Huang Et Al 2022 Solid State Batteries An Introduction

Chapter 1
Solid-State Batteries: An Introduction

Yonglin Huang, Bowen Shao, and Fudong Han*
Department of Mechanical, Aerospace, and Nuclear Engineering, Rensselaer Polytechnic

Institute, Troy, New York 12180, United States
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*Email: hanf2@rpi.edu
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The development of next-generation batteries has mainly transitioned to a concept

of the solid-state battery (SSB) because of its great potential for safe and high
energy density energy storage. This chapter aims to provide a brief introduction
of this promising technology. We first discuss its working principle by highlighting
the major difference between an SSB and a liquid-electrolyte based battery. We
then introduce the potential advantages of SSBs, including high safety, high energy
density, high power density, and a long cycle life. We also provide a chronological
overview of the development of a variety of solid electrolytes, which are the key
components of SSBs. We would like to emphasize that SSBs are not a new concept.
The development of SSBs was far earlier than that of commercialized lithium-ion
batteries. We conclude this chapter by discussing the remaining challenges for
future development of this technology.
Introduction
The conflict between the ever-increasing energy consumption and the public concern over
climate change demands a sustainable energy future for harvesting, storing, and delivering clean
energies. Rechargeable batteries that can reversibly convert electrical energy to chemical energy have
been considered as one of the most promising technologies for energy storage. Lithium-ion batteries
(LIBs) have succeeded in powering portable electronics and small electric tools. However, challenges
remain on the wide application of this technology in large-scale energy storage. Despite of the fact
that a gradual increase in the energy density of LIBs has been observed over the past three decades, it
has been predicted that the energy density values of LIBs will soon reach their physicochemical limit
(1). The continuous push on increasing the energy output of a smaller battery volume also leads to
serious safety concerns with many well-publicized battery fire accidents.
Liquid electrolytes are believed to be the root cause of many challenges of conventional LIBs.
They are typically made by dissolving lithium salts (such as LiPF6) into volatile and flammable
solvents. Most liquid electrolytes are not electrochemically stable at both high and low voltages,
hindering the utilization of high voltage cathodes such as LiNi0.5Mn1.5O4 and low-voltage anodes
such as silicon and Li metal (2, 3), thus limiting the energy density. In addition to the reactivity,
© 2022 American Chemical Society

Gupta; Solid State Batteries Volume 1: Emerging Materials and Applications
ACS Symposium Series; American Chemical Society: Washington, DC, 2022.
the utilization of liquid electrolytes with Li metal also faces serious challenges in the suppression
of short-circuit-causing dendrites. Therefore, applying nonflammable and electrochemically stable
solid electrolytes, including polymer, inorganic, and polymer-inorganic composites, to make solid-
state batteries (SSBs) has been considered as an effective approach to address these challenges.
Tremendous efforts have already been made to developing solid electrolyte materials during the
past decades, and the ionic conductivity of many solid electrolytes has been comparable to or even
higher than that of the conventional liquid electrolytes (4–6). Significant progresses have also been
made in understanding the key roles of the electrodes, electrolytes, and their interphases inside SSBs.
However, full-scale commercialization of SSBs has proven difficult because of challenges in both
manufacturing and fundamental understanding of this technology. Compared with a huge amount
of journal publications, the number of books that focus on SSBs is limited (7–11). This book aims
to provide an overview of the developments of emerging materials and their applications in SSBs.
This chapter provides a brief introduction of SSBs, from their working principles, advantages over
conventional LIBs, to the history of SSBs. At the end of the chapter, the remaining challenges for
future development of this technology are discussed. We hope that this chapter and the following
chapters will provide readers with a thorough and complete understanding of emerging materials and
battery types based on the solid state concept.
Working Principle of SSBs

The working principle of an SSB is the same as that of a conventional LIB, as shown in Figure 1.
During discharge, the cathode is reduced and the anode is oxidized, accompanied by the movement
of lithium ions from the anode to the cathode through the solid electrolyte, and the reverse process
occurs during charge. Almost all cathode and anode active materials used in LIBs can be applied
to SSBs with only a few exceptions because of the intrinsic instability between electrodes and solid
electrolytes. For example, LiFePO4, a well-known cathode for conventional LIBs, has not been
successfully used in thiophosphate-based SSBs because of the instability between LiFePO4 and
thiophosphate-based solid electrolytes. The major difference between an SSB and a conventional LIB
is the electrolyte material, and this difference also leads to many unique attributes of SSBs, which will
be introduced later.
SSBs can be divided into three types according to their geometry. The first one is thin-film
SSBs which are usually made by depositing dense layers of cathode, solid electrolyte, and anode
materials in sequence (Figure 2a). The total thickness of a thin-film battery is usually less than 15
µm. Such a thickness enables to use solid electrolytes with a relatively low ionic conductivity, and
the most successful electrolyte for thin-film batteries is lithium phosphorus oxynitride (LiPON)
which was developed by Dudney et al. from the Oak Ridge National Laboratory. Thin-film batteries
demonstrate excellent cycling stability of more than thousands of cycles. Because of transport
limitations in the dense and pure electrodes, the thickness of the electrode cannot be high and
therefore the areal capacity or the resulting energy of thin-film batteries is also limited. In order to
enhance the energy of the cell, three-dimensional SSBs were designed (Figure 2b). However, the
fabrication of three-dimensional SSBs with interdigitated electrode structure has proven difficult. The
third type is bulk-type SSBs (Figure 2c) in which the electrodes are mixed with electronically non-
conductive and ionically conductive electrolytes, an electrode structure similar to that in the liquid-
electrolyte LIBs. Thanks to the development of superionic solid electrolytes with ionic conductivity
close to or even higher than liquid electrolytes, electrodes with a thickness of a few hundreds of
microns have been used in the bulk-type SSBs, leading to a high energy of the cell.
2
Figure 1. The illustrations of (a) a conventional LIB and (b) an SSB during discharge. Reproduced with
permission from reference (12). Copyright 2020 Grady, Z. A.; Wilkinson, C. J.; Randall, C. A.; Mauro,
J. C., some rights reserved; exclusive licensee Frontiers Media S.A. Distributed under a Creative Commons
Attribution License 4.0 (CC BY) https://creativecommons.org/licenses/by/4.0/.
Figure 2. The structures of (a) a thin-film SSB, (b) a three-dimensional SSB, and (c) a bulk-type SSB.
Reproduced with permission from reference (13). Copyright 2018 Springer Nature.
Advantages of SSBs
High Safety
Unlike their liquid or polymer counterparts which have caused many fire accidents, inorganic
solid electrolytes are relatively difficult to ignite even if they are heated or highly oxidized. A detailed
study to compare the heat release of batteries with different electrolytes shows that SSBs possess a
much higher degree of safety than the conventional liquid-electrolyte batteries, as shown in Figure 3
(14), even though more quantitative studies are still needed to confirm the intrinsic safety of SSBs.
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In addition, solid electrolytes have the potential to prevent dendrite formation which is a serious
safety concern in liquid-electrolyte Li metal batteries (15). Furthermore, the thermal conductivity
of the solid materials is typically higher than that of the liquids, and therefore the utilization of
solid electrolytes may help eliminate the temperature hotspots inside the batteries. The non-uniform
temperature distribution within the battery has been reported to play an important role in initiating
direct Li plating in graphite anodes (16). Inorganic solid electrolytes can be more thermally stable at
higher temperatures than liquid electrolytes, as a result, SSBs can work more reliably than LIBs under
extreme high temperature conditions. It should also be noted that although many solid electrolytes
appear to show better thermal stability than liquid electrolytes, other safety concerns, such as the
release of toxic H2S gas because of exposure of thiophosphate-based solid electrolytes to ambient air,
should also be considered.
Figure 3. The all-inclusive microcell (AIM) structure used in the differential scanning calorimetry (DSC)
measurement, and the plot of safety degree of conventional LIB, SSB (represented as ALIB in Figure 3), and
SSB with Ketjenblack (KB) in the positive electrode (ALIB + KB). Reproduced with permission from
reference (14). Copyright 2017 American Chemical Society.
High Energy Density

One of the major motivations for the research and development of SSBs is the potential to
further increase the energy density. While simply replacing liquid electrolyte by solid electrolyte
to make an SSB does not help improve the energy density of the battery because of the higher
density of solid electrolyte, dramatic improvements in the energy density, both volumetrically and
gravimetrically, can be achieved by applying Li metal as the anode, as shown in Figure 4 (1).
Several solid electrolytes such as Li7La3Zr2O12 (LLZO) and Li1+xAlxTi2−x(PO4)3 (LATP,
0.3≤x≤0.5) have demonstrated excellent anodic stability (17), enabling the utilization of cathodes
with high potentials. In addition to the energy density gain of individual cells, the utilization of solid
electrolytes also enables bipolar stack in which multiple battery layers are stacked inside one single
package and therefore can significantly reduce the dead space and inactive parts compared with the
series connection of conventional LIBs (Figure 5) (18, 19). In this regard, SSBs demonstrate unique
advantages in increasing the energy density, especially the volumetric energy density, at the pack
level.
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Figure 4. Typical battery structures and corresponding changes in volumetric (Wvol) and gravimetric
(Wgrav) energy densities. A conventional LIB is composed of porous anode (circles to the left of the
separator), porous cathode (circles to the right of the separator), separator (the board with a thickness of 10
µm), and liquid electrolyte (the remaining space). For lithium-ion SSB (LI-SSB), separator and liquid
electrolyte are replaced by solid electrolytes. In an SSB using Li metal anode (LiM-SSB), both volumetric
and gravimetric energy densities are improved compared to LIB. Reproduced with permission from reference
(1). Copyright 2016 Springer Nature.
Figure 5. (a) Conventional series connection of liquid-electrolyte LIBs. (b) Bipolar design of multiple SSBs
in one package. Reproduced with permission from reference (18). Copyright 2017 Springer-Verlag Berlin
Heidelberg.
High Power Density

The replacement of liquid electrolytes with solid ones will cause dramatic changes in the nature
of the interfaces between electrodes and electrolytes. While many difficulties in both fundamental
understanding and optimization of the interfaces between solid electrolytes and solid electrodes
remain to be addressed, it has been demonstrated that SSBs may provide a higher power density
than conventional liquid-electrolyte LIBs (19). The excellent kinetic performance of SSBs is mainly
because of the following reasons. First, the ionic conductivity of many solid electrolytes has been
comparable to or higher than that of liquid electrolytes, especially at low temperatures (Figure 6a).
Considering that the lithium-ion transference number of solid electrolytes is very close to one,
which is much higher than that of conventional liquid electrolytes, lithium transport in many solid
electrolytes is indeed faster than that in liquid electrolytes. The depletion of lithium concentration
in the graphite anode of a liquid-electrolyte battery was considered as one of the major challenges
for developing fast-charging liquid-electrolyte batteries (20). The near unity lithium-ion transference
number also eliminates the concentration polarization in the electrolyte of the cell, and the higher
lithium concentration (36 mol/L in solid electrolytes vs. 3 mol/L in liquid electrolytes) also provides
sufficient lithium ions for charge transfer reaction at fast rates (Figure 6b). In addition, the utilization
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of solid electrolytes also eliminates the de-solvation process that has been demonstrated resistive in
some conventional liquid-electrolyte batteries. As a result, very fast charge transfer kinetics has been
observed at the Li/solid electrolyte interfaces (21), and the areal specific resistance between Li and
Li7La3Zr2O12 (LLZO) solid electrolyte can be negligibly small (0.1 ohm/cm) (22).
Figure 6. (a) Arrhenius plot of Li10GeP2S12 (LGPS) solid electrolyte and 1 M LiPF6 in EC/PC liquid
electrolyte. (b) Lithium concentration profiles in a liquid-electrolyte battery and an SSB.
Compared with SSBs using the same battery configuration and resistance, Kato et al. showed
that the room temperature capacity of conventional liquid-electrolyte batteries decreased more
rapidly at a high current density (19). This result indicates the potential of fast-charging of SSBs over
conventional liquid-electrolyte LIBs, which is attributed to the nature of solid electrolytes. Besides,
the extremely high ionic conductivities of Li10GeP2S12 (LGPS)-type solid electrolytes also enabled
SSBs to operate at −30 °C with a much better performance than conventional liquid-electrolyte
LIBs, as shown in Figure 7. Therefore, one potential advantage of SSBs is the ability to work under
extreme low temperature conditions (19).
Figure 7. (a) Arrhenius plot of Li9.6P3S12, Li9.54Si1.74P1.44S11.7Cl0.3 and the LGPS-family solid
electrolytes. (b) Rate performance of an SSB (LiNbO3-coated LiCoO2 + LGPS|LGPS|Li4Ti5O12 +
LGPS, solid line) and an LIB (LiNbO3-coated LiCoO2|1 M LiPF6 in EC/PC|Li4Ti5O12, dashed line) at
a temperature of −30 °C (1 C = 0.667 mA/cm2). Adapted with permission from reference (19).
Copyright 2016 Springer Nature.
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Long Cycle Life
SSBs are also considered as a promising technology to improve battery cycle life. One main
reason for the capacity decay of conventional liquid-electrolyte batteries is the parasitic reactions
which are often related to the electrochemical decomposition of liquid electrolytes. In this regard, the
utilization of electrochemically more stable solid electrolytes can suppress these side reactions and
thus improve the cycle life. It should be indicated that the intrinsic electrochemical stability windows
of many solid electrolytes, for example the thiophosphate ones, are also limited and therefore
interphases will also be formed at the electrode/solid electrolyte interfaces. However, because of the
immobile feature of solid electrolyte, the interphases formed in SSBs are much less dynamic than
those in the liquid-electrolyte LIBs where repeated fracture and re-formation of solid electrolyte
interphases can occur partly because of the infiltrative nature of liquid electrolytes (23). In addition,
solid electrolytes can prevent the chemical crosstalk between cathodes and anodes, which will help
improve the cycling stability because the dissolved transition metal ions from cathodes can diffuse
onto anode surfaces through liquid electrolytes and lead to continuous formation of solid electrolyte
interphases on anodes (24). The utilization of solid electrolytes also enabled many electrodes that can
be dissolved into the liquid electrolytes, such as LiTi2(PS4)3 (25) and some organic electrodes (26).
Because of all these mentioned attributes, SSBs are considered as a promising technology for long
cycle life batteries. In fact, stably cycling for thousands of times have been demonstrated in a thin-film
SSB with Li metal anode, 5-V LiNi0.5Mn1.5O4 cathode, and LiPON solid electrolyte, as shown in
Figure 8 (27).
In addition to a long cycle life, the suppression of parasitic reactions in SSBs may also improve
the calendar life. Negligible self-discharging is observed for thin-film SSBs with Li metal anodes,
as shown in Figure 9 (28), while a quick capacity loss during storage has been observed for liquid-
electrolyte Li metal batteries (29).
History of SSBs
Even though SSBs have attracted intense interest from both industry and academia, they are not
a new concept. The first SSB was developed way before the first liquid-electrolyte based batteries. In
this session, we provide a brief overview of the history of SSBs and solid electrolyte development.
1800–1980
The development of solid ionic conductors started with silver-ion conductors. Faraday
discovered the solid state transport of Ag+ ions in Ag2S in 1833 (30). Prior to 1960s, the most
conductive solid electrolyte known is AgI and its ionic conductivity value is about 10-6 S/cm at
25 °C (30, 31). Because of the low ionic conductivity, solid electrolytes had not been used in
industrial batteries. In 1960s, high ionic conductive Ag3SI solid electrolyte was developed, and the
ionic conductivity is 0.015 S/cm at room temperature (30), which exceeds that of AgI by four orders
of magnitude. Ag3SI solid electrolyte was incorporated into a Ag|Ag3SI|I2 SSB by Takahashi and
Yamamoto after its discovery (32). In 1967, two laboratories independently discovered RbAg4I5 with
an ionic conductivity higher than 0.1 S/cm; Bradley and Greene reported a conductivity value of
0.12 S/cm, while Owens and Argue observed a slightly larger value of 0.21 S/cm (33, 34).
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Figure 8. (a) Capacity retention and (b) Coulombic efficiency of high voltage LiNi0.5Mn1.5O4||Li
batteries. The solid electrolyte is LiPON, the liquid electrolyte is 1.2 M LiPF6 dissolved in a solution of EC/
DMC (1:2 by vol). All batteries were cycled under a rate of 5 C. Reproduced with permission from reference
(27). Copyright 2014 WILEY-VCH Verlag GmbH & Company KGaA, Weinheim.
Figure 9. Capacities of three Li|LiPON|LiCoO2 thin-film batteries when they were rapidly discharged after
the long-term storage in the fully charged state. Reproduced with permission from reference (28). Copyright
2005 Elsevier.
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In 1967, Ford Company reported the sodium-ion conductive sodium β-Alumina, which had
the empirical formula Na2O·11Al2O3 (35). LiI was one of the first materials used in lithium solid
electrolytes, and it is chemically stable with negative electrode materials such as Li metal. However,
its ionic conductivity is only 10-7 S/cm at 25°C. Successful utilization of LiI electrolyte into a primary
non-rechargeable solid state Li metal batteries for implantable cardiac pacemakers was demonstrated
in 1971 where a thin LiI electrolyte layer was in-situ formed after the anode Li and the cathode I2
are in contact with each other (36). Two years later, incorporating LiI into Al2O3 was found to be an
effective approach to increase the ionic conductivity to the order of 10-5 S/cm (37). In addition, Li3N
was also proposed as a solid electrolyte (38). However, the ionic transport is anisotropic in Li3N, and
the direction of maximum ionic conductivity was found to be parallel to Li3N lattice planes.
At a similar time, Armand et al. proposed to use lithium salts dissolved in polyethylene oxide
(PEO) and polypropylene oxide (PPO) as solid polymer electrolytes (39). The ionic motion inside
these polymer electrolytes is quite different from that in the inorganic solid electrolytes. From Figure
10, the Li+ ion motion is achieved by the hopping through polymer chains (40). The excellent
mechanical property of polymer electrolytes also facilitated their integration into SSBs.
Figure 10. Mechanism of lithium-ion transport in PEO-based electrolyte. Reproduced with permission from
reference (40). Copyright 2015 Royal Society of Chemistry.
Na1+xZr2P3-xSixO12 system (0≤x≤3), which was named as NASICON for sodium superionic
conductor, was first proposed by Goodenough et al. in 1976. The sodium ionic conductivity reached
0.2 S/cm at 300°C, which is attributed to the rigid three-dimensional conduction network with
three-dimensionally interconnected interstitial spaces (41). In 1978, Li14Zn(GeO4)4 (LISICON)
was reported to have a lithium ionic conductivity value of 0.125 S/cm at 300°C (42). This high
ionic conductivity was also attributed to the three-dimensional lithium conducting pathways in the
material. The diameter of the bottleneck between these interstitial spaces was more than twice the
sum of the radii of Li+ and O2- ions. Moreover, the Li-O bonding strength was weakened because
one O2- anion was bonded to four network cations.
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1980–2000
In 1985, Kelly et al. studied the effects of PEGDME additive on the room temperature ionic
conductivity of lithium salts-PEO polymer complexed electrolyte, and an optimized ionic
conductivity of 10-4 S/cm can be achieved at 40°C (43). In order to minimize the migration of
anions in polymer electrolytes, in 1989, Armand et al. recommended to complex PEO with lithium
bis(trifluoromethanesulfonyl)imide (LiTFSI) since this salt contained large anions (44). For solid
polymer composite electrolytes, research on the influence of inorganic additives on polymer
complexes began in 1982. Imperial College of Science and Technology reported that 10 vol.% α-
Al2O3 additive would reduce the ionic conductivity of LiClO4-PEO electrolyte, and the lithium-ion
transference number maintained at about 0.25 between 110 and 130 °C (45). On the other hand, in
1998, Croce et al. found that nanometer sized ceramic powders such as Al2O3 and TiO2 can make
the ionic conductivity of LiClO4-PEO electrolyte reach 10-4 S/cm at 50 °C and 10-5 S/cm at 30°C
because of the suppressed crystallization of the polymer (46).
Hong et al. studied the replacement of Na+ ions in the NASICON solid electrolyte with Li+,
Ag+ and K+ ions through ion exchange in molten salt (47). However, the ionic conductivity of
Li1+xZr2P3-xSixO12 system was poor at room temperature. Improvement in the ionic conductivity
of Li1+xZr2P3-xSixO12 electrolyte was achieved by replacing Zr4+ ions with smaller Ti4+ ions and
Li1.3Ti2Si0.3P2.7O12 exhibited a room temperature ionic conductivity of 3.2 × 10-4 S/cm. Because
of the densification of sintered products, mixing Li2O and other binders with LiTi2P3O12 was also
effective in conductivity enhancement. As reported in 1990, the room temperature ionic
conductivity increased from 2 × 10-6 S/cm to 3.6×10-4 S/cm after adding 30 mol% Li2O during
sintering. Partial substitution of Ti4+ sites with Al3+ ions can increase the ionic conductivity of
Li1.3Al0.3Ti1.7P3O12 (LATP) to 7 × 10-4 S/cm (48). Similarly, the ionic conductivity of
LiGe2P3O12 partially substituted by Al3+ and Cr3+ was also increased. The highest room
temperature ionic conductivity value of 2.4 × 10-4 S/cm was obtained for Li1.5Al0.5Ge1.5P3O12
(LAGP) in 1992 (49). In 1993, on the basis of the nominal composition of LiLaTi2O6 (LLTO), the
perovskite-structure compound with a real composition of Li0.34La0.51TiO2.94 was synthesized. The
total ionic conductivity of this solid electrolyte was 2 × 10-5 S/cm, while the bulk ionic conductivity
was 1 × 10-3 S/cm. Figure 11 shows the crystal structure of LLTO (50) . However, one major issue
for this solid electrolyte materials is its instability at low voltages. Ti contained in the compound
will be reduced when it is combined with Li metal, and the reduction of Ti4+ ions can significantly
increase the electronic conductivity of this solid electrolyte (51).
During this period, thin-film lithium batteries were successfully developed. The milestone work
was done by Dudney et al. at the Oak Ridge National Laboratory who discovered a new type of
thin-film solid electrolyte, Li3.3PO3.9N0.17, which is also called lithium phosphorus oxynitride or
LiPON. The thin electrolyte layer was prepared by RF magnetron sputtering of Li3PO4 in pure N2
atmosphere and it showed an ionic conductivity of 2.2 × 10-6 S/cm at 25°C. More importantly,
this amorphous film was stable when in contact with Li metal (52). In 1999, the RF magnetron
sputtering deposited LiCoO2|LiPON|SiSn0.87O1.20N1.72 thin-film battery provided a discharge rate
of up to 10 mA/cm2 in the most useful voltage range of 1.0 to 2.8V at room temperature. Besides, this
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battery can be heated to 250°C in air, so it can be integrated into the assembly of electronic circuits
(53). With the microstructure shown in Figure 12, the LiCoO2|LiPON|Li thin-film battery had been
cycled for more than 50000 cycles (54).
Figure 11. Crystal structure of LLTO. Reproduced with permission from reference (50). Copyright 2003
American Chemical Society.
Figure 12. (a) The structure of thin-film batteries fabricated at the Oak Ridge National Laboratory. (b) The
scanning electron microscopy image showing the cross-sectional view of a thin-film battery with deposited
LiMn2O4 cathode. Adapted with permission from reference (54). Copyright 2000 Elsevier.
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In addition to oxide and polymer based solid electrolytes, thiophosphate-based solid electrolytes
have also been developed during this period. Mercier et al. studied the lithium-ion conduction
in Li2S-P2S5-LiI glassy solid electrolyte and its ionic conductivity can be as high as 10-3 S/cm
(55). In 1991, Jansen and Henseler synthesized a sodium thiophosphate-based solid electrolyte,
Na3PS4, through solid state reactions of sodium, sulfur and tetraphosphorus decasulfide. The ionic
conductivity was 4.17 × 10-6 S/cm at 50 °C and 8.51 × 10-2 S/cm at 510 °C (56).
2000–2020
Thiophosphate-Based Solid Electrolytes

The excellent mechanical properties of thiophosphate-based solid electrolytes make it possible
to fabricate SSBs by simple cold pressing (57), and therefore during this period tremendous works
have been done on increasing the ionic conductivity of thiophosphate-based solid electrolytes.
Several types of thiophosphate-based solid electrolytes, including Li2S-P2S5 glass and glass ceramics,
thio-LISICONs, and lithium argyrodites, will be discussed here.
Li2S-P2S5 binary phases with glass, glass-ceramic, and crystalline structures have been studied
as solid electrolytes by the researchers from Tatsumisago group. The binary system maintains the
amorphous structure with the Li2S content of up to 75 mol %, and the highest ionic conductivity
of 2~3 × 10-4 S/cm was achieved for glass-state 75Li2S-25P2S5 at room temperature (58, 59).
Some other binary glass-state systems show similar ionic conductivities, such as Li2S-B2S3 and Li2S-
SiS2 show an ionic conductivity of 10-4 S/cm (60–62), but Li2S-GeS2 has a lower conductivity
of 10-5~10-7 S/cm (63). To further improve the ionic conductivity, the precipitation of superionic
crystalline phases can be achieved by heat treatment and composition control to produce a more
conductive glass-ceramic structure. For example, the precipitation of low ionic conductive Li4P2S6
and Li3PS4 phases or metastable superionic Li7P3S11, Li4P2S7, and Li3.25P0.95S4 phases is related
to the Li2S content and heat treatment temperature (58, 64, 65). The γ-Li3PS4 (3×10-7 S/cm) can
be converted to β-Li3PS4 showing an abrupt improvement of ionic conductivity to 3×10-2 S/cm at
500 K (66, 67). High energy ball milling can also form this partially crystallized structure since the
collision heat is able to recrystallize part of the electrolytes (68, 69). Solution synthesis is suitable
to make glass ceramics in large scale for industrial application (70, 71). However, the complete
crystallization would magnify the negative influence of grain boundary resistance, causing the ionic
conductivity to be about one to two orders of magnitude lower than that of the amorphous structure
(72). Besides, the amorphous structure is believed to provide higher ionic conductivity than the
crystalline structure because of the open structure and large free volume (66, 67). Hot pressing can
effectively remove the porosities and grain boundaries, and an impressive ionic conductivity of 1.7 ×
10-2 S/cm was observed for the densified glass-ceramic 70Li2S-30P2S5 at room temperature (5).
Replacing the O2- ions in the LISICON solid electrolyte by large and polarizable S2- ions to
make the thio-LISICON materials has also been pursued to improve the ion mobility by Kanno
and Murayama (73). They introduced lithium ionic conductor Li4-xGe1-xPxS4 (x=0.75) with a high
ionic conductivity of 2.2×10-3 S/cm at room temperature (73). In 2011, the same research group
reported LGPS with a greater ionic conductivity of 1.2×10-2 S/cm, which even exceeds the ionic
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conductivity of organic liquid electrolytes (6). Thio-LISICON can be divided into three composition
regions (0 < x ≤ 0.6, 0.6 < x < 0.8, and 0.8 ≤ x < 1.0). Li3.25Ge0.25P0.75S4 and LGPS are
located in the region II which has a special monoclinic superstructure and therefore a higher ionic
conductivity than the other two regions (74). The detailed LGPS crystal structure is shown in Figure
13. The unit cell consists of (Ge0.5P0.5)S4 tetrahedra, LiS6 octahedra, PS4 tetrahedra and LiS4
tetrahedra. Along the c axis, a one-dimensional chain is formed by (Ge0.5P0.5)S4 tetrahedra and LiS6
octahedra through sharing a common edge, and PS4 tetrahedra can connect LiS6 octahedra from
different chains to form the three-dimensional framework. LiS4 tetrahedra in the 16h and 8f sites can
share a common edge with each other to form the one-dimensional conduction pathway, and these
conduction pathways are also connected by the common corners of LiS4 tetrahedra (6). In 2016,
Li9.54Si1.74P1.44S11.7Cl0.3 (LSPSCl) also with LGPS-type crystal structure was reported by the
same group and this electrolyte showed the highest room temperature ionic conductivity of 2.5×10-2
S/cm (19). SSBs using Li9.54Si1.74P1.44S11.7Cl0.3 (LSPSCl) solid electrolyte demonstrated superior
rate performance than the conventional liquid-electrolyte batteries.
Figure 13. (a) (b) Crystal structure and (c) conduction pathways of LGPS. Reproduced with permission
from reference (6). Copyright 2011 Springer Nature.
Lithium argyrodite Li6PS5X (X = Cl, Br, or I) is another family of fast lithium-ion conductor.
The high ionic conductivity of argyrodites is based on two reasons: a soft framework for lithium-ion
migration and the disorder associated with halide ions. The network of isolated PS4 tetrahedra forms
connected hexagonal cages for lithium-ion migration. The framework constructed by PS4 tetrahedra
is with relative soft stiffness that lowers the activation energy for conduction. Halide ions Cl- and
Br- form sublattice with S2- ions, which results in the disorder, benefiting ionic conductivity. The
ordering of I- ions induces the low ionic conductivity. In 2020, a prototype pouch cell (capacity: 0.6
Ah, Figure 14) using Li6PS5Cl solid electrolyte showed a superior cycle life of more than 1000 times.
From this work, the ionic conductivity of Li6PS5Cl (LPSCl) sulfide electrolyte mixed with a binder
was 1.31×10-3 S/cm (75).
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Figure 14. (a) The structure of a 0.6 Ah pouch cell. The composite cathode is composed of Li2O/ZrO2-
coated LiNi0.90Co0.05Mn0.05O2, LPSCl, polytetrafluoroethylene binder, and carbon nanofibers. The
thickness of LPSCl solid electrolyte is 30 µm. The Ag-C anode layer is prepared by mixing Ag and carbon
black powders in a weight ratio of 1:3. (b) The rate performance of this pouch cell at 60 °C (1.0 C = 6.8
mA/cm2). Adapted with permission from reference (75). Copyright 2020 Springer Nature.
Lithium Garnet Oxide Solid Electrolytes

Garnet-type oxides, whose general formula can be presented as A3B2(XO4)3 (A is the 8-
coordinated hexahedral cation such as Mg, Ca, Y, La, and rare earth elements; B is the 6-coordinated
octahedral cation such as Al, Mn, Fe, Ni, Ga, Ge, and V; X is the 4-coordinated tetrahedral cation
such as Si, Ge, Al) with a space group Ia d, is a type of well-studied structural family. The first
lithium-based garnet oxide Li3Ln3M2O12 (Ln = Y, Pr, Nd, Sm-Lu; M = Te, W) was reported
in 1968 (76). In 2003, Li5La3M2O12 (M = Nb, Ta) with a garnet structure was reported as a
lithium-ion conductor, and it exhibited an ionic conductivity of ~10-6 S/cm at 25 °C (77). A higher
content of Li+ ions per unit, so called “Li-excess” or “Li-stuffed” was considered as an effective
approach to further improve ionic conduction. For garnet-type solid electrolytes with higher lithium
content, lithium cannot be completely accommodated by the tetrahedral sites so the octahedral
sites will be occupied by the excess lithium. In order to increase the lithium content in the garnet
structure, aliovalent substitution is applied which leads to lithium ions distributing in the tetrahedral
and octahedral sites, and thus increases the ionic conductivity of garnet-type solid electrolytes.
Figure 15 shows the occupation of lithium sites in the cubic garnet unit and the corresponding
ionic conductivity (78). The ionic conductivity increases with the increased occupation in the highly
mobile octahedral sites and decreases with the lithium content because of the ordering of Li+ ions
at high lithium content. While the reduction of Zr and other dopants such as Al and Nb has been
reported (79, 80), lithium garnet based oxide electrolyte is still by far one of the most stable solid
electrolytes when in contact with Li metal anodes (81), offering great promises for the development
of solid state Li metal batteries.
Many reported references of possible solid electrolytes are limited to the fundamental research
on ionic conductivity and ion transport mechanisms. It should be noted that the integration of
solid electrolytes into SSBs depends not only on ionic conductivity, but also on electrochemical
stability, mechanical properties and so on. For example, Li3N decomposes under high voltages,
which restricts the use of high voltage cathode materials in SSBs. So far, polymer, LiPON, and
thiophosphate-based solid electrolytes have been successfully integrated into SSBs.
14
Figure 15. The variation of lithium site occupancy and room temperature ionic conductivity as a function of
lithium content per cubic garnet unit. Reproduced with permission from reference (78). Copyright 2015
John Wiley & Sons.
Remaining Challenges for Future Development of SSBs

Past decades have observed dramatic increase in the ionic conductivity of solid electrolytes,
and the development of superionic solid electrolytes with ionic conductivity comparable to or even
higher than that of conventional liquid electrolytes laid the foundation for the development of SSBs.
However, it has been recognized by the community that ionic transport is not the only property
that is needed for a high-performance SSB. A thorough understanding of some other properties of
solid electrolytes, including electronic conductivity (82), electrochemical stability (79), mechanical
property (83), thermal stability (84), processibility and scalability (85), is also necessary. Besides,
the interfacial stability between electrodes and solid electrolytes is fundamentally different from that
in conventional LIBs and thus future efforts are needed to understanding and addressing the large
interfacial resistance between solid electrodes and solid electrolytes. Given the challenges of using Li
metal as anodes for SSBs, alternative anodes including three-dimensional Li metal anodes or alloy
anodes may be needed to realize the advantages of SSBs. Although many key challenges still exist for
the full-scale commercialization of this technology, with a concerted effort all over the world from
both academia and industry, it is reasonable to expect the bright future for the SSB development.
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Chapter 1

Solid-State Batteries: An Introduction

Department of Mechanical, Aerospace, and Nuclear Engineering, Rensselaer Polytechnic

The development of next-generation batteries has mainly transitioned to a concept

© 2022 American Chemical Society

Working Principle of SSBs

High Energy Density

High Power Density

Thiophosphate-Based Solid Electrolytes

Lithium Garnet Oxide Solid Electrolytes

Remaining Challenges for Future Development of SSBs

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