Interfaces in Solid-State Lithium Batteries

Please cite this article in press as: Xu et al., Interfaces in Solid-State Lithium Batteries, Joule (2018), https://doi.org/10.1016/j.joule.2018.07.
009
Review
Interfaces in Solid-State
Lithium Batteries
Lin Xu,1,6 Shun Tang,2,6 Yu Cheng,1,6 Kangyan Wang,3,6 Jiyuan Liang,2 Cui Liu,2 Yuan-Cheng Cao,4,*
Feng Wei,5 and Liqiang Mai1,*
The influence of interfaces represents a critical factor affecting the use of solid- Context & Scale
state batteries (SSBs) in a wide range of practical industrial applications. How- Lithium-ion batteries (LIBs) are the
ever, our current understanding of this key issue remains somewhat limited. promising power sources for
Therefore, this review presents the mechanisms and advanced characterization portable electronics, electric
techniques associated with interfaces in SSBs. First, we compare liquid- and vehicles, and smart grids. The
solid-state batteries and emphasize the challenges in solid-solid interfaces. Sec- recent LIBs with organic liquid
ond, we discuss different aspects of interfaces including interphase formation, electrolytes still suffer from safety
cathode-electrolyte interface, anode-electrolyte interface, and interparticle issues and insufficient lifetime.
interface, which contain a detailed description of the formation mechanisms Solid-state batteries (SSBs) are
and current research. Third, the characterization strategies for effective interfa- expected to address these issues.
cial observation and analysis are summarized and discussed. In particular, two In principle, the nonflammable
unique characterization techniques, vibrational sum-frequency generation solid electrolytes could prevent
spectroscopy and on-chip single-nanowire battery characterization, are high- battery combustion and
lighted. Lastly, we summarize the scientific issues associated with solid-solid explosion, and only Li ions are
interfaces and provide our perspectives to better understand the fundamental mobile in solid electrolytes, which
issues and improve the performance of SSBs. could suppress side reactions.
Some solid electrolytes, such as
Introduction sulfides, have sufficiently high
As a key element in today’s information-rich world and the devices that power it, ionic conductivity, which is
rechargeable lithium-ion batteries (LIBs) are considered to be essential devices for comparable to that of with organic
a cleaner and more sustainable distributed energy supply.1 However, safety issues liquid electrolytes. Thus, solid-
and limited energy density are two of the major problems of current LIBs that feature solid interfaces appear to be the
organic liquid electrolytes. In contrast, the development of Li-air/Li anodes,2–6 Li-S key to push SSBs toward practical
anodes,2,4,7,8 and Si anodes2,9,10 show promise for increasing energy density, applications. In this review, we
providing that certain challenges can be overcome. For example, sharp, sticky Li start by introducing the
dendrites that grow on the Li-metal anode during cycling, which can then penetrate challenges in solid-solid interfaces
through the separator between two electrodes, will induce sudden failure of the bat- versus liquid-solid interfaces. We
tery and the unwanted release of heat, the result of which is an increased fire hazard then discuss different interfaces in
due to short-circuiting.6,11 For an Li-S battery, in addition to safety concerns associ- SSBs, including cathode-
ated with dendrites, the polysulfides that form during cycling can dissolve into the electrolyte interface, anode-
liquid electrolytes, thus rendering the cell life too short for most applications without electrolyte interface, and
specified electrode modifications.12–14 In addition, the insoluble Li2S and/or Li2S2 interparticle interface. Lastly, we
products that cover the anode add extra internal resistance to the battery. With present the advanced
respect to an Si anode, the highest theoretical charge capacity of 4,200 mAh g 1, characterization techniques to
which is due to multistep solid alloy reactions, is very impressive and has attracted help deepen understanding of the
a great deal of interest.15 However, the huge volumetric change (400%) upon lith- composition and structure
iation and delithiation limits its application due to structural pulverization and a evolution at the interfaces during
limited cycle life.9 Considering both safety and performance, and the urgent chal- battery cycling. The on-chip
lenges of meeting 21st-century power demands, the most promising direction for single-nanowire electrochemical
battery development is to use solid electrolytes, and preferably all solid-state batte- devices developed by our group
ries (SSBs).3
Joule 2, 1–25, October 17, 2018 ª 2018 Elsevier Inc. 1

Please cite this article in press as: Xu et al., Interfaces in Solid-State Lithium Batteries, Joule (2018), https://doi.org/10.1016/j.joule.2018.07.009
A solid-state system yields many intriguing advantages.16 First, a solid-state system

alleviates safety concerns by abandoning the use of flammable organic liquid elec- are highlighted as a unique
trolytes. Second, it can potentially prevent short-circuits by blocking Li dendrites on platform for in situ
one side. Third, some SSBs can be bent, punched, or even pierced without risking characterization.
unwanted safety hazards. Fourth, the stable solid electrolyte potentially facilitates
a wider electrochemical window, thereby enabling the use of certain cathode mate- We suggest and emphasize some
rials with higher voltage capability. It is worth noting that a recent study shows the future directions for SSBs. First,
electrochemical stability window of most inorganic solid electrolytes to be overesti- different in situ or operando
mated by the traditional Li/solid electrolyte/inert metal cell test (see detailed discus- characterization techniques
sion in the subsection ‘‘Electrochemical Characterization’’).17 All told, it is expected should be developed and
that SSBs will exhibit excellent cycle life, high reversibility, wider working tempera- combined to track the real-time
tures, and other highly advantageous features. However, four specific standards composition and structure
must be met if the use of solid electrolytes is to be expanded: (1) high ionic conduc- changes at the interfaces in SSBs.
tivity, sLi+ > 10 4 S cm 1; (2) sufficient strength and minimum defects to inhibit Li Second, in addition to metal ions,
dendrite penetration18–20; (3) affordable raw materials and facile fabrication metal-air and metal-sulfur
methods; and (4) low activation energy for Li+ diffusion. systems with much higher energy
density should also receive
In general, solid electrolytes can be divided into two major groups: organic solid sufficient attention for SSBs.
polymers and inorganic solids, including oxides and sulfides, etc.21 At present, a Lastly, a unique advantage of
number of solid electrolytes with superb ionic conductivity have shown great prom- SSBs over liquid-electrolyte
ise to replace current commercial organic electrolyte batteries, especially for Li10- batteries is that SSBs could be
GeP2S12 and Li2S-P2S5 with their high ionic conductivities of 1.2 3 10 2 S cm 1 flexible, stretchable, and shrunk
and 1.7 3 10 2 S cm 1, respectively. Their conductivity is comparable with that of on a chip. Thus, SSBs are
organic liquid electrolyte (usually on the order of 10 2 S cm 1, 25 C), indicating promising for integration with
that solid electrolyte materials show great promise for next-generation batte- microelectronic circuits to
ries.22,23 However, a key scientific issue that will hinder the practical application of fabricate self-powered wearable
SSBs concerns solid-solid interfaces. or implantable micro-/nanoscale
devices.
In this review, we assess solid-state interfaces with respect to a range of important
factors: interphase formation, interface between cathode and inorganic electrolyte,
interface between anode and inorganic electrolyte, interface between polymer elec-
trolyte and Li metal, and interface of interparticles. This review also summarizes ex-
isting characterization strategies, including microscopy observation, chemical
composition analysis, and electrochemical characterization. Finally, we introduce
several advanced methods that are used to comprehensively study interfaces in 1State Key Laboratory of Advanced Technology
SSBs. for Materials Synthesis and Processing,
International School of Materials Science and
Engineering, Wuhan University of Technology,
Challenges in Solid-Solid Interfaces versus Liquid-Solid Interfaces Wuhan 430070, China
For a liquid-electrolyte system, wetting enables the liquid electrolyte to be fully in- 2Key Laboratory of Optoelectronic Chemical
filtrated in the electrode, thereby facilitating simultaneous Li+ intercalation/conver- Materials and Devices, Ministry of Education,
School of Chemical and Environmental
sion/alloying reactions for all active materials in the electrode, assuming that the Engineering, Jianghan University, Wuhan 430056,
time gap for electron transport can be overcome. Charge carriers in the electrolyte China
reduce with the consumption of Li+ during solid-electrolyte interphase (SEI) forma- 3Department of Chemical Engineering, University
of Melbourne, Melbourne, VIC 3010, Australia
tion, further increasing the resistance for ion transfer and therefore hindering the
4State Key Laboratory of Advanced
ability for high-rate charging/discharging. Although electrolyte decomposition
Electromagnetic Engineering and Technology,
can be partially recovered through the use of a stable SEI and additional electrolytes School of Electrical and Electronic Engineering,
in the battery wetting the electrode, this phenomenon is less obvious for anodes Huazhong University of Science and Technology,
Wuhan 430074, China
such as Li4Ti5O12 (LTO, ca. 1.5 V versus Li+/Li), Li-In alloy (0.6 V versus Li+/Li), and 5Institutefor Interdisciplinary Research, Jianghan
others.24 University, Wuhan 430056, China
6These authors contributed equally
Briefly there are four key challenges in SSBs versus liquid batteries. First, the ionic *Correspondence: [email protected] (Y.-C.C.),
conductivity of most solid-state electrolytes is lower than that of liquid electrolytes. [email protected] (L.M.)
Although some sulfide electrolytes can achieve high ionic conductivity, a number https://doi.org/10.1016/j.joule.2018.07.009
2 Joule 2, 1–25, October 17, 2018

Figure 1. Schematic of
Different Interfaces in Solid-
State Batteries
For the purpose of highlighting
the interfaces, the size of
particles and grain boundaries
in this schematic are not
proportional. The schematic
only presents the general
structures of inorganic solid-
electrolyte batteries, and some
specific components—notably
conductive additives and
polymer electrolytes in other
batteries—are not shown.
of instability issues at the interface must be addressed. Second, in contrast to

liquid electrolytes, the interfacial compatibility between solid electrolytes and
electrodes is usually poor and needs significant improvement for application in
SSBs. The interfaces in an inorganic solid-electrolyte battery can feature several
basic structures: the cathode-electrolyte interface, the anode-electrolyte interface,
and the interparticle interface, as illustrated in Figure 1. In addition to the ionic
conductivity of the electrolyte, ionic transport of Li+ at the interfaces also deter-
mines the overall ionic conductance that ultimately defines the rate performance
of these batteries. This relationship explains why overall electrochemical imped-
ance can be high, even in cases when the ionic conductivity of a solid electrolyte
is excellent, as well as why achieving high Li+ conductance in the solid state com-
parable with existing liquid electrolytes is a challenging task. In industrial settings,
for example, the best electrolyte-electrode interaction is achieved by enabling the
wetting of the electrodes with electrolytes for a week or even two (and even in a
laboratory setting, a day’s wetting is required). Adopting a solid bulk that has liter-
ally no self-diffusion—in other words, a ‘‘wetting effect’’—can lead to severe inter-
face impedance. In addition to the conventionally conceived electrolyte-electrode
interface, an electrode’s interparticle interface also plays a prominent role in a
composite electrode material. For example, the relatively low electronic and ionic
conductivities of cathodes that occur as a result of poor contact at the phase-phase
or particle-particle interface could limit efforts to improve the power density of
SSBs.25 Third, preventing Li dendrite penetration is still challenging in SSBs,
even for ceramic electrolytes with high mechanical strength. Fourth, despite
growing research efforts to elucidate the formation of interphases between solid
electrolytes and electrodes, we still do not have a complete understanding of
the microstructure, dynamic behavior, and chemical reactivity of SEI during
cycling. Thus, advanced characterization techniques that provide in situ and real-
time information about batteries in a working environment are essential for the
further development of SSBs.
Interfaces in Solid-State Batteries

We define the term ‘‘interface’’ as a combination of interphase formation, contact
condition, energy status, and defects. Physical and chemical processes that take
place at an interface during cycling should be taken into consideration. These essen-
tial processes include SEI formation, dendrite growth, Li-depleted space-charge
layer, and interfacial adhesion variation due to structural and volume change, among
Joule 2, 1–25, October 17, 2018 3

Figure 2. Open-Circuit Energy Diagrams of Different Battery Systems

(A) Overall illustration of a battery with a liquid electrolyte. m a and m c refer to energy levels of anode and cathode materials, respectively. LUMO and
HOMO represent the lowest unoccupied molecular orbital and highest occupied molecular orbital of liquid electrolyte, respectively. C.B. refers to the
conducting band of solid electrolyte and V.B. indicates the valance band. V oc refers to the open-circuit voltage of the battery. Reprinted from
Goodenough and Kim, 26 with permission. Copyright 2009, American Chemical Society.
(B) Stable energy window for liquid electrolyte.
(C) Stable energy window for solid electrolyte.
(B) and (C) are reprinted from Goodenough and Park,1 with permission. Copyright 2013, American Chemical Society.
others. This section features a detailed discussion of interphase formation and

different categories of interfaces and their particular characteristics.
Interphase Formation
Understanding the interfacial reaction is important, as it provides critical information
on the interfacial products (interphase) and their various effects on the stability and
electronic performance of a SSB. The chemical stability of an electrolyte can be pre-
dicted using the energy diagram shown in Figure 2. The ‘‘window’’ for both liquid
and solid electrolytes can be determined by the energy separation Eg between
the lowest unoccupied molecular orbital (LUMO) or conducting band (CB) and the
highest occupied molecular orbital (HOMO) or valence band (VB)1,26 of the electro-
lyte material, which is thermodynamically stable when the chemical potential (ma for
anode and mc for cathode) of the electrode materials is within the LUMO-HOMO
range. In other words, the interface is not stable if ma > LUMO (or CB) or mc <
HOMO (or VB), unless an SEI forms at the interface as the passivation layer. The for-
mation of SEI has been widely studied in liquid-electrolyte batteries, and the
concept can potentially be extended to SSBs upon careful comparison of these
two very different battery systems.27–29
The interfacial reaction and the interphase products play important roles in reaching
the full potential of SSBs, as Li+ ions diffuse from the bulk electrolyte mostly via
Schottky vacancy and grain boundaries.30,31 The structure, contact condition,32
and even the electronegativity33 of the interphase all affect the resulting energy
4 Joule 2, 1–25, October 17, 2018

delivery of SSBs. Zhu et al. carried out theoretical predictions of the reduction/oxida-
tion potential and the phase equilibria of many conventional solid electrolytes.34,35
Importantly, their theoretical results agree with a series of recent experiments. For
example, X-ray diffraction (XRD) was used to characterize Li2S at the Li/LGPS inter-
face (LGPS stands for Li10GeP2S12) and unknown products at the acetylene black/
LGPS interface.36 Additional studies have characterized Li3P, Li2S, and Li15Ge4 at
the Li/LGPS interface, as well as the reduction product of Li3xLa2/3 xTiO3 (LLTO)
and Li1+xAlxTi2 x(PO4)3 (LATP).37,38 Furthermore, in situ X-ray photoelectron spec-
troscopy (XPS) has been utilized to characterize Li3N, Li2O, and Li3P at the Li/LiPON
(lithium phosphorous oxynitride) interface.39 Quite recently, XPS was also used to
confirm that the once-believed extremely stable Li7La3Zr2O12 (LLZO) was reactive
with Li at 300 C–350 C.40 Additional studies conducted by Wenzel et al. using
in situ XPS determined that (1) the decomposed Li10GeP2S12 interphase consists
of Li3P, Li2S, and Li-Ge alloy,37 and (2) decomposed LLTO interphase consists
of Ti3+, Ti2+, and Ti metal.41 A detailed discussion of several characterization
techniques is included in the section ‘‘Advanced Characterization Techniques’’.
It is worth noting that some sulfide materials have been found to exhibit both excel-
lent Li+ ion conductivity and electrochemical stability—principally Li9.54
Si1.74P1.44S11.77Cl0.332,42 and Li9.6P3S12.42 A further understanding of the nature
and behavior of interphase materials, including their formation mechanisms, con-
ductivity for electrons/ions, mechanical strength, and crystal structure is absolutely
essential for advancing the science of battery chemistry.
Interface between Cathode and Inorganic Electrolyte

Unlike metal anodes, cathode materials are composed of particles of active mate-
rials such as LiCoO2 (LCO), LiMn2O4 (LMO), LiNiMnCoO2, LiNiCoAlO2, and LiFePO4
that are mixed with appropriate amounts of solid electrolytes (ionic conductors), car-
bon (electronic conductors) and/or binders to enhance the ionic and electronic
transport. In liquid-electrolyte batteries, the liquid electrolyte wets the gaps be-
tween the cathode particles as well as the gaps between the electrode and electro-
lyte; in contrast, physical contact is expected for solid-solid interfaces in SSBs. To
clarify the effects of each interface, Luntz et al.43 employed a symmetric cell to
evaluate the internal resistance (IR) drop at the cathode-electrolyte interface and
anode-electrolyte interface. Their assessment scheme and results are shown in Fig-
ures 3A–3D. In their experiment, an Au/SSE/Au cell (SSE refers to solid-state electro-
lyte) served as the baseline for their IR drop measurements. The SSE featured LiPON
with low reduction voltage and Li+ conductivity at a magnitude of 10 5–10 6 S cm 1.
For the Li/SSE/Li cell, a slight IR drop was evidenced, confirming an interface resis-
tance between Li and SSE. However, when they combined SSE with carbon cathodes
(Figures 3C and 3D), the IR drop increased much more significantly in comparison
with analogous results for Li, indicating a much higher interfacial resistance. The IR
drop on the Li/SSE interface could be attributed to the formation of SEI and an
incomplete contact; for the cathode-electrolyte interface, however, the electro-
chemical processes can be much more complicated. Although their results do
shed light on the different contributions of interface resistance at the cathode and
anode, they only considered carbon cathodes in reporting that the highest interface
resistance occurs at the cathode-electrolyte interface.
Several kinds of interfacial resistance can coexist at the same time. One type of resis-
tance is contact resistance, which results from poor interfacial contact or contact loss
during cycling44,45; thus, secure contact will reduce interfacial resistance. For
instance, Ohta et al.44 assembled a LCO/Li6.75La3Zr1.75Nb0.25O12/Li SSB with ultra-
fine LCO/LLZO interfacial contact (Figures 3E–3G). This battery exhibits excellent
Joule 2, 1–25, October 17, 2018 5

Figure 3. Typical Examples of Cathode-Electrolyte Interfaces in Solid-State Batteries

(A–D) Various symmetric cell models and potential profiles. Note that SSE refers to solid-state electrolytes. Au|SSE|Au symmetric cell (A). Li|SSE|Li symmetric cell (B). Li|
SSE|C asymmetric cell (C). C|SSE|C symmetric cell (D). Reprinted from Luntz et al.,43 with permission. Copyright 2015, American Chemical Society.
(E–G) Cross-section scanning EM image (E), backscattering electron image after 100 cycles (F), and charge/discharge curves in first and 100 th cycles (G)
of the LCO/LLZO/Li battery, respectively. Reprinted from Ohta et al., 44 with permission. Copyright 2012, Elsevier B.V.
(H–J) Schematic of the battery configuration (H), cross-section scanning EM image and EDS mapping (I), and charge-discharge curves (J) of flexible
SSBs. Reprinted from Nam et al., 45 with permission. Copyright 2015, American Chemical Society.
cycling reversibility. Han et al.46 modified the interface between LCO and LLZO by
thermally soldering them together with Li2.3 xC0.7+xB0.3 xO3 SEI, which effectively
decreased the interfacial resistance and achieved high cycling stability. Additionally,
Nam et al.45 assembled flexible SSBs by utilizing polymer scaffolding (Figures 3H–
3J), whereby an interfacial contact was maintained. There is another type of resis-
tance that results from the nanoionic effect, which is a space-charge layer generated
at the interface between two ionic conductors with different chemical potentials of
the ions. In brief, a sulfide solid electrolyte has lower chemical potential of Li+ and
weaker attraction to Li+ compared with a high-voltage cathode, such as LiCoO2.
When a sulfide solid electrolyte comes into contact with LiCoO2, Li+ will diffuse
from the electrolyte side to the cathode side, generating a high-resistance Li deple-
tion layer at the interface on the electrolyte side (Figures 4A and 4C).33,47 Such a
space-charge zone is detrimental and severely affects the high-rate charge/
discharge ability of SSBs, while also serving as the rate-determining step.48–50 Sup-
pression of this effect is essential for producing high-power density SSBs. One
possible way to inhibit the nanoionic effect is to shield the sulfide with a thin oxide
buffer layer that prevents direct contact with the cathode (Figures 4B and 4D). For
example, coating LiNbO3 on LCO50 and LMO51 could successfully suppress the
6 Joule 2, 1–25, October 17, 2018

Figure 4. Illustration of Nanoionics Effect in Sulfide Electrolyte Interface

(A and B) Lithium concentration profiles at the LCO-LPS interface without (A) and with (B) an LNO
buffer layer. The dashed lines represent lithium chemical potential as the reference. Here LCO, LPS,
and LNO refer to LiCoO2 , Li3 PS 4 , and LiNbO3 , respectively. Reprinted from Haruyama et al., 47 with
permission. Copyright 2014, American Chemical Society.
(C and D) Space-charge zone in LCO-sulfide electrolyte interface without (C) and with (D) buffer.
Reprinted from Takada, 33 with permission. Copyright 2013, Elsevier B.V.
space-charge layer effect. In many cases, capacity fading is caused by simultaneous

negative effects. Koerver et al. discovered that at the interface of LiNi0.8
Co0.1Mn0.1O2 and b-Li3PS4, capacity fading stems from the decomposition of sulfide
electrolytes and volume shrinking of cathode materials, which results in contact
loss.52
It has been widely observed that intercalation reaction electrodes exhibit better
cycling reversibility than alloy and conversion reactions in LIBs. The structure stability
is even more important in solid-state systems. Thus, a complex framework such as
carbon coating is required, especially for alloy or conversion reactions involving a
sulfur cathode. However, at the interface between the cathode and sulfide electro-
lyte, the carbon additives that provide electronic percolation paths accelerate the
interfacial oxidation reaction. The formed polysulfide by-products block Li+ conduc-
tion paths, leading to significant interfacial resistance and irreversible capacity
loss.53 Hence, the compatibility between electrolytes and electrodes should be
carefully considered when designing the composition and structure of electrode
materials.
Interface between Anode and Inorganic Electrolyte

In this section only a Li anode will be discussed, although it must be noted that this
analysis is also applicable to Si anodes and carbon anodes. We begin this discussion
by examining Li nucleation and growth in liquid electrolytes to better understand the
fundamental issues involved in this process, and then extend this analysis to include
Li penetration through solid electrolytes. A long-standing problem for Li anodes is
associated with dendrite growth that penetrates the electrolyte and causes short-cir-
cuiting,31,54 which also contributes to the intrinsic high activation energy.55 The
nucleation and growth of Li on Li metal upon cycling occurs quite rapidly. SEI on
Joule 2, 1–25, October 17, 2018 7

Li cannot provide sufficient mechanical strength to prevent dendrite formation if

penetrated. Thus, atomic force microscopy (AFM) represents a powerful tool to
monitor the surface topography and modulus of the interface, while in situ AFM
studies have been conducted to show that the Young’s modulus of natural SEI layer
in organic electrolyte is within the range of 50–400 MPa.56,57 The result is that the Li
surface may become bumpy, resulting in undesirable interfacial contact. Various Li
growth mechanisms have been assessed in prior reviews.6,30
The Cui group studied the effects of overpotential on Li nucleation and growth at the
nanoscale level, which include several key results.58 First, the Li nucleation energy
barrier increases with overpotential (Figure 5A). Second, during galvanostatic Li
deposition, the potential initially drops to hn (hn refers to nucleation overpotential)
to initiate the nucleation, then rises to hp (hp refers to plateau overpotential) for
steady-state Li growth (Figure 5B). Third, an inverse relationship exists between
the size of Li nuclei and overpotential; additionally, there is a cubic relationship be-
tween the density of Li nuclei and overpotential (Figure 5C). Fourth, experimental
data indicate that the nucleation barrier and growth plateau increase with galvano-
static current density (Figure 5D). Overall, these results suggest that small, dense,
and uniform Li nuclei can grow when the overpotential is increased via high current
density. This fundamental study on Li nucleation and growth can rationally guide the
design of micro-/nanostructures for Li-metal anodes and the optimization of charge/
discharge conditions.
Compared with liquid electrolytes, different issues must be considered in the case of
solid electrolytes. Recently, Porz et al. reported the process of Li dendrite growth
and infiltration in inorganic solid electrolytes.31 For their study, they selected
different inorganic solid electrolytes including sulfide and garnet electrolytes. Their
results confirmed that Li penetration depends on defect size and density rather than
on the impact of electrolyte shear modulus and surface roughness. Moreover, the re-
searchers showed that the flaws/cracks, grain boundaries, and/or micro-/nanoscale
pores usually lead to faster Li dendrite growth and crack propagation. Accordingly,
they developed a model and studied the dependence of Li deposition overpotential
and the stress-crack propagation relationship on defect size for Li6La3ZrTaO12 and
glassy Li2S-P2S5 (Figure 5E). Both the minimum overpotential and crack-extension
stress decreased with defect size with inverse square-root dependence. Thus, stra-
tegies for minimizing interfacial defects represent a critical design principle for inhib-
iting Li dendrite penetration in inorganic solid electrolytes.
Interface between Polymer Electrolyte and Lithium Metal

Although current polymer electrolytes cannot compete with ceramic or glass elec-
trolytes in terms of ionic conductivity, the versatility of polymer electrolytes is still
highly desirable in the development of flexible batteries and electronics.59,60 The
advantage of using a liquid electrolyte is that the flowability of liquid ensures the
maximum electrolyte-electrode contact area and minimum electronic resistance.32
These desirable attributes can be inherited by polymer electrolyte that also features
good adhesiveness and malleability. In addition to low conductivity, another issue
for a polymer electrolyte is Li dendrite formation. Utilizing Mullins-Sekerka linear sta-
bility analysis and the Barton and Bockrisis dendrite-propagation model, Monroe
and Newman concluded that (1) dendrite growth at all applied current values, and
(2) morphological instability are both essentially insurmountable for a Li-polymer
interface once the system has reached the propagation regime.20,54 However,
they predicted that interfacial stability can be achieved when the shear modulus of
the polymer is in the gigapascal (GPa) range.
8 Joule 2, 1–25, October 17, 2018

Figure 5. Lithium Nucleation, Growth, and Penetration

(A) Schematic relation of overpotential and Li nucleation energy barrier.
(B) Schematic voltage profiles of Li deposition with galvanostatic and double-pulse method.
(C) Schematic plots of the size and density of Li nuclei versus overpotential.
(D) Experimental voltage profiles of Li deposition at different current densities.
(E) Diagram of the relation of Li plating overpotential, crack-extension stress, and defect size. Here,
LPS and LLZTO refer to Li 2 S-P2 S 5 and Li 6 La 3 ZrTaO 12 , respectively. Reprinted from Porz et al.,31 with
permission. Copyright 2017, Wiley-VCH.
(A)–(D) are reprinted from Pei et al., 58 with permission. Copyright 2017, American Chemical Society.
For years, one of the primary challenges in utilizing polymer electrolytes had been
increasing mechanical properties without sacrificing ionic conductivity. Mechanical
strength can be enhanced through a variety of approaches, including increasing
Joule 2, 1–25, October 17, 2018 9

molecular weight, adding substitute groups, crosslinking, copolymerization, and

enhancing crystallinity. Meanwhile, ionic conductivity can be simply enhanced by
adding and optimizing salt component.61 However, there are other methods for
achieving both high ionic conductivity and mechanical strength. For instance,
Schulze et al. applied a polymerization-induced phase separation method where
ion-conducting domains and high-modulus domains are mixed in one system,
thereby achieving 1 GPa elastic modulus and 1 mS cm 1 ionic conductivity at the
same time.62 Note that the Newman model is only applicable for polymers and
not inorganic solid-state electrolytes, because the defects and grain boundaries
significantly affect the penetration of Li dendrites through inorganic solid-state
electrolytes.
In addition to Li dendrite penetration, chemical stability and Li-polymer adhesion

should also be considered when designing polymer electrolyte batteries. One
important application for a Li anode is in Li-air batteries. During battery discharge,
oxygen will first reduce to superoxide radical anions and then form LiO2 and Li2O2
consecutively. Meanwhile many aprotic electrolytes are not stable against these
two products, which has the unwanted outcome of shortening the cycle life of the
batteries. Amanchukwu et al. analyzed nine types of polymers and discovered that
only three were chemically stable.63 Thus, understanding the reactivity of polymers
and reaction products provides critical information for the design of polymer elec-
trolytes for use in next-generation batteries and devices. In terms of Li-polymer
adhesion, this facet is not well understood because conventional models view the
electrolyte-electrode interface as simply a boundary condition.20,54 Dendrite pene-
tration in polymers is unlike what occurs with solid-state oxides or sulfides where Li
grows through the grain boundaries and defects. Therefore a shear modulus in the
range of GPa is needed to suppress dendrite formation, as Monroe and Newman
predicted.20,54 Moreover, Li anodes are known to recede a few microns during
discharge if the polymer does not have a good adhesion to the Li; thus, the resulting
void will eventually increase interfacial resistance and decrease overall ionic conduc-
tivity.64 In short, excellent adhesion between a Li metal and the selected polymer is
essential to ensure efficient ion transfer and long cycle life.
Interface of Interparticles
In general, ionically and/or electrically conductive particles must be added and
mixed with the active material particles during the fabrication process of a cathode
or anode of a SSB if the active materials are not highly ionically and/or electrically
conductive. Thus, the interparticle interface in a composite cathode or anode is
also important. The definition of this interface includes both the interface between
active materials and the contact between active material particles and ionically/elec-
trically conductive particles. Lithium ions transport through the electrodes via grain
boundaries. The volume change of the cathode particles during charge/discharge
would lead to contact failure in composite electrodes.65
Strauss et al. studied the effect of the size of cathode composite materials, reporting
that cathode materials of a smaller particle size (much less than 10 mm) will deliver
near-full capacity in the first cycle, which is due to both increased electrical contact
as well as the fact that there are more consecutive grain boundaries—meaning that
ions will transport with less resistance.66 They pointed out that the ratio of solid-elec-
trolyte particles to cathode particles in a given composite cathode should be deter-
mined according to the desired purpose.66 For example, a high-energy-density bat-
tery requires fewer solid-electrolyte particles; in contrast, a high-power-density
battery requires more solid-electrolyte particles in the composite cathode. It is worth
10 Joule 2, 1–25, October 17, 2018

Figure 6. Schematics of Typical Interfacial Contact in a Liquid Electrolyte Battery and a Solid Electrolyte battery
Illustration of the difficulty of investigating a liquid-electrolyte battery (A) and a solid-electrolyte battery (B).
noting that there should be a balance of ionic and electronic paths within a compos-
ite electrode. On the one hand, the presence of too many electrolyte particles blocks
the electronic path. On the other hand, too many active cathode particles will limit
ionic transport. Rational micro-/nanostructure designs—for example, adopting hier-
archically mixed ion- and electron-conducting networks—could facilitate ionic trans-
port while reducing electronic resistance.
Advanced Characterization Techniques

The type and behavior of an interface in a SSB represent key issues due to the degree
of contact and high charge transfer impedance at the interface.67–69 Therefore, it is
essential to clarify the interfacial impedance phenomena as evidenced by morpho-
logical changes and electrochemical processes via the use of advanced characteriza-
tion techniques. Only then can next-generation SSBs that meet a wide range of in-
dustrial and personal consumer demands be developed. Although various
methods have been established to investigate liquid-electrolyte battery systems, a
formidable obstacle remains in determining interfacial behavior in SSBs. Indeed,
such interfaces are difficult to isolate compared with their counterparts in liquid-
electrolyte systems. As can be seen in Figure 6, electrode materials in liquid-electro-
lyte systems are rather easy to extract for post-experimental analysis without
damaging the sample materials. In contrast, to fabricate a SSB various methods
such as hot-pressing technology and chemical/physical evaporation are usually car-
ried out to obtain a relatively superior interfacial contact.70 Thus, these tightly
embedded interfaces cannot be fully exposed without damaging the surface condi-
tion, making it difficult to obtain essential information about their interfacial reac-
tions and kinetics, especially in the case of Li anode/solid-electrolyte systems.41
Hence a different approach, ideally involving an in situ experimental methodology,
must be designed.71 Typically electrode materials are studied by ex situ experiments
in coin cells, but interfacial studies could be carried out by hybrid cell,70 symmetric
cell,43 or through a combination of ex situ and/or in situ experiments. As evidenced
in the energy diagram (Figure 2), two kinds of interfaces can be distinguished: ther-
modynamic stable interface and thermodynamic unstable interface (representing
the majority at present). In this section, the currently available interfacial
Joule 2, 1–25, October 17, 2018 11

characterization methods are organized into three categories. In addition, two ad-
vantageous characterization methods developed by our collaborative group are
highlighted.
Microscopy Observation
Unlike conventional microscopic investigations of liquid-electrolyte batteries, the
intact interfaces in SSBs are difficult to isolate for microscopy characterization. A
cross-section image of the anode-electrolyte interface or cathode-electrolyte inter-
face provides more convincing results, but specific techniques for sample prepara-
tion are required. If a more effective way, such as focus ion beam, could be devel-
oped to cut the cross-section of the sample with precision, many conventional
methods such as cross-section scanning electron microscopy (EM) (Figures 7I and
7P show the clear cross-section scanning EM images of the interface between elec-
trode and electrolyte,72 transmission electron microscopy (TEM), energy-dispersed
X-ray analysis (EDX), and electron energy loss spectroscopy (EELS) could be utilized
to elucidate the nature of the interface. Moreover, by switching different modes of
TEM (image, diffraction, and spectroscopy) and combining results with those ob-
tained using EDX73 and EELS, more detailed information about morphology, struc-
ture, and composition of the Li2SiO3-coated LiCoO2/Li2S-P2S5 interface could also
be accurately obtained (Figure 7E).
As shown in Figure 7, there are numerous successful microscopic observations.

These photos include one or two kinds of interfaces in one frame. The difficulty in
obtaining two kinds of interfaces in one frame is related to microbattery sample
preparation. Special sample holders are essential to prevent air exposure. Brazier
et al.77 used pulsed laser deposition (PLD) to prepare a microcell and was the first
to perform direct in situ TEM observations. Later, cross-section images of the inter-
face between LiCoO2 and Li2S-P2S5 were obtained by high-angle annular dark-field
scanning TEM (HAADF-STEM) (Figures 7A–7D and 7M–7O)74; this study, in partic-
ular, opened up the door for interfacial TEM observations and later in situ experi-
ments. The charge-discharge reaction process of a Li-oxygen battery was observed
in real time by the operando liquid cell EM. The reaction details for Li ions and oxy-
gen at the interface between the carbon cathode and the liquid electrolyte could be
observed at the nanometer and millisecond levels.78 Santhanagopalan et al.
improved upon their previous ex situ scanning TEM (STEM)-EELS79 technique, and
introduced an in situ STEM-EELS (Figures 7F–7H)75 interfacial approach. Subnanom-
eter resolution, subsecond temporal resolution, and even atomic percentage light
element detection can be achieved with this state-of-the-art STEM-EELS tech-
nique.75,76,79,80 Furthermore, Li3N, Li2CO3, and LiOx were found along the grain
boundaries of HP-LLZ:Ta (hot-pressed Ta-substituted Li7La3Zr2O12) (Figures 7J–7L)
by high-resolution TEM (HRTEM)-EELS.76 AFM is another popular method for ob-
taining surface characterization information.31,56,57 Recently, Shen et al. utilized in
situ electrochemical AFM to investigate Li dendrite growth on graphite anodes81 us-
ing different liquid electrolytes. This approach has not yet been applied to solid sys-
tems, but we are optimistic that this possibility will eventually become a reality.
Other methods such as Auger electron spectroscopy, time-of-flight secondary ion
mass spectroscopy, and scanning tunneling microscopy can also be implemented
with ex situ experiments or designed for in situ investigations.
Chemical Composition Analysis

The instability of an interface often stems from the degradation of electrolytes, which
is an important factor affecting the performance of SSBs. The Ceder group has ob-
tained a large number of calculations with DFT82 and first principles83 on the
12 Joule 2, 1–25, October 17, 2018

interfacial stability between the electrode and the solid electrolyte. In particular,
they studied the thermodynamics of interfacial phases and found that generally,
electrolytes that are stable at the cathode voltage show low reaction energies.
They calculated that thiophosphate electrolytes have especially high reactivity
with high-voltage cathodes (such as LCO) and a narrow electrochemical stability win-
dow. They also proposed a number of intriguing battery combinations with high en-
ergy that had not been employed, such as Li3PS4 or Li7P3S11 combined with LiVS2,
LiTiS2 cathode with Li2S-P2S5, and LiBH4-LiTiS2 cells.84 Most recently, they reported
that Li demonstrates the highest stability at the tetrahedral site and that the body-
centered cubic-like anion framework is the most desirable for achieving high ionic
conductivity.16 These novel and significant design advances serve as a good guide
for the development of fast ion-conducting materials.
Chemical composition investigations are mainly utilized to verify the chemical stabil-
ity of the electrolyte-electrode interface, which can share the same purpose as cyclic
voltammetry (CV) but with higher accuracy since it can be measured quantitatively.
XPS and Fourier transform infrared spectroscopy are the most widely used tech-
niques for SEI investigations.27 For organic liquid-electrolyte batteries, coin cells
are dissembled in a glovebox and samples are washed with an organic solvent
before undergoing examination. While these techniques can be employed if SSBs
have similar circumstances, for most cases a cross-section cut is needed. XRD has
long been utilized as a standard method to assess composition analysis,36 and sin-
gle-crystal XRD remains the most effective and convincing way to determine the
anisotropic displacement parameter of a new material.85 Crystals can be regarded
as diffraction gratings for X-rays, and the coherent scattering produced by a large
number of these particles will interfere with the light, thereby increasing or
decreasing the intensity of scattered X-rays. Therefore, the crystal phase composi-
tion and unit cell parameters can be detected by XRD, and different peak positions
are caused by different crystal structures. In contrast, amorphous materials do not
have a complete crystal structure and are difficult to detect by XRD. Unlike XRD,
XPS works on the chemical bond, and X-rays can interact with atoms in the material’s
surface layer to produce photon energy. When the photon energy generated ex-
ceeds the binding energy in the electronic nucleus, it will stimulate the inner layer
of electrons in the atom, thereby producing photoelectrons. Detecting the quantity
and kinetic energy of photoelectrons through the corresponding testing instruments
enables XPS technology to accurately analyze the content and chemical state of the
elements in the sample surface. Zhang et al. coated LLTO with Li2O-B2O3, and result-
ing XRD characterization results showed no added peaks compared with the pure
LLTO. The researchers then speculated that Li2O-B2O3 was present in the grain
boundary of LLTO, which was later confirmed by XPS.86 Although Demir-Cakan
et al. detected the deposition of Li2S on a Li anode via XRD, they also conducted
XPS characterization to clearly verify the surface decomposition.87 Hence, XPS is a
vital tool in interface detection.
Dedryvère and colleagues studied SEI formation87,88 and the Li-ion transfer mecha-
nism89 between the electrode and liquid-electrolyte interface by ex situ XPS. They
observed that in the silicon anode SEI initially forms on the anode, after which Li
and silicon formed an alloy to achieve the lithiation process, with the generation
of Li2O and LixSiO4. After full charging, the thickness of the SEI decreased only
slightly and the Li2O disappeared.89 In the case of electrolytes they reported that
EC0.45:PC0.45:DMC0.1 (EC, PC, and DMC refer to polycarbonate, ethylene carbon-
ate, and dimethyl carbonate, respectively) with 1 M of Na salt was an optimal elec-
trolyte formulation that could effectively suppress the degradation of the electrolyte
Joule 2, 1–25, October 17, 2018 13

Figure 7. Selection of Images Obtained via Various Microscopic Methods

(A–D) HAADF-STEM images of the electrode-electrolyte interfaces. Reprinted from Kitaura et al., 74 with permission. Copyright 2011, Royal Society of
Chemistry.
(E) HAADF-STEM and linear EDX images of the Co element near the LiCoO 2 electrode/Li 2 S-P 2 S 5 solid-electrolyte interface. Reprinted from Sakuda
et al., 73 with permission. Copyright 2010, American Chemical Society.
14 Joule 2, 1–25, October 17, 2018

Figure 7. Continued
(F–H) STEM (F) and STEM-EELS (G and H) images of the nano battery stack along with Li k-edge concentration mapping. Reprinted from Wang et al., 75
with permission. Copyright 2016, American Chemical Society.
(I) Scanning EM cross-section image of an LATGP sample after approximately 12 hr contact with Li metal. LATGP stands for Li-Al-Ti-Ge-P-O electrolyte.
Reprinted from Hartmann et al., 38 with permission. Copyright 2013, American Chemical Society.
(J–L) High-resolution transmission electron microscopy (HRTEM) (J) and EELS (K and L) images of HP-LLZ:Ta (hot-pressed Ta-substituted Li 7 La 3 Zr 2 O 12 ),
where Li 3 N, Li 2 CO 3 , and LiO x were found along the grain boundaries. Reprinted from Tsai et al., 76 with permission. Copyright 2016, American Chemical
Society.
(M–O) HAADF-SEM (M), EDX (N), and SAED pattern (O) images of the Co element near the LiCoO2 electrode/Li 2 S-P2 S 5 solid-electrolyte interface.
Reprinted from Sakuda et al., 73 with permission. Copyright 2010, American Chemical Society.
(P) Scanning EM image of the interface between composite cathode containing 15 wt% polymer and the composite electrolyte. Reprinted from Chen
in sodium-ion batteries.88 XPS also performs well in SSB interfacial detection. For
example, ex situ XPS verified the decomposition of LGPS.37,90 Furthermore, Janek
and coworkers have conducted several investigations using in situ XPS to study
metal/solid-electrolyte stability; moreover, several in situ XPS experiments have
been reported to verify the electrolyte decomposition of various solid electrolytes
such as LLTO,41 NASICON structure electrolyte like LATP,38 and Li7P3S11.91 The
schematic diagram for the device is shown in Figures 8A and 8B, where Li is vapor-
ized by an argon beam and deposited on the electrolyte surface. The Li can either be
adjacent to the electrolyte sample or have a certain space relationship with the sam-
ple. This simple device allows the stability of the interfaces between a metal elec-
trode and a solid electrolyte to be detected, and the decomposition will show the
stability of the interface. It must be noted, however, that this work would be more
useful if cycling full cells were used in the device.
Various modifications to XPS such as hard XPS and soft XPS have resulted in a much
wider probing depth range that is also more sensitive than traditional XPS.93
Another fascinating method that is being applied to the problem is nuclear magnetic
resonance (NMR)69,76 and in situ NMR.92 As an example, Nakayama et al. first assem-
bled in situ NMR to observe elemental distribution and determine the uneven elec-
trolysis of anion components at the interface between a cathode and solid polymer
electrolyte92 (Figure 8C) due to the high sensitivity of the technique toward Li-ion
transport in bulk battery materials. It should also be noted that Yu et al. tested the
quantity of the Li ions spontaneously transported between the Li6PS5Br solid electro-
lyte and the Li2S cathode by NMR (Figure 8D).69 Yet another approach is provided by
solid-state NMR using multi-phase battery materials—even for multiple electrode
phases or a mixture of electrode and electrolyte phases—to measure the
spontaneous Li-ion transfer between different Li-containing phases. This approach
provides unique selectivity for charge transfer over phase boundaries, and offers
complementary information with respect to interfacial behavior. Remarkably, the
nondestructive, contactless nature of the technique makes NMR friendly to sample
pretreatment.
According to studies devoted to calculating the interfacial stability and design of

SSB materials, augmented by powerful characterizations of interfacial by-prod-
ucts,36,73,94,95 numerous sulfide-based compounds have been fabricated with
higher ionic conductivities. The Kanno group proposed that with the doping of
germanium into Li3PS4, the conductivity of the electrolyte can be greatly
increased.22 As a result, several sulfide electrolytes with high ionic conductivity
have been fabricated, such as Li3.25P0.75Ge0.25S4 (2.2 3 10 3 S cm 1)96 and Li10
GeP2S12 (10 2 S cm 1).22 Based on this known relationship, other doping ap-
proaches, for instance using Li9.54Si1.74P1.44S11.7Cl0.3 (25 mS cm 1)42, have also
been employed. Interfacial impedance has always hindered the development of
Joule 2, 1–25, October 17, 2018 15

Figure 8. Selective Examples of Chemical Examinations

(A) In situ lithiation of solid electrolytes during XPS surface analysis. The argon ion gun is used to sputter a Li-metal foil placed in the vicinity of the
sample of interest. Reprinted from Hartmann et al.,38 with permission. Copyright 2013, American Chemical Society.
(B) The basic idea and setup of the in situ XPS technique. An argon ion beam is used to sputter lithium, gold, or aluminum metal on the sample surface.
After deposition, the reaction products at the interface are investigated using photoelectron spectroscopy. Reprinted from Wenzel et al., 41 with
permission. Copyright 2015, Elsevier B.V.
(C) Schematic diagram of cell for in situ NMR imaging, and definition of x, y, and z axes of inserted Li polymer battery. Fluorine distribution in solid
polymer electrolyte (SPE) measured by 19 F-NMR before (a1, a2) and after (b1, b2) electrochemical cycling. Reprinted from Nakayama et al.,92 with
permission. Copyright 2010, The Royal Society of Chemistry.
(D) NMR test result of the Li-ion transport between the Li 6 PS 5 Br solid electrolyte and the Li 2 S cathode. Reprinted from Yu et al., 69 with permission.
Copyright 2017, Macmillan Publishers Limited.
16 Joule 2, 1–25, October 17, 2018

SSBs featuring glass-ceramic electrolytes. To achieve close contact and good stabil-
ity, the Tatsumisago group developed various interfacial modification methods.
Coating the buffer layer on cathode materials represents a simple and effective
way to soften the contact, and cathode coatings are known to improve the perfor-
mance of high-voltage electrolytes by isolating the electrolyte materials from the
low Li potential. Accordingly, Tatsumisago and colleagues coated a LiCoO2 cathode
with Li4GeS4-Li3PS4; the resulting solid-electrolyte coating formed a favorable and
effective ion-conductive path to LiCoO2 particles.97 In another recent study, 50Li4
SiO4$50Li3PO4 (mol%) film was coated on LiCoO2 active material particles by PLD,
with the coated electrolyte layer effectively decreasing interfacial resistance.98 The
mixing of metal oxides with Li2S-P2S5 by mechanical milling can also enhance the sta-
bility of sulfide electrolyte in air. For example, combining a favorable metal oxide
MxOy (M = Zn, Fe or Bi) with sulfide can decrease the Gibbs energy for H2S formation,
which is an effective way to improve the chemical stability of sulfide electrolytes.99
Tatsumisago’s group also described a heat-treatment method for improving ionic
conductivity. They heated Li2S-P2S5 glass ceramics to transform the particles into
a dense material free from grain boundaries, which would decrease the porosity
and the grain boundary resistance.23
Electrochemical Characterization
CV and electrochemical impedance spectroscopy (EIS) are two traditional electro-
chemical characterization approaches that focus on the entire battery, with each
test performing a specific function. CV reports the current versus changing voltage
to present a current-voltage graph, which provides information about chemical re-
actions and cycling reversibility. In contrast, EIS indicates the ionic impedance
(high-frequency area) and the diffusion impedance (low-frequency area) of either a
specific material or the overall cell (Figures 9A, 9H, and 9I).22,100 The charge-
discharge curves present the overall energy density and cycling reversibility, in
which the plateaus correspond to the redox peaks in CV (Figures 9B and 9C).22
The stability window of solid electrolytes can be characterized by CV. However,
the stability window is usually overestimated by the traditional Li/solid electrolyte/
inert metal cell test, in which the contact area between solid electrolyte and metal
plate current collector is small, which results in slow kinetics of the electrolyte
decomposition reaction. Han et al.17 designed a novel Li/electrolyte/electrolyte-car-
bon cell composed of a mixture of carbon and solid electrolyte as the electrode to
increase the contact area between electrolyte and current collector. This novel cell
design can improve the electrolyte decomposition kinetics to a level similar to
that of real SSBs. Their results show the intrinsic electrochemical stability window
of LGPS to be only 1.7–2.1 V, which is much narrower than the window (0–5 V) char-
acterized by traditional Li/solid electrolyte/inert metal cells.
In addition, symmetrical cells can be assembled to elucidate the details surrounding

electrode-electrolyte interfacial contact via polarization testing. As illustrated in Fig-
ures 9E–9G and 9J,100 this polarization test can be carried out via an electrode/elec-
trolyte/electrode cell, and a set current can be run at certain temperature, whereby
the overpotential refers to an additional IR drop. Similar testing was conducted by
Luntz et al. in a prior context (Figures 3A–3D).43 Recently, Wang et al. successfully
distinguished the electronic conductivity and ionic conductivity of the materials by
employing a combination of EIS and direct current polarization. Studies show that
in ternary materials, with an increase in Ni content the activation energy of ion and
electron conduction can be significantly reduced, which can improve the materials’
electron-conduction and ion-conduction characteristics, and enhance the rate per-
formance.101 Moreover, the IR drop alone can provide sensitive information about
Joule 2, 1–25, October 17, 2018 17

Figure 9. Selective Examples of Electrochemical Tests

(A–C) Impedance plots of the conductivity data from low to high temperatures and Arrhenius conductivity plots of Li 10 GeP 2 S 12 (A); charge-discharge
curves of an all-solid-state battery consisting of LiCoO 2 cathode, Li10 GeP 2 S 12 electrolyte, and In metal anode (B); and current-voltage curve of
Li/Li 10 GeP 2 S 12 /Au cell (C). Reprinted from Kamaya et al., 22 with permission. Copyright 2011, Macmillan Publishers Limited.
(D) Comparison of the hysteresis of Li deposition/dissolution for the modified electrode and the control electrode with Li metal as the reference/counter
electrode. Reprinted from Zheng et al., 11 with permission. Copyright 2014, Macmillan Publishers Limited.
(E–J) Schematic of symmetrical cell (E), EIS (H and I), and polarization test (F, G, and J) of the symmetric Li/FRPC (fiber-reinforced polymer composite)
electrolyte/Li cell.
the interfacial connection (Figure 9D).11 As the IR drop is an indication of resistance,

a stable IR drop would indicate relatively stable interfacial contact; conversely, a se-
vere IR drop change points to a change in contact circumstances.
Other Advanced Techniques

In addition to the aforementioned standard assessment approaches, a number of
unconventional, yet interesting, experiments have been conducted. These include
real-time thickness measurements,92 thermogravimetric analysis,102 differential
scanning calorimetry, accelerated rate calorimetry, temperature programmed
desorption, and atomic absorption spectroscopy. Here, we would like to provide
a short introduction to two unique characterization techniques: (1) vibrational
18 Joule 2, 1–25, October 17, 2018

Figure 10. VSFG and On-Chip Single-Nanowire Battery Characterizations

(A) Schematic of the spectroelectrochemical apparatus.
(B) Potential-dependent SFG intensities of the carbonyl stretch during 12 CV cycles. Red lines denote the potential ramp. Reprinted from Nicolau
(C) Schematic of a chip-based single-nanowire solid-state battery. In this schematic, a single nanowire is the cathode (or anode) and nanofilm is the
anode (or cathode). A solid-state electrolyte thin film is coated on top of the chip. ‘‘S’’ indicates the source electrode and ‘‘D’’ indicates the drain
electrode for nanowire conductance characterization.
(D) Optical microscopy image of a representative single-nanowire battery. Single Si/a-Si core/shell nanowire is the anode and LiCoO 2 film is the
cathode. Scale bar represents 10 mm.
(E) In situ conductance characterization of a Si/a-Si nanowire at different charge/discharge states: red, primary state/100; yellow, after first charge and
discharge; green, after second charge; blue, after second discharge.
(F–I) In situ Raman mapping of a Si/a-Si nanowire at different charge/discharge states. (F) Optical microscopy image; (G) primary state; (H) after first
cycle; (I) after second cycle. Scale bar represents 2 mm.
(J) Schematic of a single-nanowire electrode with multicontacts for ion-transport study. Reprinted from Xu et al., 113 with permission. Copyright 2015,
American Chemical Society.
(K) Schematic of a porous graphene-wrapped single-nanowire electrode to improve electron and ion transport. Reprinted from Hu et al., 114 with
permission. Copyright 2016, American Chemical Society.
(C) to (I) reprinted from Mai et al., 112 with permission. Copyright 2010, American Chemical Society.
sum-frequency generation spectroscopy and (2) on-chip single-nanowire battery

characterization.
Vibrational Sum-Frequency Generation Spectroscopy. Vibrational sum-frequency

generation spectroscopy (VSFG) has been proved to be a unique and effective
chemical characterization technique for molecular interfaces (Figure 10A).103 A
number of advantages—such as interfacial specificity, high sensitivity, no vacuum
requirement, real-time results, and in situ detection—have enabled VSFG to
perform nondestructive characterizations in many fields. VSFG has been applied
to various materials and interfaces such as polymers,104 electrodes,105,106 bio-
membranes,107 DNA,108,109 and proteins.110,111 To elucidate the SEI formation
Joule 2, 1–25, October 17, 2018 19

mechanism in LIB liquid-electrolyte batteries, Mukherjee et al. designed an in situ

VSFG device to monitor molecular changes106 during CV cycling. Despite the fact
that the signal contributions from the electrode interface and the diffuse layer elec-
trolyte cannot be easily separated,112 gradual changes in the VSFG signals in the
carbonyl region were observed during potential cycling and the Li deposition/strip-
ping at the anode (Figure 10B). It is clearly shown that dilithium ethylene glycol di-
carbonate (LiEDC) molecules were formed after the sixth potential forward-back-
ward scanning cycle. By monitoring the SFG intensity modulations of the -CH
scissoring mode of LiEDC, and the -CH2 wagging mode of tetrahydrofuran during
the potential scanning cycle, the molecular mechanisms involved in SEI formation
can be elucidated. In short, these results confirm that VSFG is capable of monitoring
Li deposition and Li stripping during the potential scan. After successful demonstra-
tion of potential-dependent VSFG characterizations, the application of VSFG on
other types of electrode interfaces can also be expected. It must be noted, however,
that the requirements for Raman/infrared reactivity, non-centrosymmetrical struc-
ture, and light accessibility will limit the application of VSFG on certain interfaces.
Indeed, there will certainly be more challenges in applying in situ VSFG characteriza-
tion to SSB systems, in that they require special optical design for propagation of
incident lights and collecting SFG signals. Accordingly, we would like to suggest
more collaborative efforts toward this experimental goal.
On-Chip Single-Nanowire Battery Characterization. An on-chip single-nanowire

battery could serve as a unique platform for in situ characterization of electron/ion
transport and structure evolution in a battery. Mai et al.112 described the develop-
ment of a single-nanowire solid-state Li-ion battery to conduct in situ probing of
the intrinsic reason for capacity fading. In this device (Figure 10C), a single nanowire
serves as the cathode (or anode) and a nanofilm serves as the anode (or cathode).
The nanowire and nanofilm are then put into contact with micro-/nanoscale metal
electrodes, respectively, which have dual functions as current collectors during bat-
tery cycling and source/drain contacts during nanowire conductance characteriza-
tion. Both the cathode and anode are fabricated on the same chip and wired up
with the outer electric circuit without adding conductive additives or a binder. A
solid-state electrolyte is deposited on top of the chip. To achieve in situ character-
ization, one could carry out battery cycling, nanowire conductance monitoring,
and Raman mapping characterization simultaneously on this chip-based battery.
Figure 10D shows an optical microscopy image of a representative single-nanowire
battery. A single silicon nanowire is the anode, a LiCoO2 nanofilm is the cathode,
nickel microelectrodes serve as current collectors and source/drain contacts, and
a polyethylene oxide-based solid-electrolyte film is coated on the chip. In situ
current versus voltage (I-V) characterization shows that the conductance of silicon
nanowire continuously decreases during charge/discharge cycling (Figure 10E).
Specifically, the conductance decreases over two orders of magnitude after one cy-
cle, which agrees with the ex situ I-V characterization of silicon nanowires described
in the literature.9 We also note that the I-V curves become nonlinear after charge/
discharge cycling, indicating that the contacts of silicon nanowire and nickel current
collectors also degrade during the electrochemical reaction, which cannot be easily
confirmed using other characterization techniques. In situ Raman mapping reveals
the inhomogeneous degradation of silicon nanowires during battery cycling (Figures
10F–10I), which results from amorphous Li-Si alloy formation. Another example
involving H2V3O8 nanowire as the cathode and graphene as the anode has been
investigated on the basis of this single-nanowire battery platform.112 Interestingly,
unlike silicon, the conductance of a H2V3O8 nanowire decreases after shallow
discharge but can be recovered after shallow charge. However, the conductance
20 Joule 2, 1–25, October 17, 2018

of a H2V3O8 nanowire permanently decreases after deep discharge and charge.

Taken together, these findings confirm that conductance decrease and the structural
degradation of electrodes represent the two key issues leading to capacity fading.
The concept of this single-nanowire battery can be further extended with improved
nanowire electrode design. Mai and colleagues can be credited for two improved
design advancements: (1) multicontacts for ion transport (Figure 10J) and (2) porous
graphene-wrapped nanowires to improve electron and ion transport (Fig-
ure 10K).113,114 In brief, fabricating multiple metal microelectrodes on a single
nanowire can enable one to record the conductance change of different sections
of a single nanowire, thereby revealing ion transport characteristics along the nano-
wire (Figure 10J). Porous graphene wrapping on a single nanowire will not only
improve electronic conductance but will also maintain efficient ion transport at the
interface between the nanowire electrode and the electrolyte, while a dense solid
graphene film coating hinders ion transport between the two (Figure 10K). These
two improved single-nanowire battery designs could potentially be combined
with newly developed micro-/nanoscale solid-state electrolyte patterns115 to fabri-
cate more advanced on-chip micro-/nanoscale SSB for comprehensive in situ
characterizations.
Conclusion and Perspectives

In this review we present the challenges associated with interfaces in SSBs, discuss
different types of solid-solid interfaces, and review a range of advanced character-
ization techniques. The challenges involving solid-solid interfaces can be generally
summarized as those pertaining to physical contact and chemical contact. Specif-
ically, two issues of interest involving physical contact are (1) the point contact be-
tween the electrolytes and electrodes that limits ionic transport, and (2) volume
changes during battery cycling that could result in contact failure. In contrast,
problems pertaining to chemical contact principally refer to side reactions between
electrolyte and electrodes, which significantly decrease the stability and increase
interfacial resistance. In short the major solid-solid interfaces consist of cathode-
electrolyte interface, anode-electrolyte interface, and interparticle interface. For a
cathode-electrolyte interface, the formation of a highly resistive interphase and/or
a Li-depleted layer at the interface between the sulfide electrolyte and the high-
voltage cathode represents a critical problem. For an anode-electrolyte interface,
the major issue is Li dendrite growth and penetration through solid electrolyte,
coupled with the side reactions between the sulfide electrolyte and Li anode. Inter-
particle interface should also not be neglected because continuous and efficient
ionic and electronic transport paths within composite electrodes are difficult to
achieve simultaneously. In addition, contact loss at the interfaces caused by the
volume variation of electrode materials during electrochemical cycling represents
a pervasive problem. It should be noted that even a slight volume change in interca-
lation-type materials would lead to severe contact failure in SSBs, which is a more
serious issue for alloy and conversion-type materials. Although a theoretical study
could provide a more nuanced understanding of the issues surrounding solid-solid
interface, advanced characterization techniques must be developed to determine
the required evidence experimentally. In particular, essential characterization tech-
niques include microscopy observation, chemical composition analysis, and electro-
chemical characterization.
On the basis of current knowledge surrounding interfaces in SSBs, we would like to

suggest some additional avenues for investigation. First, although a variety of
advanced characterization techniques have successfully determined important
Joule 2, 1–25, October 17, 2018 21

mechanisms associated with interfaces, most of them are ex situ characterizations

that do not offer sufficient real-time information. In contrast, in situ/operando
methods should be utilized to obtain a fundamental understanding of the composi-
tion and structures of interfaces, both of which are critical for designing SSBs. The
challenge for an in situ study is that the solid-solid interfaces are embedded in
SSBs, making it difficult to separate them (e.g., in liquid-electrolyte batteries).
Thus, on the one hand the rational design of battery configurations to expose the
interfaces at the micro-/nanoscale level should be considered for high-resolution
characterization in the laboratory. On the other hand, nondestructive characteriza-
tion techniques such as X-ray computed tomography could be very promising for
revealing the inner interfaces for scanning and tracking SSBs in industry. Second,
some applications rely on excellent power density only, while other applications
just require high-energy density. Thus, SSBs must be designed to meet the needs
of a broad range of applications, as it is unrealistic to assume that one type of battery
will satisfy all the high-performance requirements/parameters seen in industry. For
example, fine-tuning the ratio of active electrode particles and electrolyte particles
within a composite electrode could determine whether it is high-energy density or
high-power density.116 Third, in addition to metal ions, metal-air117 and metal-sul-
fur118 systems featuring much higher energy density should also be investigated
for use in SSBs. Last but not least, an important advantage of SSBs versus liquid-elec-
trolyte batteries is that SSBs are more feasible for miniaturization. Thus, SSBs exhibit
great potential for integration with microelectronic circuits—for example, in the
development of self-powered micro-/nanoscale biological sensors.119
ACKNOWLEDGMENTS
Y.-C.C. acknowledges funding from the 4th Yellow Crane Talent Program of Wuhan
City (08010004). C.L. acknowledges funding from China NSF (51703081). L.M. ac-
knowledges funding from the National Natural Science Fund for Distinguished
Young Scholars (51425204), National Key Research and Development Program of
China (2016YFA0202603), the National Basic Research Program of China
(2013CB934103), the Program of Introducing Talents of Discipline to Universities
(B17034), the Yellow Crane Talent (Science & Technology) Program of Wuhan
City, the National Natural Science Foundation of China (51521001), and the Funda-
mental Research Funds for the Central Universities (WUT: 2016III001, 2017III009).
L.X. acknowledges support from the Fundamental Research Funds for the Central
Universities (WUT: 2018IVA091).
AUTHOR CONTRIBUTIONS
Y.-C.C. and L.M. proposed the topic of the manuscript. L.X., S.T., Y.C., and K.W.
wrote the manuscript. Y.-C.C., L.M., L.X., S.T., Y.C., K.W., J.L., C.L., and F.W. dis-
cussed and revised the manuscript. L.X., S.T., Y.C., and K.W. contributed equally
to this work.
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Joule 2, 1–25, October 17, 2018 25

Interfaces in Solid-State Lithium Batteries

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Please cite this article in press as: Xu et al., Interfaces in Solid-State Lithium Batteries, Joule (2018), https://doi.org/10.1016/j.joule.2018.07.

Joule 2, 1–25, October 17, 2018 ª 2018 Elsevier Inc. 1

A solid-state system yields many intriguing advantages.16 First, a solid-state system

2 Joule 2, 1–25, October 17, 2018

of instability issues at the interface must be addressed. Second, in contrast to

Interfaces in Solid-State Batteries

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Figure 2. Open-Circuit Energy Diagrams of Different Battery Systems

others. This section features a detailed discussion of interphase formation and

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Interface between Cathode and Inorganic Electrolyte

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Figure 3. Typical Examples of Cathode-Electrolyte Interfaces in Solid-State Batteries

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Figure 4. Illustration of Nanoionics Effect in Sulfide Electrolyte Interface

space-charge layer effect. In many cases, capacity fading is caused by simultaneous

Interface between Anode and Inorganic Electrolyte

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Li cannot provide sufficient mechanical strength to prevent dendrite formation if

Interface between Polymer Electrolyte and Lithium Metal

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Figure 5. Lithium Nucleation, Growth, and Penetration

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molecular weight, adding substitute groups, crosslinking, copolymerization, and

In addition to Li dendrite penetration, chemical stability and Li-polymer adhesion

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Advanced Characterization Techniques

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As shown in Figure 7, there are numerous successful microscopic observations.

Chemical Composition Analysis

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Figure 7. Selection of Images Obtained via Various Microscopic Methods

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According to studies devoted to calculating the interfacial stability and design of

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Figure 8. Selective Examples of Chemical Examinations

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In addition, symmetrical cells can be assembled to elucidate the details surrounding

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Figure 9. Selective Examples of Electrochemical Tests

the interfacial connection (Figure 9D).11 As the IR drop is an indication of resistance,

Other Advanced Techniques

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Figure 10. VSFG and On-Chip Single-Nanowire Battery Characterizations

sum-frequency generation spectroscopy and (2) on-chip single-nanowire battery

Vibrational Sum-Frequency Generation Spectroscopy. Vibrational sum-frequency

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mechanism in LIB liquid-electrolyte batteries, Mukherjee et al. designed an in situ

On-Chip Single-Nanowire Battery Characterization. An on-chip single-nanowire

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of a H2V3O8 nanowire permanently decreases after deep discharge and charge.

Conclusion and Perspectives

On the basis of current knowledge surrounding interfaces in SSBs, we would like to

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mechanisms associated with interfaces, most of them are ex situ characterizations

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