch, lattice mismatch, and the corresponding
interface reaction during charge/discharge. In particular, commercially-
relevant LCO and Ni-rich cathodes have been paired with NASICON-
type electrolytes to study the stability of the NASICON/cathode inter-
face [29,214–217]. In this configuration, undesirable reaction products,
such as Co3 O4 for LCO/NASICON systems, leads to the decrease in the
number of active sites for charge transfer at the interface, owing to the
inactive oxide phase which inhibits efficient charge transfer at the NA-
SICON/cathode interface [29]. To address this, intentional formation of
materials that can conduct Li-ions, such as LiNbO3 , becomes a neces-
sary step. The underlying challenges at the NASICON/cathode interface
is in large part due to the interfacial potential drop. Modification of
the interlayer between this interface has been shown to stabilize the
interfaces when the cathode material comes into contact with the SSE.
In this manner, according to the space-charge layer theory, a gradual
potential drop is exhibited to relieve the high polarization of materi-
als with differing chemical potentials. Two dominating strategies that
thus improve the NASICON/cathode interface has been to optimize pro-
cessing conditions (e.g. sintering) of the cathode active material with
the SSE powder and incorporating oxide-based buffer layers to reduce
the potential drop across this interface. As referenced above, the critical
challenge for NASICON-type electrolytes is owed to the chemical insta-
bility at the NASICON/anode interface, and much of the efforts in the
research community has focused on this particular challenge.
NASICON/anode interface: The highly reducing nature of lithium
metal poses the greatest challenge for NASICON-type electrolytes, owing
to the spontaneous reduction of the SSE[101,102,218]. This reduction
has shown to occur at a high lithium half-cell potential of 2.17 V ver-
sus Li/Li+1 [90]. The lingering issue leads to the formation of an inter-
phase region arising from direct electrochemical reactions, which drives
forth mechanical failure, where the NASICON-type electrolyte will form
cracks. This crack propagation then governs the stability of this SSE;
thus, having significant consequences into both the cycling stability and
thermal stability of the cell. Moreover, the instability of this interphase
were found to be highly dependent on current density where higher
rate operation caused greater non-uniformity of the interphase, and led
to severe crack growth of the NASICON-type SSE [38,50]. Though me-
chanical degradation is in essence a severe roadblock to NASICON-type-
based ASSBs, a prior study has shown that induced mechanical failure
leads to thermal runaway, particularly at high temperature (> 200 °C)
[211]. This understanding of the chemomechanical behavior, coupled
with thermal failure underscores the importance of innovative strate-
gies for improving the NASICON/anode interface. Two main strategies
exist with which to stabilize NASICON-type SSEs when paired with a
lithium metal anode, and those are inorganic and organic buffer layers.
The existence of these buffer layers are suggested to lead to the forma-
tion of stable interphase products that maintain the mechanical integrity
at the NASICON/anode interface, and leads to stable cycling and overall
stability during charge/discharge operation.
3.2.2. Interfacial strategies: NASICON-based SSEs
Interfacial buffer layers: Taking into the consideration the aforemen-
tioned challenges of the NASICON/anode interface, numerous studies
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Energy Storage Materials 45 (2022) 969–1001
have sought to incorporate a thin, interfacial buffer layer to act as a
barrier to improve chemical stability. Though a nearly endless list of
materials exist with which to deposit interfacial buffer layers, we will be-
gin by reviewing the most commonly used materials for NASICON-type
electrolytes. Boron nitride (BN) has been investigated for the purposes
of having a higher Young’s modulus than ceramic electrolytes; thus, pro-
moting high mechanical strength to obstruct dendrite growth, while also
providing chemical stability in combination with trace amounts of liq-
uid electrolyte in polyethylene oxide. Symmetric cells comprising the BN
interfacial buffer layer exhibited steady cycling over 500 h at 0.3 mA
cm−2 and demonstration of a lithium/BN/LATP/LiFePO4 cell achieved
96.6% capacity retention for 500 cycles; a higher capacity cell compris-
ing NMC yielded a capacity retention of 93% up to 100 cycles (Fig. 6a)
[219]. Related to nitride-based compounds, lithium phosphorous oxyni-
tride (LiPON) has found much success as an ionic conductor, and is now
considered as an interlayer owing to its mechanical strength to suppress
dendrites, and can be easily fabricated in the form of a thin film [220].
Sputtering metals is yet another strategy with which to improve
Li-ion transport across the anode/SSE interface. When a thin layer
of germanium is sputtered onto LAGP, this buffer layer circumvents
spontaneous Ge4+ to Ge2+ /Ge0 (Fig. 6b) [200]. The achieved perfor-
mance of a Li/Ge/LAGP/Ge/Li symmetric cell in terms of cycle life and
charge-transfer resistance was dramatically improved compared to a
Li/LAGP/Li cell. Considering the second lowest electronic conductiv-
ity in all metals, Bi, this buffer layered was sputtered onto LAGP based
on the hypothesis that the lower electronic conductivity is beneficial to
maintain interfacial stability [201]. Similarly, the incorporation of the Bi
buffer layer yielded far superior plating/stripping as compared to with-
out the layer. Moreover, stable cycling using Li/Bi@LAGP/LiFePO4 was
achieved up to 120 cycles at 1C. Oxides have also been employed as an
interfacial buffer layer, and in a prior study, it was shown that an ultra-
thin Al2 O3 layer enhances the wettability and chemical stability against
Li metal, which drives the formation of a stable interphase that is con-
ducive to Li-ion transport. The incorporation of this Al2 O3 layer yielded
stable cycling with smaller voltage hysteresis for up to 600 h and lower
charge-transfer resistance compared to bare lithium/LATP [221]. Zinc
oxide (ZnO), which is lithiophilic, has also shown to improve the com-
patibility between LATP and Li by reducing the interfacial impedance
from 80,554 to 353 Ω [222].
Composite organic–inorganic SSEs: Composite electrolytes com-
prising inorganic SSEs and organic polymers have been an intense
area of focus for stabilizing the interface and cyclability of ASSBs
[223,224], particularly for NASICON-based SSEs. Numerous combi-
nations of polymers and NASICON-type SSEs, primarily using acry-
lates, poly(acrylic acid), polyethylene oxide, poly(vinylidenefluoride-
hexafluoropropylene), polyacrylnitrile, and polypropylene, have been
studied to address both anode/ and cathode/SSE interface issues. More-
over, owing to the ambient stability of NASICON-type SSEs, several bat-
tery configurations can be coordinated for the purposes of electrochem-
ical energy storage, such as Li-metal batteries, Li-sulfur, Li-air, and Li-Br
batteries.
Beginning with Li-metal batteries, Zhou et al. utilized a combina-
tion of a cross-linker containing a polymer with a ceramic LATP elec-
trolyte (Fig. 6c) [202]. Therein, a lithium-containing cross-linked acry-
late (poly(ethylene glycol) methyl ether acrylate) at the electrode sur-
face with LATP sandwiched between was used. This creates what they
refer to as a lithium/polymer/ceramic/polymer electrolyte (PCPSE), and
provides the benefits that both polymer and LATP provide. The poly-
mer allows for better wettability at the surface and higher ion mobility
while simultaneously utilizing LATP to reduce the anion transfer; thus,
dramatically improving cell performance where a Coulombic efficiency
of > 99.8% is maintained over 640 cycles in a complete ASSB config-
uration (Fig. 6d). Self-healing Janus interfaces were also investigated
by Liu et al, where they demonstrate the use of acrylate chemistries
that could mitigate electrolyte leakage, retard flammability, and de-
crease the propensity for Li dendrite growth [203]. This was done with
P.P. Paul, B.-R. Chen, S.A. Langevin et al. Energy Storage Materials 45 (2022) 969–1001

Fig. 6. (a) Electrochemical characterization of LATP and LATP/BN Pellets in Li/Li symmetric cells. The schematic and the Nyquist plots of bare LATP and LATP/BN
pellets in Li/Li symmetric cells with PEO infiltrating. The evolution of real impedance of Li/Li cells with bare LATP and LATP/BN pellets. 1-2 mm thick PEO was
added on each side to wet the interface. The long-term cycling of Li/Li symmetric cells with bare LATP (red) and LATP/BN (blue) were tested at current density of
0.3 mA cm−2 at 60 °C. Reproduced with permission from Ref. [219] © 2019 Elsevier. (b) Schematic diagrams of the amorphous Ge film coating between LAGP solid
electrolyte and lithium metal. Ge film coating LAGP ensures intimate contact between LAGP and Li metal. Before Ge film coating, Ge4+ in the LAGP pellet would be
reduced to Ge2+ and Ge0 upon contacting with Li metal; after sputtering Ge film between LAGP and Li anode, Ge4+ is protected and remains stable after cycling.
Reproduced with permission from Ref. [200] © 2018 John Wiley and Sons. (c) Illustration of all-solid-state battery design with PCPSE electrolyte. Reproduced with
permission from Ref. [202] © 2016 American Chemical Society. (d) Cycling and C-rate performance of the Li/LFP cells with CPMEA and CPMEA-LATP-based PCPSE.
Reproduced with permission from Ref [202]. © 2016 American Chemical Society. (For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)

two separate examples of self-healing electrolytes, such as pentaerythri-
tol tetraacrylate (PETEA) as the cross-linker and 2-[3-(6-methyl-4-oxo-
1,.4-dihydropyrimidin-2-yl)-ureido]ethyl methacrylate (UPyMA) mixed
with LiTFSI and EMITFSI with varying carbonates (for anode, ASHE)
and adiponitrile solvents (for cathode, CSHE). LAGP is also known to
be highly reactive with molten Li; thus, He et al. thoroughly studied
the reaction mechanism between molten lithium and LAGP and deter-
mined that Ge4+ was reduced to Ge0 [209]. To address this problem,
He et al. utilized a co-polymer of poly(acrylic acid and poly(maleic acid)
to coat the LAGP surface to form a barrier between Li and LAGP. How-
ever, the polymer coating also increased the resistance of the LAGP SSE.
To increase the ionic conductivity of the polymer, lithium chloride was
added. He et al. were able to demonstrate that P(AA-co-MA)Li coated
LAGP cells could cycle at 15, 30, and 70 mA cm−2 over 100 cycles with
stable over potentials of 0.036, 0.105, 0.257 V, respectively.

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P.P. Paul, B.-R. Chen, S.A. Langevin et al.
Polyethylene oxide (PEO) is another commonly used polymer addi-
tive for Li-polymer batteries, but have since been extended to compos-
ite organic–inorganic SSEs. The polymer PEO is a very widely popular
polymer electrolyte due to its inherent nature to readily dissolve many
different lithium salts. Zhao et al. showed that LAGP could be used as
active fillers in a PEO composite [198]. This increased the ionic con-
ductivity of the PEO electrolyte and widened the voltage window. They
were able to demonstrate capacities as high as 166 mAh g−1 when paired
with LFP. Wang et al. also demonstrated that PEO could be utilized as
both an anode protecting layer and an electrolyte composite with LAGP
[225]. PEO was mixed with LiTFSI onto the lithium surface to increase
wettability as well as protect the lithium surface from direct contact
with LAGP. Through this technique they were able to demonstrate dis-
charge capacities as high as 161 mAh g−1 when paired with LMFP. Sim-
ilarly, PEO-LATP composites were also prepared to help mitigate the
spontaneous reduction of Ti, and this composite was able to decrease
overpotential for lithium plating/stripping from 2.03 V to 0.4 V, allow-
ing for stable cycling enduring up to 400 h at 0.05 mA cm−2 [226].
However, it has been shown recently that PEO-based electrolytes have
have relatively low ionic conductivity and narrow electrochemical win-
dow and have poor interfacial stability with electrodes. To address this,
Peng et al. demonstrated that they could circumvent these problems
through the use of plasticizers, specifically succinonitrile (SN) [227].
Here, they use PEO with SN and LAGP particle fillers to take advan-
tage of the polymer properties of PEO to increase the stability and ionic
conductivity. Additionally, SN increases the mechanical properties of
the PEO-based polymer, allowing for flexible ASSBs. This PEO-LAGP-
SN composite solid polymer electrolyte showed a high ionic conduc-
tivity of 1.26 × 10−4 S cm−1 and was stable up to 4.9 V. To further
stabilize the electrochemical stability of PEO-based composite SSEs, ex
situ LiF and Li3 N was utilized as an artificial SEI layer in combination
with an LAGP-PEO composite, which achieved 95% over 200 cycles us-
ing LFP was the cathode [228]. PEO-LATP composites have been well
demonstrated, but have been shown to have poor ionic conductivity. To
overcome this Yang et al. utilized boronized polyethylene glycol (BPEG)
as an organic filler [229]. These BPEG oligomers disorganize the crys-
tallinity of the PEO structure thereby increasing the ionic conductivity
of the PEO/LATP composite. The addition of BPEG also increases the
contact with the electrode surface and increases the Li-ion conductivity
over PEO/LATP alone. Through the addition of BPEG dendrite growth
was decreased and showed capacities as high as 158 mAh g−1 when
paired with LFP cathodes.
Though acrylate- and PEO-based composite SSEs with LAGP or LATP
continue to dominate the literature for strategies on improving interfa-
cial stability for NASICON-type electrolytes, other polymers that have
been investigated include polypropylene [204,230,231], polycaprolac-
tone [232], polyaniline [205], polyvinyl butyral (i.e. Butvar B98) [233],
polyvinylidene fluoride-based polymers [206,234,235]. All of these em-
ploy analogous strategies as those mentioned above, and have shown
that cycle life and discharge capacities can be further enhanced. For Li-
metal batteries comprising NASICON-based SSEs, the use of polymers
have gained sufficient attention as a proven strategy for developing
ASSBs.
Li–S chemistry is a contender as a novel electrochemical energy stor-
age system that can exceed the performance of current state-of-the-art
LIBs. For this configuration, NASICON-type SSEs have been considered
as a potential system that provide stable cycling by mitigating lithium
polysulfide shuttling. The PEO-LiTFSI composite SSE has been further
extended to Li–S systems, where a combination of ALD-deposited Al2 O3
onto the surface of an PEO-based protective layer on LATP yielded a
capacity of 823 mAh g−1 after 100 charge/discharge cycles [236]. In a
later study, Wang et al. showed they could use a PEO-LiTFSI solid poly-
mer electrolyte to protect lithium metal in a Li–S battery by sandwiching
PEO on both sides of the LATP electrolyte between the lithium metal
surface and the sulforonized polyacrylonitrile (SPAN) cathode [237].
Through this technique they were able to demonstrate ultrahigh initial
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Energy Storage Materials 45 (2022) 969–1001
discharge capacities as high as 1793 mAh g−1 at 75 °C. Another type of
polymer, Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-co-
HFP), was used to prepare PVDF-co-HFP/LATP composite SSEs for Li–S
batteries [238]. This allowed for a flexible ionically conducting poly-
mer electrolyte composite that demonstrated high mechanical strength,
thermal and chemical stability. Utilizing this composite, they were able
to demonstrate capacities as high as 1614 mAh g−1 .
Other post Li-ion technologies, such as Li–air and Li–Br batteries also
include the usage of NASICON-type SSEs in combination with polymers.
For Li-air, PEO-LATP is primarily used for the purposes of bifurcating
the non-aqueous and aqueous electrolyte reserves to maintain recharge-
ability using electrocatalytic materials [239,240]. LAGP has also been
used in LiBr batteries [241,242]. Due to the reactive nature of LAGP
with lithium, a protective layer is necessary. Chang et al. used a PVDF-
coated glass fiber mat to separate the LAGP from the lithium surface
[241]. The mat was soaked in a LiClO4 carbonated based electrolyte.
The mat was then sandwiched with a layer of LISICON film. Lastly, the
bromide cathode in aqueous electrolyte utilized to complete the battery.
The organic soaked PVDF-glass mat protected the LASICON electrolyte
from the lithium metal as well as protected the lithium from the aqueous
electrolyte. This allowed for a cell performance of 1220 Wh kg−1 .
Other strategies: In addition to inorganic buffer layers and organic–
inorganic composites, there are other strategies that have been incorpo-
rated for the purposes of developing ASSBs. One unique attribute to
the NASICON-type framework is that certain electrode materials also
yield comparable crystal structures (e.g. LiV2 (PO4 )3 ; LVP, LiTi2 (PO4 )3 ;
LTP), which enhances stability. For example, Yu et al. reported on a
monolithic all-phosphate ASSB that is conducive towards improved in-
terfacial stability [207]. Stable cycling up to 500 cycles was achieved
by pairing LATP with LTP and LVP as the anode and cathode, respec-
tively, which derived from structural compatibility between the elec-
trode components. In a related study, other cathode materials, compris-
ing LVP, LiNi0.8 Co0.15 Al0.05 O2 , and LiNi0.5 Mn1.5 O4 , showed that LVP
sintered with LAGP showed the highest stability [243]. Another unique
approach has involved bi-layer SSEs comprising both LATP and LAGP
[244,245]. However, in these studies, the authors report that Ge4+ is
more stable than Ti4+ , in terms of spontaneous reduction; however, in
the aforementioned strategies, LAGP has shown to be unstable against
lithium metal. Lastly, an artificial SEI can be intentionally coated onto
lithium metal. In a recent study by Yang et al., the authors report a
nanocomposite protection layer comprising MgF2 , LiF, and B2 O3 , which
can serve as an artificial SEI to shield electron transfer, while retarding
Ti4+ reduction [246].
3.3. Garnet-based electrolytes
Garnet-based Li-ion conductor materials have been considered as
one of the most promising SSE materials for its high ionic conductiv-
ity at room temperature (10−3 – 10−5 S cm−1 ). The earliest member
of the garnet family, Li5 La4 M2 O12 (M = Mb, Ta), was discovered back
in 2004 [247]. Since then, the garnet family has been widely studied
in the following two decades. The most widely used SSE in the garnet
family material is Li7 La3 Zr2 O12 (LLZO). LLZO was discovered in 2007
[248] and its crystal structure was determined in 2011 [249]. Compared
to other siblings in the garnet family, LLZO has a higher Li concentra-
tion and thus exhibits high ionic conductivity of approximately 10−3
S cm−1 at room temperature [250,251]. A great number of elements
(e.g. Al, Nb, and Ti) have been substituted into LLZO to achieve even
higher conductivity [250] and structural stability [252]. The addition of
dopants have been found to stabilize LLZO in its cubic phase against the
transformation to the tetragonal phase, given that the cubic phase has
two orders-of-magnitude higher conductivity compared to the tetrago-
nal phase [250].
In addition to the high ionic conductivity, one of the biggest ad-
vantages for garnet SSEs is its chemical stability. Its stability against Li
metal allows minimized side reactions when in contact with a Li metal
P.P. Paul, B.-R. Chen, S.A. Langevin et al.
anode, and the wide voltage window (up to 5 V – 9 V vs. Li+ /Li) en-
ables a high operating voltage [251]. This stability allows garnet SSEs
to become a safer option for next-generation batteries with high power,
high energy density applications, such as electric vehicle (EV) batter-
ies [253]. Garnet materials also have robust mechanical properties that
qualify them to be processed by various industrial scale techniques, such
as tape-casting, freeze-casting, and die-pressing [254].
3.3.1. Interfacial challenges: Garnet-based SSEs
Despite the great advantages of garnet materials, there are several
factors that prohibit the implementation of garnet SSEs in ASSBs. The
most prominent issue lies in the poor contact between garnet and the re-
spective anode and cathode materials. Unlike liquid electrolytes, which
will penetrate into the gaps between electrode particles, the rigidity of
garnets leads to pores and voids at the electrolyte/electrode interface.
This physical contact issue is even more challenging for the garnet/Li
metal anode interface due to the lithiophobic nature of garnet materi-
als. Consequently, the garnet/Li interface is dewetted and leads to high
charge-transfer impedance. Other than the interface contact issues, Li
dendrite formation at the anode seriously harms the performance of
garnet-based ASSBs. Li dendrites form at the weaker spots of the gar-
net/Li interface when the current density exceeds a certain value. The
dendrites gradually propagate during cycling and eventually penetrate
the electrolyte layer, causing short circuiting and other performance is-
sues. Compared to the anode, the garnet/cathode issues are less severe,
but generally troubled by the chemical instability between garnet and
common cathode materials such as LCO, LMO and LFP. The interlayer
diffusion between garnet and the electrodes during cycling or during the
annealing step in battery fabrication will also cause decomposition and
secondary phase formation.
Garnet/cathode interface: The major challenge at the gar-
net/cathode interface is the chemical stability, specifically secondary
phase formation and inter-diffusion between cathode materials and the
garnet SSE during battery synthesis. In Miara et al.’s work in 2015 [252],
first principles calculations was used to analyze the stability of LLZO and
Li5 La3 Ta2 O12 against such commonly used cathode materials as LFP,
LMO, and LCO. At higher voltages, LMO and LFP react with garnet more
strongly, while LCO is relatively stable. In all of these cases, the inter-
face decomposes during charging and forms interphases at the interface,
such as La2 Zr2 O7 and Li2 CoO3 in the garnet/LCO pair, and Li3 PO4 and
Fe2 O3 in the garnet/LFP pair. This chemical instability will be further
exacerbated under heat treatment protocols. To experimentally investi-
gate the thermal and chemical stability of garnet and cathode materials,
garnet has also been paired with commercial cathode materials such as
LCO and NMC [22,27,255]. XAS and STEM analyses showed that the
garnet/LCO pair can be reactive as low as 300 – 500 °C, forming an
interface layer composed of Li2 CoO3 and La2 Zr2 O7 [22] (Fig. 7a, b).
This interface layer blocks Li transfer and leads to increased impedance.
Zhang et al. [255] ball-milled and co-sintered Li6.75 La3 Zr1.75 Ta0.25 O12
together with LCO or NMC (Fig. 7c), respectively. After ball milling,
the garnet coats onto the LCO or NMC surface and does not induce any
chemical reactions at room temperature. However, after co-sintering at
873 K, Ni-La and Ni-Li exchange occur due to interdiffusion, along with
the formation of La2 Zr2 O7 and LaNiO3 , which has a negative impact on
cycling performance.
Several strategies have been used to improve the phase stability
and physical contact at the garnet/cathode interface. To avoid interfa-
cial layer formation and garnet decomposition while maintaining good
interface contact, one strategy is to shorten the annealing time for
the garnet/cathode interface, such as the employment of rapid heat-
ing/annealing methodologies [256,257]. These rapid heating strategies
are used in garnet/V2 O5 cathode pair [258,259], which was heated to
800 – 900 °C within 10 s (Fig. 7d). Heating at such short time-scales en-
ables only the outer surface of V2 O5 to melt and penetrate into the voids
at the interface, forming an intimate contact [259]. Compared to the in-
terface without rapid heat treatment, the interfacial resistance of the
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Energy Storage Materials 45 (2022) 969–1001
heat treated interface significantly decreased from 2.5 × 104 to 71Ωcm2
[258].
To improve interface stability, the surface of garnet SSEs can also
be modified by adding inorganic and/or polymer-based materials. In-
organic materials, such as Li2.3 C0.7 BO3 can be added into the garnet
as a soldering additive to stabilize the LLZO/LCO interface and facili-
tate intimate contact [260]. To improve the interface physical contact,
softer polymer layers can be sandwiched in between the garnet and cath-
ode, creating a connected interface between rigid surfaces [261,262].
Another strategy is to coat the cathode particles with a layer of gar-
net. In Bi et al.’s studies, Nb-doped LLZO is coated as island-like, 3D
cross-linked networks to LMO or LCO cathode particles using a sol-gel
approach [263,264]. The Nb-LLZO (LLZNO) coating enhances charge
transfer at the cathode/SSE interface and improves capacity. Along with
the addition of carbon black and ionic liquid at the garnet/cathode in-
terface as well as in between the cathode particles, the interface contact
across the ASSB is further reinforced, thus improving electrochemical
properties. With the addition of LLZNO coating on the LMO cathode,
a capacity retention of 86.4% was maintained over 100 cycles at 0.2C,
whereas the pure LMO cathode only supported 78.6%.
Garnet/anode interface: Li wetting issues: Unlike liquid organic
electrolytes that will penetrate into the gaps between the anode and
cathode particles to ensure intimate physical contact, the poor physical
contact between solid garnet and Li metal is a significant issue. Most
of the transition metals and oxides, which are commonly used to build
batteries, are lithiophobic [265,266], and the garnet surface is no excep-
tion. Li metal wets poorly on garnet surfaces, and exhibits high contact
angles ranging from 90 to 120° from wettability tests. The consequence
of poor wetting is the existence of voids and discontinuities at the in-
terface. Another reason that results in poor wettability is the presence
of lithiophobic impurities that form during the synthesis of garnet SSEs,
or upon air exposure. Common components present in the contamina-
tion layer include Li2 CO3 , LiOH, and other carbon-based species. These
interface species not only cause poor wetting, but also slower Li ion
diffusion across the interface; thus, resulting in a dramatic increase in
impedance [97–100].
Li dendrite growth issues: While Li metal anodes provide extremely
high specific capacity (3860 mAh g−1 ) and capacity density (2046 mAh
cm−3 ), Li dendrite formation is a common issue that severely harms
the performance of ASSBs, and may cause short circuiting and other
safety-related issues [267,268]. For SSEs in general, Li nucleates at de-
fects at the anode/SSE interface, such as around grain boundaries or
pores. These spots are prone to Li nucleation due to their higher degree
of reactivity and thus lower nucleation barrier. Once Li nucleates, it
evolves into dendrites, and they readily propagate through grain bound-
aries and interconnected pores, eventually penetrating through the SSE.
Factors influencing the growth of dendrite include how quickly Li-ions
can transport and how homogeneously Li-ion transport is driven across
the interface [269]. By avoiding local accumulation of high density of
Li-ion flow and favorable conditions for Li nucleation, Li dendrite for-
mation could be successfully alleviated.
3.3.2. Strategies for improving contact at the interface: Garnet-based SSEs
To improve interface contact and wettability between garnet and
Li metal, there are several common strategies, including modifying the
interface and adjusting the properties of the garnet and/or Li metal.
The most popular approach for interface modification is adding a buffer
layer in between the garnet SSE and the Li anode. By blending garnet
and soft materials together, or by alloying Li with other elements, the
wetting properties can be tuned to yield more intimate contact. On the
other hand, to suppress the growth of lithium dendrites, avoiding local Li
accumulation is another effective method. To distribute and regulate Li-
ion transport, 3D anode structures and ionic conductors can be utilized.
In the following paragraphs, we will discuss several of the most common
strategies to improve garnet/Li interfaces.
P.P. Paul, B.-R. Chen, S.A. Langevin et al. Energy Storage Materials 45 (2022) 969–1001

Fig. 7. Common issues and solution strategies at the garnet/cathode interface. (a) TEM, STEM, and EDX analysis of LCO/LLZO interface at the as deposited state
(left) and after 500 °C annealing. Adapted with permission from Ref [22]. © 2018 American Chemical Society. (b) O K-edge X-ray absorption spectroscopy data.
The intensity of the peaks indicates the decomposition of LLZO into Li2 CO3 . Adapted with permission from Ref. [22] © 2018 American Chemical Society. (c) STEM
(up) and TEM (down) images showing smaller LMO particles deposited onto LLZNO particles. Reproduced with permission from Ref[264]. © 2020 Royal Society
of Chemistry. (d) Rapid thermal annealing apparatus (left) and the interface before and after sintering (right). Adapted with permission from Ref. [258] © 2017
American Chemical Society.

Interface buffer layer: A buffer layer between garnet and Li metal
will enhance wettability and cover pores and voids at the interface. Coat-
ing LLZO garnet surfaces with a layer of ceramics, like ZnO or Al2 O3 will
greatly enhance the interface contact [54,270]. As demonstrated in a re-
cent study [270], when molten Li contacts the ZnO coating, Li diffuses
into the ZnO layer to form a Li-Zn alloy layer that wets the garnet sur-
face. Similar to ZnO, an Al2 O3 coating that converts to a Li-Al-O bonding
allows for improved contact and more effective Li-ion transport across
the interface. The ZnO or Al2 O3 coatings can be added using atomic
layer deposition (ALD) or chemical vapor deposition (CVD). ALD has
the ability to form a conformal layer on textured surfaces. For example,
in the cases above, ALD layers were coated onto a highly porous LLZO
structure as anode. By applying the ZnO or Al2 O3 coatings, melted Li
infiltrates into the porous LLZO layer and fills in the voids. Otherwise,
Li infiltration will be halted at the outer surface. A comparison between
Li/garnet interface with and without ALD-Al2 O3 coating is shown in
Fig. 8a. With the help of ALD-Al2 O3 coating, the interfacial area spe-
cific resistance (ASR) dramatically reduced by 50-fold from 1,710 to 34
Ωcm2 .
An interface buffer layer can also be made of soft materials. A com-
mon method to create the solid polymer layer is a blend of polyethylene
oxide (PEO) and LiTFSI (Fig. 8b). The blend can be deposited onto gar-
net surfaces with relative ease using drop coating, spray coating, or spin
coating; thus, forming a continuous and conductive interface layer and
covering voids and kinks [261,271]. The soft-to-hard contact at the in-
terface allows for more contact sites to regulate Li-ion transport. The
PEO-covered LLZO electrolyte was integrated into full batteries with
NMC811 or LFP cathodes. In both cases, the specific capacity of PEO-
covered LLZO is significantly higher and maintains greater than 140
mAh g−1 over the course of 100 cycles, while the bare LLZO surface
only lasted 10 – 50 cycles.

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P.P. Paul, B.-R. Chen, S.A. Langevin et al. Energy Storage Materials 45 (2022) 969–1001

Fig. 8. Common issues and solution strategies at the garnet/anode interface. (a) Wetting behavior of molten Li on garnet surface without and with ALD-Al2 O3 coating.
Reproduced with permission from Ref [54]. © 2017 Springer Nature. (b) Schematics of inserting a PEO buffer layer between LLZO and Li interface. Reproduced
with permission from Ref [271] © 2020 Elsevier. (c) Schematics of Li3 PO4 modification layer improves the wettability between Li and garnet. Reproduced with
permission from Ref[273]. © 2020 Royal Society of Chemistry. (d) Wetting behavior of Li-Sn alloy with different wt % ratios on garnet surface. Reproduced with
permission from Ref[277]. © 2017 John Wiley and Sons. (e) Schematics of a mixed conductive layer (MCL) improves the distribution of charges at the interface and
discourages the formation of Li dendrite. Reproduced with permission from Ref[284]. © 2020 Royal Society of Chemistry.

986
P.P. Paul, B.-R. Chen, S.A. Langevin et al.
Surface conditioning of garnets: As garnet materials are exposed to
ambient conditions, Li reacts with moisture and CO2 , and forms a pas-
sivation layer consisted of LiOH and Li2 CO3 . These compounds cause
Li dewetting and increased interfacial resistance. Sharafi et al.’s work
[97] points out that Li has poor adhesion onto Li2 CO3 compared to the
innate LLZO surface. The former gave a contact angle as high as 146°
and is the cause of high interfacial resistance. Surface conditioning of
the garnet surface can remove the passivation layers. Some other meth-
ods aim at converting the passivation layers into interface modification
layers; thus, circumventing an additional coating step.
To remove the passivation layer, several routes can be employed,
such as physical polishing, heat treatments, and chemical treatment
methods. After physical treatments like wet/dry-polishing and heat
treatment, the surface of Li2 CO3 can be removed and the contact angle
between metallic Li and surface-conditioned garnet SSEs significantly
reduces to 95°. The treated interface also reaches a resistance as low
as 2 Ohm cm−2 without an additional buffer layer [97]. The chemical
method of Li2 CO3 removal involves the use of acids. Ta-doped LLZO sur-
face becomes rough due to Li2 CO3 growth after air exposure, and after
30 s immersion in 1 M HCl, the surface becomes smooth and can form
a good contact with Li [272], improving interfacial resistance from 940
to 26 𝑂𝑚𝑒𝑔𝑎cm2 .
Instead of physically removing the passivation layer, another route is
turning the layer into a modification layer that improves the interfacial
contact through chemical treatment. Phosphoric acid (H3 PO4 ) reacts
with Li2 CO3 and LiOH, forming a lithiophilic modification layer con-
sisted of Li3 PO4 on Ta-doped garnet (LLZTO) surface [273] (Fig. 8c). The
modification layer not only facilitates wetting of Li but also improves
critical current density (CCD) before Li dendrite occurs. By using this
strategy, a high CCD of 0.8 mA cm−2 was reached with a Li|LLZTO|Li
symmetric cell and the cell remained stable over 1600 h at a current
density of 0.1 mA cm−2 . Yet another method is adding a layer of liq-
uid gallium (Ga) coating to modify LLZTO garnet surface. The Ga layer
breaks the conformal layer of Li2 CO3 on the garnet surface into smaller,
discontinuous domains [274]. The downsized Li2 CO3 domains and sep-
arating each of the domains, thus avoiding Li2 CO3 to form a continuous
passivation layer to block the Li-ion transport pathways. The treated
LLZTO reached an interfacial resistance of only 5 𝑂𝑚𝑒𝑔𝑎cm2 and the Li
symmetric cell lasted for 9930 h with a current density of 0.2 mA cm−2 .
Alloyed Li anode or SSE: Instead of adjusting the surface and inter-
face properties of the garnet materials. This strategy focuses on tuning
the property of the Li metal anode itself by forming a composite or al-
loy. A successful route is to produce a Li-graphite composite anode. This
mixture, in the form of a paste, gives an intimate contact between the
Li-graphite composite and garnet [275]. The Li-graphite composite was
synthesized by mixing graphite powder and molten Li, in which Li chem-
ically intercalates into graphite, forming LiC6 that is homogeneously
distributed in the composite. The Li-graphite compound (50 wt% C in
the mixture) coats LLZTO pellet within 3 s, in contrast to the complete
dewetting of pure Li. Flexibility is also present in the Li-graphite com-
pound, providing good processability for manufacturing.
A variety of metals or inorganic compounds can be blended along
with Li to improve wetting and viscosity behavior. The metals include
Sn, Al, Ti, Zn, Na, and many more, as summarized in Ref[276]. and the
references within. By forming an alloy, the surface energy and viscosity
of Li alloy can be fine tailored to enhance the wettability on substrates.
For example, the wetting angle of Li-Sn alloy can be tuned by the differ-
ent weight ratios of Sn [277]. As the ratio of Sn increased in the alloy,
the molten alloy starts to wet an Al2 O3 substrate giving rise to a contact
angle lower than 90°. 50 wt% of Sn alloy exhibits a negligible contact
angle and can wet the garnet surface within 10 s (Fig. 8d). A very recent
report also discovered that by adding trace amount (1%) of Si3 N4 into Li,
the surface tension is significantly loosened (30° contact angle) [278].
Following the same strategy, composite Li anode include the addition
of BN nanosheet [279] and graphite-C3 N4 [280].
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Energy Storage Materials 45 (2022) 969–1001
Another route is more similar to the interface buffer layer strategy,
but the key concept is to produce a Li alloy. In 2016, Luo et al. altered the
property of LLZO SSE from lithiophobicity to lithiophilicity by deposit-
ing an ultra-thin coating of Si using plasma-enhanced chemical vapor
deposition [281]. The deposited Si forms a layer of lithiated Si at the
interface, leading to a 7-fold decrease of interfacial resistance from 925
to 127 𝑂𝑚𝑒𝑔𝑎cm2 . Similarly, Fu et al. coated an Al layer through vapor
deposition onto Li7 La2.75 Ca0.25 Zr1.75 Nb0.25 O12 (LLCZN) surface and dis-
covered that molten Li can spread onto the Al-coating surface quickly
and exhibit good wetting [253]. The intimate contact is achieved be-
cause of the formation of a Li-Al alloy at the interface. Elemental map-
ping of the interface shows that Al is diffused into the Li bulk and that
Li fills the pores and grain boundaries of the garnet. Very recently, a
multi-phase Na-K-Li electrode approach is introduced. In this approach,
a small amount of Na-K liquid alloy is added at the interface between
Li and LLZTO surface to not only improve the interface wetting but also
increase the critical current density [282].
Not only Li can be made into an alloyed anode, the alloy strategy
can be reversely applied to the electrolyte itself. In 2018, Tian et al.
blended LLZTO and 2 wt% anti-perovskite Li3 OCl together to form a
composite SSE [283]. This LLZTO-Li3 OCl composite not only exhibits
better ionic conductivity but also wettability with Li metal. Through
SEM observation, no crack is found at the interface between Li metal
and the LLZTO-Li3 OCl. The Li|LLZTO-Li3 OCl|Li symmetric cell can be
cycled for 100 h without short circuiting.
Regulation of Li ion transport and design of electrode architec-
ture: Interface buffer layers not only enhance the physical contact, but
also regulate the flow of Li-ions across the interface. As one of the root
cause of Li dendrite is excess amount of Li accumulating at the gar-
net/Li anode interface, a strategy to address this issue is to add a ”Li
regulation” function onto the buffer layer. The Li regulation function is
usually achieved by the ion and electron conductivity that the interface
layer can offer. For example, a Li3 N/Cu mixed ionic-electronic conduc-
tor (MIEC) layer for both ion and electronic conductance is introduced in
Huo et al. ’s work [284]. In this strategy, The Li3 N/Cu layer is produced
in situ by sputtering a Cu3 N thin film onto LLZTO, followed by reaction
with molten Li at 200 °C, forming a Li3 N matrix with Cu nanoparticles
decorated within. This MIEC layer serves multiple purposes at the in-
terface, as Li3 N possesses high Li-ion conductivity and the Cu particles
spread out the electron distribution, this layer alleviates Li-ion localized
concentration and suppresses the nucleation of Li dendrites (Fig. 8e).
Due to the chemical connection between the MIEC layer and Li metal,
the garnet and MIEC interface shows good wettability. A similar ap-
proach using sputtered SnNx to react with Li and produce Liy Sn and
Li3 N at the interface also serves the same purpose [285].
Another type of design is a porous anode and cathode structure sand-
wiching a thin, dense solid-state layer in between. This tri-layer struc-
ture can be synthesized by using tape casting or freeze casting[286–
288]. The highly porous (70%) layers host Li and cathode materials
within, which also provides mechanical support to the ultra-thin (20
𝜇m) garnet layer. By dividing Li into smaller volumes in the porous
structure, volume change issues and Li penetration issues can be effec-
tively mitigated [288], as well as creating more interface contact area
between the SSE and electrodes. To improve the contact between infil-
tered Li and the garnet porous structures, a coated buffer layer, such as
ZnO or Al2 O3 will greatly enhance the interface contact [54,270].
3D structures can also be implemented into the Li anode and create
an internal framework allowing Li deposition to occur within the frame-
work instead of onto the surface directly. In Chi et al. ’s work [261], a
3D Ni foam structure was infused with Li to form a 3D structure. The 3D
foam serves as a skeleton for Li ion deposition to happen preferably onto
the framework. Recently, Wan et al. [289] reported that the interface
between Ta-doped LLZO and Li metal can be strengthened by a layer
of porous Zn. This 3D-Zn structure is built using magnetron sputtering,
and will react with Li metal anode under 30 °C and form Li-Zn alloy.
The Zn metal backbone and Li-Zn interfacial layer allow a fast and uni-
P.P. Paul, B.-R. Chen, S.A. Langevin et al.
form Li ion transport and significantly reduces the LLZTO/Li interface
impedance from 319.8 to 1.9 𝑂𝑚𝑒𝑔𝑎cm2 .
4. From the laboratory to the market: Scalable manufacturing
and future outlook
The global market of ASSBs is estimated to grow dramatically from
62 million US dollars in 2020 to 483 million by 2027 [290]. With such
a dramatic growth rate, manufacturing capabilities will be the key to
accelerating the production and commercialization of ASSBs. As dis-
cussed in Ref. [291] just published in 2021, there are rich amounts
of laboratory-based research regarding materials discovery and inter-
face design, but knowledge about manufacturing and integrating labo-
ratory discoveries into practical-scale devices are still lacking. Currently,
there are few articles dedicated on reviewing manufacturing strategies
for ASSB materials at the industrial scale [292–296]. Nevertheless, very
little discussion has touched on scaling up the interface stabilization
strategies coupled with ASSB manufacturing [297]. A major challenge
is that the workflow that has been established in a laboratory-scale en-
vironment could differ dramatically from large-scale implementation.
Therefore, not all of the interface strategies are applicable given the
current manufacturing processes.
Additionally, most of the techniques and schemes discussed earlier in
Section 2 are used for characterization of laboratory-scale cells. While
such analyses are invaluable in order to obtain in-depth understand-
ing of the interfacial behavior at fine spatial and temporal resolutions,
scaling-up of cells to the commercially and industrially-relevant length
scales comes with different requirements. Experimental techniques must
be versatile (provide diverse information), easy and inexpensive to ac-
cess, and the data easy to process. Relatively accessible techniques such
as optical microscopy have been used for characterizing particle-level
dynamics using high throughput scans across a matrix of common cath-
ode materials [298]. Using the cell/pack-level electrochemical data to
infer mechanisms is another ideal candidate for such characterizations.
The voltage-current-charge cycling data contains a wealth of informa-
tion, including the rise in interfacial impedance, and contributions of
different loss mechanisms to degradation [299]. To extract this informa-
tion, increasingly sophisticated and multimodal computational methods
are being used in different ways. On one hand, using the cycling data
on one cell, information can be obtained on the progression of different
degradation mechanisms over cycling on that same cell [300,301]. On
the other hand, predictor models can use the data of previously cycled
cells/packs to accurately predict the progression of degradation in other
cells/packs. This information can then be leveraged to change the cy-
cling conditions, in a way that minimizes the progression of degradation
in a cell/pack [302].
Thus, in the following section, we provide our perspective on the
fabrication of ASSBs, through the lens of their commercial appeal and
viability. In Section 4.1, we discuss the processing methods employed
for electrolyte materials. We will elaborate the distinct advantages and
limitations of each methods, especially their applicability for different
classes of ASSBs as well as the ability to be scaled up. Subsequently
in Section 4.2, we discuss the manufacturing strategies for ASSB en-
sembles. The strategies will include scaling-up the interface stabilizing
approaches discussed in the previous sections, as well as the use of ad-
vanced manufacturing technologies such as 3D printing. Subsequently,
we provide a perspective on how the interface stabilization strategies
can lead to fast charging of ASSBs in Section 4.3. Fast charging is a
key aspect towards wider adoption of EVs commercially, by establish-
ing charging protocols that allows EV charging time to be comparable
to refueling in traditional gasoline-powered vehicles. While much of the
present focus on fast charging involves traditional liquid electrolyte–
cells [303], we find that lessons learnt there can be paralleled towards
ASSBs, given that one of the dominating reactions involves efficient
lithium plating and stripping.
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Energy Storage Materials 45 (2022) 969–1001
4.1. Processing methods of SSE materials
To serve their primary purpose of providing consistent conducting
pathways for the movement of ions during cell operation, the conduc-
tivity of the SSE must remain as high as possible. Additionally, since
the SSE itself is not made of active material (unlike the electrodes), the
weight of the SSE should be kept to a minimum, to maximize the en-
ergy density of the entire ASSB. Thus, thin-film SSEs with a high initial
conductivity, and stable conductivity over cycling are desired in ASSBs.
With such thin-film SSEs, the stability of interfaces of the SSE with either
electrode comes into even sharper focus.
The most common SSEs and their associated ionic conductivities as
a function of temperature are illustrated in Fig. 9, compared to a stan-
dard liquid organic electrolyte (shown in dark green line in Fig. 9). The
ionic conductivity of SSEs is in general, orders of magnitude lower than
commercial-based liquid electrolytes. However, we see that some SSEs
(such as Li10 GeP2 S12 , marked in dark red line) can show a compara-
ble conductivity to standard liquid electrolyte at room temperature (27
°C, as indicated by the marker on the upper temperature axis). With
improved processing methods of SSEs to tune the structure, microstruc-
ture and chemistry, comparable conductivities compared to their liquid
counterparts at room temperature can be achieved [124,128]. Addition-
ally, we see that in general, SSEs exhibit more favorable temperature
sensitivity, which is indicated by a lower slope of their conductivity-
temperature curve in Fig. 9. For example, the conductivity of cubic LLZO
(blue line in Fig. 9) changes by ≈ 9.75 × 10−3 S cm−1 over a temperature
range of 120 °C, while for the conventional organic liquid electrolyte
(dark green line in Fig. 9), a slightly greater change in conductivity (≈
10.0 × 10−2 S cm−1 ) is exhibited over a narrower temperature range of
100 °C.
The initial ionic conductivity of SSEs is greatly dictated by the pro-
cessing methods, while the retention of ionic conductivity is intrinsically
tied to the stability of the interfaces in the ASSB. Since the conductiv-
ity and microstructure of the SSE has a major role in determining the
rate and efficacy of Li transport through it, optimizing of processing pa-
rameters is extremely important for ASSBs to achieve realistic loading
rates without a breakdown in their interfacial regions [112]. Casting and
sintering are key aspects for processing ASSBs, as these are critical for
ensuring uniformity of properties across the SSE and are key drivers for
reducing the electrolyte thickness as well as minimizing porosities. Ad-
ditionally, the fabrication pressure is also intricately linked to the ionic
conductivity of the SSE [304]. This section provides an overview on
the various types of processing techniques comm for various SSEs. The
optimization of these processes is necessary to improve interfacial prop-
erties across various classes of SSEs by microstructural optimization of
the SSE to minimize interfacial instabilities [11]. For more detailed in-
sights into the processing techniques and their effect on the microstruc-
ture/crystallinity/structure of SSEs or SSE-active material composites,
we refer the readers to other more comprehensive reviews [125,305].
We briefly discuss four primary processing techniques used for SSEs,
with a couple of examples for each technique, each of which have in-
herent advantages and disadvantages and can furnish various conduc-
tivites given the same SSE chemistry, as well as their adaptability to-
wards large-scale manufacturing.
Melt processing is typically used for glassy SSEs, though it has
also been used for glass-ceramic and crystalline sulfide-based SSEs
[113,306]. The primary advantage of melt processing is the low equip-
ment requirement, rendering ease of preparation for SSEs in bulk. The
main challenge is that melt processing is not the safest or cheapest prepa-
ration method, since the required processing temperatures are high.
Mechanical ball milling is a popular method for fabricating SSEs
[172,173], primarily due to the wide range of applicability to SSEs
across their crystalline state (it has been used even for amorphous SSEs).
The main advantage of mechanical ball milling is that it is a relatively
simple and safe method, compared to other processing techniques. The
primary challenges associated with this technique include it being a very
P.P. Paul, B.-R. Chen, S.A. Langevin et al.
time-consuming process (with implications for large-scale fabrication)
and it is often difficult to obtain uniform stoichiometry/microstructure
throughout the SSE.
Wet chemical methods are another ubiquitously-used processing
technique for fabricating SSEs [155,175]. These methods project low
processing costs, require less processing time, and can be performed us-
ing powder materials with ease. Additionally, it is easier to obtain uni-
form stoichiometry and morphology across the SSE compared to other
techniques; thus, increasing its attractiveness. The primary challenge as-
sociated with these methods is the lower conductivity of the resulting
SSE compared to other methods, which derives from solvent impurities
and remnant amorphous phases lodged into grain boundaries and de-
fects.
Atomic layer deposition (ALD) is yet another popular processing
technique employed for the synthesis of thin-film ASSBs [307]. ALD
allows to achieve Ångstrom-level control [308], making it a popular
deposition technique for fabrication of uniform, thin, conformal films
[309]. Such conformal interfaces minimize non-uniform Li flux at the
anode/SSE interface, which mitigates Li dendrite formation. Addition-
ally, ALD is usually conducted under vacuum, which is particularly use-
ful when considering the high reactivity of Li metal, which is consid-
ered to be the anode material-of-choice for ASSBs [310]. The primary
challenge for this method is governed by scalability limitations when
transitioning from the laboratory-scale to batch manufacturing.
Thus, the successful production SSEs with high ionic conductivity,
favorable chemistries and microstructures, and stable interfaces with
electrodes will be dictated to a large degree by optimization of the pro-
cessing methodology. Subsequently, we discuss the scalability of various
experimental processes from the laboratory scale towards batch manu-
facturing. In general, focus should be on processing techniques that do
not require very high temperatures (they are not the most cost-effective),
as well as those than can produce homogeneous properties across a sin-
gle SSE, and consistent properties across multiple batches of fabricated
SSEs. In this transition, the role of advanced computation methods is
also key in this step towards scalability. Chen et al. demonstrate how
machine learning can be used to guide the processing of thin-film SSEs
[311]. They first deconvolute the effect of different processing parame-
ters on the performance of the ASSB, and subsequently find the optimal
set of processing conditions required to obtain an SSE with desired prop-
erties (high conductivity, uniformity of microstructure and stoichiom-
etry across the SSE, and low variation across different SSEs made via
the same process). Cunha et al. used a similar machine learning based
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Energy Storage Materials 45 (2022) 969–1001
Fig. 9. Ionic conductivity of several commonly used SSEs, in
comparison to their liquid counterparts as a function of tem-
perature in an Arrhenius-type plot.
approach to deconvolute the most important processing parameters that
influence the performance of NMC-type cathodes [312]. Such computa-
tional approaches hold the key to transition from the laboratory scale
towards batch manufacturing of ASSBs, by identifying the steps that are
most important towards achieving uniform and desireable properties in
mass produced ASSBs.
4.2. ASSB manufacturing strategies
To integrate electrode/electrolyte interface stabilization strategies
into the manufacturing of ASSBs, one needs to start from understanding
the ASSB process chains. In most of the lab-scale synthesis, cell assem-
bly steps are usually performed manually. For industrial-scale fabrica-
tion processes, several start-up companies and automobile manufactur-
ers have released patents and prototypes for large-scale ASSB produc-
tion. However, detailed descriptions and discussions about the process
chains have not yet been publicized. In the latest perspective articles,
Hatzell et al. [294] and Schnell et al. [293] point out that there are
two potential designs of process chains: (i) cathode-supported and (ii)
tri-layer design cells.
In the cathode-supported cell, the cathode composite consists of a
mixture of active materials, electrolytes, and binders [313]. This cath-
ode composite can be produced using tape-casting or similar large-scale
casting technologies. Subsequently, an SSE layer is deposited on top of
the cathode layer. The anode will be stitched to the cathode-SSE lami-
nate accordingly in the subsequent assembly steps (Fig. 10a, b). Unlike
the cathode-supported cells, the tri-layer cell is a specific SSE design,
which consists of two highly-porous scaffolds that sandwich a dense
SSE layer. The two porous scaffolds will be infiltrated with cathode
active materials and Li metal to function as the electrodes[286–288].
The porous and dense layers in the tri-layers can be fabricated using
tape-casting or freeze-casting. In the casting process, the layers will be
stacked to reach the desired thickness. Then, the cathode material and
melted Li are infiltrated into the porous layer to form the electrodes
(Fig. 10c, d).
The two process flows are significantly different from what conven-
tionally occurs routinely in the laboratories, where the SSE layers are of-
ten made into individual pellets instead of continuous sheets. Therefore,
interface strategies developed using the lab-scale settings may not be di-
rectly applicable to the two large-scale process flows suggested above.
For example, using sandpaper to remove surface contamination on an
mm-thick SSE pellet is feasible at the laboratory scale. However, the
P.P. Paul, B.-R. Chen, S.A. Langevin et al. Energy Storage Materials 45 (2022) 969–1001

Fig. 10. Schematics of proposed ASSB fabrication chains. (a, c) Fabrication of cathode-supported cells. In this design the SE layer is supported onto a thicker cathode
composite. (b, d) Fabrication of tri-layer cells. In this design molten Li and cathode materials are infiltrated into the porous structure around the thin SE layer. (a, b)
Adapted with the permission from Ref[293]. © 2019 Royal Society of Chemistry. (b, d) Adapted with the permission from Ref[295]. © 2018 Elsevier.

polishing procedures and apparatus would need to be re-designed to manufacturing technology for battery manufacturing, which offers an
fit into a roll-to-roll manufacturing line. Another example is interface alternative strategy to address interface issues in ASSBs.
buffer layer coating using ultra-high vacuum (UHV) thin-film deposi-
tion technologies. When integrating UHV deposition with large-scale
4.2.1. Strategies to create interface coatings and modification layers
processes, the limit of sample size and cost has to be taken into consid-
Vacuum Deposition Methods: Inorganic interface coatings for SSEs
eration. In the following paragraphs, we will discuss: (i) the prospects
can be synthesized by thin-film deposition techniques. These technolo-
of the interface strategies presented in this review for scale up, and (ii)
gies have dominated the semiconductor and solar cell industry for more
processing technologies that better fit into existing ASSB manufactur-
than half a century and are reliable in creating conformal, high quality
ing strategies. A summary of the discussions is provided in Table 2. In
thin-films and coatings for a wide breadth of electronic devices [314].
the same section, we will also include 3D printing, an uprising additive
The deposition methods, depending on the film growth mechanism can

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P.P. Paul, B.-R. Chen, S.A. Langevin et al. Energy Storage Materials 45 (2022) 969–1001

Table 2
Fabrication techniques of the interface strategies at the lab-scale and potential scalability in industry.

SSE/Anode

Interface strategy Lab-scale approaches Large-scale adaptions and scalability Examples

Interface coating and Sputter deposition
buffer layer
Atomic layer deposition (ALD)
Spin-coating and spray-coating.
Flexible composite Wet chemical process to
electrolyte synthesize flexible electrolyte
sheets
Doping of SSE Replace elements in Sulfur-based
SSE with other elements
Alloyed Li or alloyed Blend Li or SSE with elements or
SSEs compounds to improve interfacial
contact
Surface conditioning Manually polishing SE with
sandpapers followed by heat
treatment
Acid treatment (e.g. diluted HCl
and H3 PO4 ) to remove impurities
on SSE surface
Li regulation structures Porous-dense-porous tri-layer
structure using tape-casting or
freeze-casting
3D structure embedded into Li
anode
SSE/Cathode
Sample size limited. Must operate under
high vacuum (1–20 mTorr). Challenging
to scale up or adapt to continuous type of
fabrication
Larger sample size. Capability to deposit
on uneven surfaces
Have been widely adapted to industrial
scale
Conventionally adaptable to large scale
Compatible with current Li anode
processing such as lamination or
melt-processing [295]
Large scale chemical-mechanical
polishing is mature in semiconductor
industry for Si wafers
Acid treatment on surface is a mature
technology in industry
The tri-layer is a promising design for
ASSB process chains [293]
• NASICON-based SSEs:Ge or Bi thin layer coated on
LAGP [200]. ZnO or Al2 O3 on LATP [201].
• Garnet-based SSEs:Cu3 N on LLZTO [284]. SnN
reaction with LiSn and Li3 N [285]
• Garnet-based SSEs: ZnO or Al2 O3 coating onto
porous LLZO garnet [54,270]
• Garnet-based SSEs: PEO spin coating onto garnet
SSEs [261,271]
• NASICON-based SSEs: Cross-linker Li containing
polymer blended with LATP electrolyte [202]
• Sulfur-based SSEs: Substitution doping: replace S
with O [114]. Interstitial doping: doped with In [163].
• Garnet-based SSEs:Li-Sn anode [275] Li-C anode
[277] LLZTO-Li3 OCl SSE [283]
• Garnet-based SSEs:Physical polishing and heat
treatments of LLZO surface [97]
• Garnet-based SSEs: Li2 CO3 removal from garnet
surface [97,272,273]
• Garnet-based SSEs: Garnet 3D porous structure
[286–288]
• Garnet-based SSEs: 3D Ni and Zn network in Li
anode [261,289]

Reducing inter-diffusion
at the interface
Cathode surface coated
with SSE materials
Cathode surface coated
with buffer layer
Reduced sintering temperature or Rapid sintering profiles, Spark plasma
time duration sintering can potentially be scaled up
[330]
Sol-gel or other wet-chemical Common for industry scale adaption
process
ALD Larger sample size. Capability to deposit
on uneven surfaces
• Garnet-based SSEs: LLZO/V2 O5 cathode [258,259]
• Various SSEs: Various combinations of cathode/SSE
pairs[257]
• Garnet-based SSEs: LiCoO2 (or LiMn2 O4 ) coated on
LLZNO [263,264]
• Sulfur-based SSEs: ALD Li-containing thin films,
such as LiNbO3 coated on LiCoO2 as buffer material
[331]

be divided into physical or chemical approaches. Physical vapor depo-
sition (PVD), including sputtering, pulsed laser deposition, and other
evaporation techniques, physically transport the coating materials from
a target to the coating surface [315]. Chemical approaches, such as
chemical vapor deposition (CVD) and atomic layer deposition (ALD),
allow chemical reactions that produce the coating materials onto the
surface. Both physical and chemical approaches have the capability to
handle a rich library of metal and oxide materials for SSE/electrode
interface coatings, such as ZnO [270], Al2 O3 [54], Ge [200], and Bi
layers [201] as SSE interfacial buffer layers. At the laboratory scale,
CVD [316], PVD [315], and pulsed laser deposition [317] are examples
of techniques that are pronounced within a laboratory setting. Never-
theless, vacuum-based deposition technologies are not favorable from a
large-scale processing perspective, as the sample sizes are greatly lim-
ited, plus the cost to maintain the instruments under ultra-high vacuum
conditions.
To apply coatings on electrodes that display complex 3D structures,
ALD can achieve conformal coatings on complex surfaces, such as the
porous electrolyte structure reported in prior studies [270,286]. Com-
pared to CVD and PVD, the advantage of ALD is the applicability on sig-
nificantly larger sample sizes and has been commercialized in the semi-
conductor industry and other thin-film growth industries for decades.
With the thin-film deposition technologies, solid-state electrolyte
materials themselves can also be processed into the form of thin films,
known as ”thin-film ASSBs” and has reached some level of commercial-
ization [307,315].
Soft materials and wet chemical coating methods: For soft and
organic materials, interface buffer layers, such as PEO [261,271], the
relevant methods used are drop casting, doctor blading, spin coating,
and spray coating. The coating materials are processed in the form of a
solution or sol-gel, distributing evenly as a thin film onto a flat sample
surface. These methods have been established in large-scale processing
of polymer- and perovskite-based photovoltaic devices [318,319], and
are frequently used to create artificial interfaces to protect Li metal an-
odes in lab-scale [320].
Soft-material processing approaches can be extended to the fabrica-
tion of composite organic-inorganic SSE materials as well. In this ap-
proach, fibers of ceramic SSEs can be embedded into a polymer matrix.
In the work by Zhao et al. [321] and Fu et al. [322], precursors of garnet
(salts of Li, La, Zr, and Al) and polyninyl pyrrolidone (PVP) are blended
using the sol-gel process. The sol-gel is directed through an electrospin-
ning process, in which nanofibers of ceramic precursor will form, which
is then followed by calcination.
Wet chemical methods are another popular approach to make labo-
ratory scale coatings. While they are inexpensive and simple, the thick-
ness, morphology and homogeneity of the coating thickness can be dif-
ficult to control. Sol-gel approaches [186] and slurry-based approaches
[323–325] are two popular wet chemical coating methods. Tradition-
ally, scaling up of electrodes with coatings is challenging, with dry pre-
mixing of the components. Wet slurry-based methods have now been
successfully shown to be more conducive towards scaling up, by also
incorporating polymer bindings to stabilize the system.
Li and Li-alloy anodes: Currently, Li metal anodes are fabricated
using the following methods: foil processing, melt/infiltration, elec-
trochemical plating, and vapor deposition [295]. Foil processing and
infiltration of Li are commonly used in laboratory-scale settings. Foil

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P.P. Paul, B.-R. Chen, S.A. Langevin et al.
processing directly laminates Li foil onto the surface of a SSE. In
melt/infiltration processes, Li is first melted at 180 – 200 °C and then
the melt infiltrates onto the SSE surface.
To further improve the interfacial contact between Li anode and SSE,
specifically for garnet-based ones, alloyed Li anodes are introduced, of-
fering desirable interfacial stabilization. Alloyed Li can be tuned in ad-
hesive properties by blended Li with modifiers such as metals (Si, Sn,
Al, Ti) [276,277,281,326], or inorganic compounds (graphite [275], g-
C3 N4 [280], Si3 N4 [278], BN nanosheets [279]). To scale up the pro-
duction of alloyed Li anodes, the approaches established for Li melt
or infiltration can be readily adapted and can be further expanded to
industry-relevant scale production by using a suitable apparatus.
Rapid sintering techniques: Cathode composites comprise of cath-
ode active materials (AM), SSE materials, and binders. Compression and
sintering reduce porosity and enhance contact between the AM and SSE
in the cathode as well as the cathode/SSE interface. A sintering step will
be required to achieve this compaction. However, cathode/SSE interface
issues, such as interdiffusion and interface layer growth tend to occur
[22] and reduce the performance of the battery. On the other hand, a
sintering time from a few of hours to couple of days over 1000 °C will be
conventionally required to densify SSE materials in the processing. This
prolonged process will cause undesirable side reactions, such as grain
coarsening, materials decomposition, and Li evaporation in the SSE ma-
terials that will deteriorate the electrochemical properties. To cope with
side reactions during sintering, a tunable and rapid temperature profile
is required to precisely control the temperature and time, thus achieving
desirable microstructures [256].
Recently, rapid thermal annealing methods are introduced for the
fabrication of cathode/SSE interface and the SSE materials. Ultra-high
heating profiles can be realized by sandwiching ceramic pellets between
Joule-heating carbon strips [256,327,328] that bring the temperature as
high as 3000 °C in approximately 10 s . Spark plasma sintering (SPS),
or field-assisted sintering [257,329], is another emerging method that
allows a high temperature ramp rate of several hundred °C per second.
SPS has been successfully utilized in the fabrication of a wide breath of
SSE materials as well as the cathode/SSE stacks [257], effectively reduc-
ing the sintering time from hours to seconds. As the high temperature
holding time is minimized, the side effects due to prolonged sintering
can be effectively reduced. Although traditionally considered a lab-scale
and cost-ineffective instrument, in recent years, industrial-scale relevant
SPS systems that allow automatic sample handling are being designed
[330], increasing the potential for SPS to serve as a practical manufac-
turing tool. With rapid sintering technologies, a huge amount of time
and energy during sintering steps can potentially be saved.
4.2.2. 3D printing and additive manufacturing technologies
3D printing has revolutionized the fabrication of devices in recent
times. Unparalleled control of the structure, microstructure, as well as
the flexibility of use across a wide gamut of materials systems have been
the primary drivers behind this boom in 3D printing technologies. 3D
printing has also started to receive increasing attention in the energy
storage field [332–334]. Particularly in the context of ASSBs, the ability
to tune the structure and microstructure can be exploited to optimize the
conductivity, ability to accommodate interfacial stresses, and maintain
intimate interfacial contact over cycling. Extrusion-based 3D printing
is the most commonly used class of 3D printing employed in battery
fabrication [335]. Apart from material extrusion-based methods [336],
lithography-based [337], selective laser melting [338], photopolymer-
ization, sheet lamination, and directed energy deposition are some of the
other classes of 3D printing for fabricating electrode composites [339],
conductive binders for electrodes [340], and SSEs [341]. Additionally,
3D printing naturally lends itself towards cost-effective scale-up, from
laboratory scale test-beds to industrial manufacturing.
In particular, the flexibility of architectures afforded by 3D printing
allow for the construction of flexible interfaces, that better accommo-
date the interfacial stresses during charge/discharge of the ASSB [342].
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Energy Storage Materials 45 (2022) 969–1001
Saconne et al. recently demonstrated a novel 3D printing method ‘emul-
sion stereolithography’ for fabricating Li2 S-C composite cathodes for Li-S
batteries [149]. This method provides a spatial resolution of 50μm for
printed features, compared to the standard 150-200μm spatial resolu-
tion for standard 3D printing methods. This superior spatial resolution
allows for building more flexible structures which can better accommo-
date the volume changes of the sulfur cathode, resulting in enhanced
capacity retention over cycling.
A distinct advantage of 3D printing of SSE fabrication is the ability
to directly print/write the SSE onto the surface of the SSE/SSE-cathode
composite; thus, achieving intimate interfacial contact. Additionally, the
control over structure of the 3D printed SSE can offset the challenge of
long diffusion paths for Li+ through the SSE fabricated through tradi-
tional processing techniques. Zekoll et al. demonstrated the fabrication
of 3D structures of LAGP SSE with 3D printing [204]. These 3D porous
structures showed superior ability to accommodate compressive loads.
Delannoy et al. employed ink-jet printing to fabricate a silica-based
SSE, which was written onto an LFP-based porous composite cathode,
showing good capacity retention (≈300x10−6 Ah cm−2 ) up to 100 cycles
[343]. McOwen et al. printed garnet type LLZO-binder SSE composite
onto an LLZO substrate, which demonstrated the clear link between the
conformal interfacial contact between Li metal and the printed LLZO
SSE, resulting in a significant decrease in the cell impedance over cy-
cling [344]. Blake et al. employed direct ink writing to print polymer-
ceramic composite SSEs [345]. They demonstrated remarkable control
over the porosity of the printed composite SSE through manipulation
of additives used in the slurry for printing. These composite electrodes
exhibited capacity retention (over 100 cycles) comparable to standard
polymer-based electrolytes, and high power capability (up to 5C charg-
ing), while showing higher resilience over a wider temperature range.
Finally, conductive additives, such as carbons employed in the elec-
trodes can be optimally mixed to create composite electrodes that have
enhanced conductivities, as well as minimal side reactions at the in-
terface due to deleterious side reactions [346]. In the future, advanc-
ing beyond 3D printing individual battery components, whether they
are composite electrodes, binders or SSEs, towards 3D printing of en-
tire batteries holds a huge potential to enhanced interfacial stability in
ASSBs, particularly through printing conformal interfaces and flexible
architectures with optimized chemistries [347,348].
4.3. Commercial viability: Fast charging of ASSBs
For liquid electrolyte–based LIBs, the issue of extreme fast charg-
ing (XFC), meaning that 80% charge can be achieved under 15 min, has
been extensively discussed [349–351]. XFC is considered to be a particu-
larly immediate focal point to increase the commercial appeal of EVs by
reducing recharging time, allowing for the charge time of EVs to be com-
parable to refueling of traditional gasoline-powered vehicles. Compared
to the conventional liquid electrolyte Li-ion batteries, ASSBs carries sev-
eral advantages for realizing XFC. However, so far XFC in ASSBs has not
been explored as much, due to the relatively poor capacity retention
compared to their liquid counterparts [352]. Following our discussion
on the scaling up of manufacturing of ASSBs, we briefly discuss the im-
plications of such wider manufacturing, such as their implementation
in EVs, at XFC rates. The key towards realizing XFC for ASSBs is mini-
mizing the previously discussed interfacial instabilities (viz. mechanical,
chemical and electrochemical) to enable higher current densities across
the interfaces at such fast charging rates [353].
Advantages of ASSBs in XFC: Recent research on XFC in LIBs with
liquid electrolyte has shown that the degradation is highly heteroge-
neous across the cell [354,355]. Such heterogeneity is due to heteroge-
neous reaction rates across the cell, caused by Li polarization gradients
either across the anode or the liquid electrolyte, resulting in parasitic
Li plating [356]. This problem of polarization gradients in theory is re-
duced in ASSBs, which eliminate such gradients across a SSE, as well
as having Li itself as the anode as opposed to graphite, that is used in
P.P. Paul, B.-R. Chen, S.A. Langevin et al.
traditional LIBs. Moreover, ASSBs are intrinsically more thermally sta-
ble than organic liquid electrolytes (see Section 4.1 for electrochemical
sensitivity with temperature of SSEs compared to their liquid counter-
parts), which becomes important due to the large thermal gradients in-
duced during XFC cycling [357]. This enhanced thermal stability also
reduces deleterious side reactions which impact calendar life of cells
compared to liquid electrolyte-based cells, as well as reducing the need
for large thermal management to cool down after a fast charge [358].
Additionally, the risk of catastrophic thermal runway during XFC charg-
ing would be reduced due to the higher thermal stability. Finally, in
traditional LIBs, SEI species form continuously and are exposed to the
liquid electrolyte, which results in continuous depletion of the active
inventory of Li in the cell through deleterious side reactions [359,360].
In contrast, ASSBs can mitigate such continuous depletion of Li due to
not having a liquid electrolyte flowing to exposed regions of the elec-
trodes over cycling. Kazyak et al. exploited this advantage of ASSBs in a
unique manner, by incorporating a thin SSE film in between a graphite
anode and liquid electrolyte, showing enhanced fast charging capabili-
ties [361]. Overall, ASSBs have several inherent advantages over liquid
electrolytes for XFC charging.
Challenges at the anode/SSE interface in XFC of ASSBs: Despite
the intrinsic advantages of ASSBs compared to conventional Li-ion bat-
teries, several challenges remain before their implementation in cells
that charge at XFC rates. The formation of parasitic Li dendrites at the
anode/SSE interface that penetrate into the SSE via grain boundaries
increases with increased current density [44,67]. The formation of Li
dendrites reduces the maximum current density, or the “critical cur-
rent density (CCD)” that can be applied across the cell, which limits the
charging rate. The formation of Li dendrites is preceded by the formation
of voids at the anode/SSE interface. For XFC cycling of ASSBs, the CCD
during plating (charging of the cell) determines the current rate above
which voids form, therefore, leading to growth of Li dendrites into the
SSE [362]. This CCD above which Li forms filaments is a function of both
external factors such as the cell stack pressure, temperature, and charg-
ing protocols and internal factors such as the interfacial stability in the
ASSB. Spencer et al. showed the dependence of the formation of voids
at the Li anode/SSE interface (and therefore dendrite growth) on the
cycling temperature and pressure [110]. Higher temperatures showed a
marked reduction in the propensity to form voids, and subsequently Li
dendrites into the SSE.
For optimizing the external factors, inspiration can also be taken
from work done on XFC for LIBs with liquid electrolytes. For example,
Song et al. recently showed how manipulation of the electrical and ther-
mal controls during cycling can result in improved XFC performance
of graphite/NMC-based LIBs with a standard organic electrolyte [363].
Data science and machine learning approaches can also play important
roles in realizing XFC [364]. Attia et al. used a data-driven approach
to search for the optimal charging protocol and predict cell lifetime,
maximizing the performance of liquid electrolyte–based LIBs at XFC
rates[302]. They found superior capacity retention by using such op-
timized protocols than conventionally used XFC protocols, which aim
to minimize current rates at higher SOCs during charging. Conversely,
interfacial improvements should be focused on maintaining a uniform
contact between the Li metal anode and the SSE over rapid charging
and discharging, to minimize the formation of such parasitic Li den-
drites, which greatly compromise the capacity retention and safety of
the ASSB over cycling. For example, Parejiya et al. used a novel method
to improve interfacial contact by using short, high voltage pulses to in-
duce localized Joule heating; in turn, resulting in improved Li flow and
reduced void formation at the anode/SSE interface [365].
Challenges at the cathode/SSE interface in XFC of ASSBs: On the
cathode side, the loss of active material with cycling due to physical
degradation (leading to local delamination in some cases) and poor con-
tact at the cathode/SSE interface are critical bottlenecks to achieving
XFC. The severe volume changes of the cathode over continuous lithia-
tion and delithiation is made severe at faster charging rates [352]. Cre-
993
Energy Storage Materials 45 (2022) 969–1001
ating cathodes with a stable 3D structure [366] via techniques such as
3D printing [149] that can intrinsically withstand the rapid stresses in-
duced by the ’breathing effect’ can help mitigate some of the instabilities
at the cathode/SSE interface during XFC. For example, composite cath-
odes created with a polymer-type binder material can help alleviate the
stress that results from the breathing effect [367], apart from reducing
degradative chemical reactions at the cathode/SSE interface. However,
Davis et al. recently found that composite electrodes are not necessarily
optimally conducive towards high rate cycling [368]. On one hand, they
observed a drop in electrostatic potential across the SSE portion of the
composite electrode, which exacerbated heterogeneity across the depth
of the composite. On the other hand, increasing the active material to
SSE ratio in the composite electrode resulted in a drop in the overall con-
ductivity of the composite. These competing factors therefore limit the
accessibility to higher charging rates, showing that interfacial strategies
can face unique challenges at XFC rates.
In summary, apart from the considerations of batch manufacturing,
charging the ASSBs at higher rates brings an additional set of electro-
chemo-mechanical instabilities at the interfaces that are not apparent at
slower kinetics. Minimizing these instabilities in a commercially viable
manner necessitates the use of advanced computational methods such as
machine learning with optimized processing methods, to optimize oper-
ating conditions towards stable cycling. Through a combination of inter-
facial tailoring, structural modifications, and optimization of operating
cycling parameters such as temperature, stack pressure and charging
protocols, the aim should be to maintain conformal contact at the an-
ode/SSE and cathode/SSE interfaces, while minimizing the deleterious
stresses induced due to the breathing effect. Such improvements will in
turn unlock higher CCDs without compromising capacity retention and
safety.
5. Future outlook
All solid-state batteries hold great promise as a next-generation,
energy-dense, safe energy storage solution. While the prospects of high
specific energy (> 500 Wh kg−1 ) and energy densities (> 1500 Wh
L−1 ) are promising, the success of this technology is contingent upon
addressing critical challenges in materials chemistry, processing, and
scalability. Interfacial challenges for these types of electrolytes arise
from chemical, electrochemical, and mechanical instabilities. At the an-
ode/SSE interface, the key issue to address is deleterious reactions of the
electrolyte that can form undesirable decomposition products, volume
change during charge/discharge that leads to void formation, and the
propensity for lithium migration through grain boundaries. Similarly,
at the cathode/SSE interface, the primary concerns involve mechani-
cal degradation and electrochemical instability when cathode materi-
als decompose at the interface and volume changes are induced during
charge/discharge. This review article outlines the underlying challenges
and strategies for addressing interfacial issues at the electrode/SSE inter-
faces for three of the most studied electrolyte types: sulfides, NASICON,
and garnets.
With research and development efforts underway to understand the
complex processes of solid/solid interfaces, there is much to look for-
ward to in the development of ASSBs. On the materials chemistry side,
the implementation of novel interfacial stabilization chemistries that
are commercially viable at a larger scale and not just at a laboratory
scale is a priority. Computational methods can accelerate the discov-
ery of novel chemistries to chemically and electrochemically stabilize
interfaces [86,106]. Data science–based approaches can further bridge
the gap between experiments and cell life predictions [302]. Benayad
et al. review the importance of high throughput screening of materials
for the development of new battery chemistries, while high throughput
experiments hold the key to manufacturing reproducible batteries on
a larger scale [369]. In this regard, the use of high throughput virtual
screening, which leverages the ability of machine learning/artificial in-
telligence to make predictions and comfortably handle large data sets
P.P. Paul, B.-R. Chen, S.A. Langevin et al.
holds the key for the battery improvements to match our ever-increasing
demands for them. However, such approaches have to be complemented
with market analyses (from the processing of cell components, to the
assembly of cells and operation of the cell pack) to understand their
commercial viability [370,371]. Mechanically, the synergy between op-
erating conditions such as temperature and pressure, especially in large
battery packs and nanoscale interfaces at the individual cell level need to
be integrated, to realize wider operating temperatures and faster charg-
ing rates [362].
After an extensive review of the state-of-art strategies for stabilizing
interfaces, we summarize below a list of focal points that would benefit
the research efforts in ASSBs with the following statements:
• A critical cog in the acceleration of our understanding of chemical,
electrochemical and mechanical instabilities at the anode/ and cath-
ode/SSE interfaces requires a combination of experimental, numer-
ical, and modeling techniques: multimodal characterization. With a
myriad of tools available to us today, investigating reaction mecha-
nisms at interfaces across length and time scales will lead to under-
standing of degradation mechanisms, and in turn the discovery of
new strategies for stabilizing the solid/solid interface.
• For the three widely-studied classes of SSEs (sulfide-based,
NASICON-type, and garnet-based), several strategies for enhancing
interfacial stability for each electrolyte class are summarized. Paral-
lels can be made where a combination of predominately inorganic
buffer layers and organic-inorganic composites are being investi-
gated across all SSEs.
• The development of improved ASSBs begin at the initial processing
stage of bulk SSEs, where optimizing processing conditions lead to
improved ionic conductivity, desired microstructures, and minimizes
contaminants. All of these properties in turn govern the stability at
the SSE/electrode interface.
• The incorporation of interface coatings and modification layers need
to be geared towards large-scale implementation, where laboratory-
scale demonstrations that are amenable to current Li-ion battery or
ASSB manufacturing are focused on.
• Recent efforts in leveraging 3D printing as a means to scale up ASSB
manufacturing shows great promise in creating conformal interfaces
that are more inherently stable. 3D printing an entire cell will be the
next challenge, for producing more complex multi-layer stack cells
with flexible structures and higher energy densities.
• To further their commercial appeal, the next focal point will be lever-
aging ASSBs’ inherent advantages over traditional liquid electrolytes
to reduce recharging times and access extreme fast charging rates
for EVs. Improving interfacial stability, coupled with real-time opti-
mization of operating conditions, such as temperature, pressure and
cycling protocols will become the underpinning studies required for
realizing ASSBs that operate under XFC conditions.
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.
Acknowledgements
P.P.P and J.N.W. acknowledge funding from the Vehicle Technolo-
gies Office of the U.S. Department of Energy’s Office of Energy Efficiency
and Renewable Energy under the guidance of the Advanced Battery Cell
Research Program (eXtreme Fast Charge Cell Evaluation of Lithium-ion
Batteries, XCEL). The manuscript has been partly authored by SLAC Na-
tional Accelerator Laboratory, operated by Stanford University under
Contract No. DE-AC02-76SF00515. B.R.C. and E.J.D. acknowledge sup-
port from the Idaho National Laboratory and Battelle Energy Alliance
under contract DE-AC07-05ID14517. B.R.C. acknowledge the support
994
Energy Storage Materials 45 (2022) 969–1001
by the Department of Energy, Laboratory Directed Research and Devel-
opment (LDRD) program under DOE Idaho Operations Office Contract
DE-AC07-05ID14517. J.S.K and S.A.L. acknowledge support from the
Johns Hopkins University Applied Physics Laboratory (Janney Energize
Award). J.S.K. and S.A.L. also thank Ben Smith for assistance with the
graphics.
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