Research Article

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Super Long-Cycling All-Solid-State Battery with Thin

Li6PS5Cl-Based Electrolyte
Sijie Liu, Le Zhou, Jian Han, Kaihua Wen, Shundong Guan, Chuanjiao Xue,
Zheng Zhang, Ben Xu, Yuanhua Lin, Yang Shen,* Liangliang Li,* and Ce-Wen Nan*

high interfacial impedance between SSEs

All-solid-state batteries (ASSBs) using sulfide electrolytes have attracted ever- and electrodes, and relatively high fabrica-
increasing interest due to high ionic conductivity of the sulfides. Neverthe- tion cost, which impede their applications.
less, a thin, strong solid-state sulfide electrolyte membrane maintaining high SSEs with high ionic conductivity, wide
electrochemical window and low interfa-
ionic conductivity is highly desired for ASSBs. Here, a thin, flexible composite
cial impedance are critical in developing
solid electrolyte membrane composed of argyrodite sulfide Li6PS5Cl and a ASSBs with high specific energy and
polar poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)) framework is power density.[2,3]
prepared via an electrospinning-infiltration-hot-pressing method. The interac- Currently, among various SSEs, sulfide
tion between Li6PS5Cl and polar P(VDF-TrFE) ensures a high lithium-ion con- SSEs have a Li-ion conduction capability
comparable to that of organic liquid
ductivity (≈1.2 mS cm–1) at room temperature and good mechanical ductility
electrolytes (≈10–2 S cm–1 at room tem-
of the composite electrolyte membrane. The coin-type ASSB cells with the perature).[4–10] Various sulfide materials
thin composite electrolyte membrane, a composite cathode of LiNbO3-coated with a high Li-ion conductivity of 10–3–
LiNi0.8Co0.1Mn0.1O2 and Li6PS5Cl, and a lithium-indium anode, show super 10–2 S cm–1 at room temperature, such
cycling performance, and the capacity retention is 92% after 1000 cycles and as Li10GeP2S12 (LGPS),[5] Li10SnP2S12,[6]
71% even after 20 000 cycles at 1.0 mA cm–2 (i.e., 1.61 C) at room temperature. and Li9.54Si1.74P1.44S11.7Cl0.3,[7] have been
investigated. Among them, a family of
Moreover, pouch-type ASSB cells with a high mass loading of active materials
sulfide SSEs, lithium argyrodites Li6PS5X
are made to demonstrate the potential and feasibility in future commercial (X = Cl, Br),[8] are attracting more atten-
applications. tion due to high Li-ion conductivity
(e.g., Li5.3PS4.3ClBr0.7: 2.4 × 10–2 S cm–
1 [9]
; Li6PS5Cl (denoted as LPSCl):
1. Introduction 3.15 × 10–3 S cm–1 [10]) and relatively good electrochemical com-
patibility. The ASSB cells using argyrodites have demonstrated
Lithium (Li)-ion batteries (LIBs) have been widely used in port- good cycling and rate performance. For example, recently, a
able electronic devices, electric vehicles, smart grids, etc.[1] sandwiched SSE separator of LPSCl-LGPS-LPSCl has been
However, organic liquid electrolytes in commercial LIBs are designed to prevent the growth of Li dendrites and thus enable
flammable due to the low flash point of carbonic ester, espe- superior cycling performance of ASSB cells;[11] and LPSCl SSE
cially at high voltages, which often causes safety hazards in has also been matched with the silicon anode, capable of oper-
practical applications. Thus, all-solid-state batteries (ASSBs) ating with high current densities and achieving a long cycle.[12]
using solid-state electrolytes (SSEs) have recently attracted a One drawback of pressed sulfide SSE separator layers is that
lot of interest, because they are safer and more stable after the micro-cracks easily appear and expands during Li plating/strip-
replacement of liquid electrolytes.[2] Nevertheless, ASSBs still ping in sulfide electrolytes due to the rigidness of sulfide pow-
have some drawbacks such as low ionic conductivity for SSEs, ders, leading to short circuit in ASSB cells.[13] Thus a thicker
sulfide SSE layer (e.g., ≈0.5–1.2 mm) via pressing sulfide
S. Liu, L. Zhou, J. Han, K. Wen, S. Guan, C. Xue, Z. Zhang, Y. Lin, powder was usually used in laboratory-type cells to guarantee
Y. Shen, L. Li, C.-W. Nan the long-term cycling performance of the ASSBs,[13a,b,14] but this
State Key Laboratory of New Ceramics and Fine Processing way reduces the cell-level energy density and is detrimental to
School of Materials Science and Engineering
scalable fabrication. Thus, it is desired to prepare sulfide SSE
Tsinghua University
Beijing 100084, China membranes with a small thickness and compact structure for
E-mail: shyang_mse@tsinghua.edu.cn; liliangliang@tsinghua.edu.cn; advanced ASSBs.
cwnan@tsinghua.edu.cn To obtain a thin, free-standing sulfide SSE membrane, a soft
B. Xu polymeric component is often used. Recently, much progress
Beijing Computational Science Research Center in sulfide-polymer composite solid electrolytes (CSEs) has been
Beijing 100084, China
made.[15–18] Among them, Luo et al. prepared a 65 µm-thick
The ORCID identification number(s) for the author(s) of this article bendable sulfide SSE using LPSCl and poly(ethylene
can be found under https://doi.org/10.1002/aenm.202200660.
oxide) (PEO),[16] and their ASSB cell of LiNi0.7Co0.2Mn0.1O2
DOI: 10.1002/aenm.202200660 (LiNixCoyMn1–x–yO2, denoted as NCM)||CSE||lithium-indium

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(Li-In) delivered 1000 cycles with a capacity retention of 74% at
60 °C. Oh et al. prepared a 80 µm-thick CSE composed of Li+-
conductive dry polymer electrolytes (nitrile butadiene rubber-
poly(1,4-butylene adipate)) and sulfide Li6PS5Cl0.5Br0.5, which
exhibited a high Li-ion conductivity of 2.2 mS cm–1 at 30 °C and
excellent thermal stability.[17] Their NCM||CSE||graphite ASSB
cells showed a capacity retention of 86% after 100 cycles at 0.1 C
and 30 °C. Lee et al. prepared 30–40 µm-thick CSEs composed
of LPSCl and a non-aqueous acrylate-type binder by using a
doctor blade,[18] and their NCM||CSE||Ag-C prototype pouch
cell exhibited a capacity retention at 89% after 1000 cycles at
0.5 C and 60 °C. These efforts mainly emphasized increasing
the energy density of ASSB cells by thinning CSE layers and
did not focus on the cycling performance of ASSBs. The cycle
life and rate performance of the ASSBs with thin CSE mem-
branes in these works are not well satisfactory. The thickness
of CSE membranes may play an important role in determining
the cycling performance of ASSBs.[19] In addition, the study on
comparing the cycling performance of ASSBs to that of normal
LIBs with liquid electrolytes is rare.
Herein, we report a thin (30–40 µm-thick) CSE made of
LPSCl and a three dimensional poly(vinylidene fluoride-co-
trifluoroethylene) P(VDF-TrFE) network skeleton via a facile
electrospinning-infiltration-hot-pressing method. P(VDF-
TrFE) exhibits more stronger polarity with high dielectric con-
stant and is more flexible than commonly used PVDF, since
P(VDF-TrFE) has a dominant β-phase with an all-trans confor-
mation by incorporating TrFE groups into PVDF.[20] Thus it is
expected that P(VDF-TrFE) has some interactions with LPSCl
to ensure excellent performance of the CSE. A well-designed
P(VDF-TrFE) electrospun framework with an adjustable porous
structure allows thorough infiltration of LPSCl particles to
form interpenetrating LPSCl@P(VDF-TrFE) membranes. The
closely packed sulfide particles form Li-ion conduction chan-
nels, while the P(VDF-TrFE) component makes the whole elec-
trolyte flexible and bendable. We demonstrate the interaction
between LPSCl and polar P(VDF-TrFE) to improve Li+ trans-
port in the CSE through various tests and theoretical simula-
tions. The as-prepared CSE shows high Li-ion conductivity of
1.2 × 10–3 S cm–1 at room temperature. In particular, the ASSB
cells with the CSE membranes present super cycling perfor-
mance, i.e., the ultra-long cycle life with 71% capacity retention
after 20 000 cycles at 1.0 mA cm–2 (i.e., 1.61 C) among all so-far
reported ASSB cells operated at room temperature. This work
may shed light on preparing thin, high-performance CSEs, and
pave the way toward practical sulfide-based ASSBs with high
performance.
2. Results and Discussion
2.1. Characterization of LPSCl@P(VDF-TrFE) CSEs
Figure 1a schematically illustrates the fabrication procedure of
the interpenetrating LPSCl@P(VDF-TrFE) CSEs. Here, argyro-
dite LPSCl powder was prepared by ball-milling, followed by
heat treatment as before.[10] The X-ray diffraction (XRD) pattern
of as-prepared LPSCl powder and the Nyquist plot of the LPSCl
electrolyte at room temperature are shown in Figure S1a,b
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(Supporting Information), respectively. The room-temperature
ionic conductivity of the LPSCl electrolyte is about 3.9 mS cm–1.
The as-prepared LPSCl powder was grinded for preparing CSEs.
The scanning electron microscopy (SEM) images in Figure S2
(Supporting Information) show that the LPSCl particles after
grinding and sifting have a smaller diameter (about 1–3 µm
as shown in Figure S3, Supporting Information) compared to
pristine powder. As for the polymeric part, the viscoelastic and
strong polar P(VDF-TrFE) with high dielectric constant was
chosen.[20] A self-supporting P(VDF-TrFE) electrospun mem-
brane with an adjustable porous framework structure with void
diameter of about 10–20 µm was fabricated. The SEM image in
Figure 1b clearly shows the porous network structure made of
uniform fibers with a narrow diameter distribution (Figure S4,
Supporting Information). Large voids in the framework are
important for the infiltration processing of sulfide particles.
High thermal stability (Figure S5, Supporting Information) of
the P(VDF-TrFE) is suitable for the subsequent hot-pressing
process and is helpful to improve the thermal stability of the
CSEs. With infiltration of LPSCl-toluene slurry into the porous
P(VDF-TrFE) framework, following by solvent evaporation
and hot-pressing (see Experimental Section), the free-standing
CSE membranes (about 30–40 µm in thickness) with good
mechanical ductility and bendability were obtained, as shown
in the photograph at the bottom right corner of Figure 1a. The
top-view SEM image in Figure 1c shows a dense structure. The
cross-sectional SEM images in Figure 1e and Figure S6 (Sup-
porting Information) demonstrate that the sulfide particles are
closely packed and tightly bonded in the polymer framework,
which is beneficial to ionic conduction. The energy-dispersive
spectroscopy (EDS) mapping images of S and F elements in the
LPSCl@P(VDF-TrFE) CSEs show uniform dispersion of LPSCl
particles in the CSEs (Figure 1e and Figure S7, Supporting
Information). The proportions of LPSCl particles and P(VDF-
TrFE) in the CSEs are estimated as about 79 and 21 wt%, respec-
tively, based on the thermogravimetric analysis (Figure 1d and
Figure S5, Supporting Information).
The XRD patterns in Figure 1f show that all the characteristic
peaks of LPSCl can be indexed into a cubic argyrodite phase
without impurity (ICSD No. 97-041-8490). The comparison in
the XRD patterns demonstrates that the crystallinity of LPSCl
does not change after the infiltration process and hot-pressing.
The diffraction spectrum for the P(VDF-TrFE) shows three
broad peaks at 19°, 36.7°, and 40.7°, corresponding to (110),
(001), and (111) indexes, respectively. According to the peak fit-
ting (Figure S8, Supporting Information), the broad peak at 19°
can be divided into two peaks at 18.6° and 19.8°, corresponding
to the γ-phase (3/1-helical conformation) and β-phase (all-trans,
TTT configuration), respectively.[21] The peak at 19.8° is much
stronger than that at 18.6°, indicating that the crystalline region
of the P(VDF-TrFE) is mainly the polar β-phase. The compar-
ison of the XRD pattern for the LPSCl@P(VDF-TrFE) CSEs
also indicates that the crystalline region of the P(VDF-TrFE)
also mainly keeps the polar β-phase.
Figure 2a shows the Nyquist plots of the CSE at 25–70 °C. The
ionic conductivity of the CSE membrane is about 1.2 mS cm–1
at 25 °C due to the high conductivity of LPSCl (≈3.9 mS cm–1,
Figure S1b, Supporting Information). The Arrhenius plot of the
ionic conductivity σ is exhibited in Figure 2b. The σ−T relation
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Figure 1. a) Schematic illustration for the fabrication procedure of the interpenetrating LPSCl@P(VDF-TrFE) CSEs via an electrospinning-infiltration-
hot-pressing method. The photograph at the bottom right corner shows a thin, flexible CSE. b) SEM image of a porous P(VDF-TrFE) membrane.
c) Top-view SEM image for the CSE. d) Thermogravimetric analysis of the CSE and LPSCl powder under a flow of N2. e) Cross-sectional SEM image of
the CSE and corresponding EDS mapping images of S and F elements. f) XRD patterns of the porous P(VDF-TrFE) membrane, CSE and LPSCl powder.

accords with the formula σ = Aexp (−Ea/kBT), where A is a pre-
exponential factor, Ea is the activation energy for ionic conduc-
tion, kB is the Boltzmann constant and T is the absolute tem-
perature. Ea is calculated to be about 0.3 eV, which is similar
to that of pristine LPSCl.[10] The electronic conductivity of the
CSE was measured to be 3.4 × 10–9 S cm−1 by direct-current
polarization measurement (Figure 2c). The electrochemical
stability of the CSE from the cyclic voltammogram (CV) of a
CSE+carbon||CSE||In cell (Figure 2d) shows that the CSE has
a quite similar electrochemical window to LPSCl, in which the
oxidative stability limit is ≈2.5 versus In/InLi, corresponding
to 3.1 V versus Li+/Li,[22] while the CV (Figure S9, Supporting
Information) for a stainless steel (SS)||CSE||Li cell as usual
shows a wide electrochemical window up to 5 V. The lithium-
ion transference number of the CSE and LPSCl was calculated
to be ≈0.993 and ≈0.999, respectively, both of which are about
equal to 1 (Figure S10, Supporting Information). The critical
current density (CCD) of the CSE (Figure S11, Supporting Infor-
mation) is about 6.5 mA cm–2 with a capacity of 3.25 mAh cm–2,
which is higher than that for Li||LPSCl||Li. Moreover, galva-
nostatic cycling performance (Figure S12, Supporting Infor-
mation) of Li||CSE||Li symmetric cells was also measured at a
high current density of 6.0 mA cm–2 (and a constant capacity of
3.0 mAh cm–2) at room temperature, though LPSCl is not quite
stable with Li metal.[22] As expected, the cell with pristine LPSCl
becomes failure due to short circuit quickly at such a high cur-
rent density. The over-potential of the Li||CSE||Li symmetric cell
gradually increases from about 0.6 to 1.08 V within the first
30 h, due to interfacial interaction between LPSCl and Li,[22a,b]
but then almost keeps steady within 200 h.
To further investigate the structure of the CSE, we conducted
series of measurements including Fourier transform infrared
(FTIR) spectroscopy, Raman spectroscopy, nuclear magnetic
resonance (NMR), X-ray photoelectron spectroscopy (XPS), and
theoretical simulations. Figure 3a presents the FTIR spectra of
the P(VDF-TrFE) and CSE. For the porous P(VDF-TrFE) frame-
work, there are six bands related to the three axes of the crystal-
line phase of P(VDF-TrFE). The peaks at 878 and 1174 cm–1 are
corresponding to the a-axis, those at 845 and 1285 cm–1 are asso-
ciated with the b-axis, and those at 1075 and 1400 cm–1 corre-
spond to the c-axis.[23] Specifically, the characteristic absorbance
band at 845 cm–1 can be ascribed to the symmetric vibration
of the CF2 group (νsCF2) coupled with the symmetric stretching
vibration of C–C (νsCC), and that at 1284 cm–1 can be assigned
to νsCF2 coupled with νsCC and the bending vibration of
C–C–C (δCCC).[23] The peaks at 845 and 1285 cm−1 can be

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Figure 2. a) Nyquist plots of the LPSCl@P(VDF-TrFE) CSE at 25–70 °C. b) Arrhenius plot of the ionic conductivity of the CSE. c) Current–time curve
of the CSE sandwiched between two pieces of stainless steel. d) Current–voltage curve of a CSE+carbon||CSE||In cell.

Figure 3. a) FTIR spectra of the porous P(VDF-TrFE) and CSE membranes. b) 31P NMR spectra of the CSE and LPSCl powder. c) XPS patterns (C 1s)
of the CSE. d) 7Li NMR spectra of the CSE and LPSCl powder. e) Possible complex structures in the CSE based on theoretical simulations.

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a­ssociated with trans sequences longer than TTTT and TTT,
confirming the presence of polar β-phase of P(VDF-TrFE).[23]
Compared with the P(VDF-TrFE), the peaks of the CSE are
almost at the same positions, indicating that the β-phase does
not change with the infiltration of LPSCl. It is worth noting that
the new band at 1037 cm−1 could originate from the bonding of
LPSCl and P(VDF-TrFE), corresponding to the coupling of the
C–S stretching vibration with the C–H–S deformation vibra-
tion.[24] Additionally, the new absorbance band at 579 cm−1 is
designated to the vibration of F–P–F coupled with F–S–F.[25]
The Raman spectrum of the porous P(VDF-TrFE) framework in
Figure S13a (Supporting Information) also shows the six peaks
at 845, 878, 1075, 1174, 1285, and 1400 cm–1. The band at around
3000 cm–1 is assigned to the C–H stretching vibration.[26] For
the Raman spectrum of the CSE, a red shift of the C–H band
(2855 cm–1) can be clearly observed, which is due to the new
chemical environment appeared in the middle of the structural
group. The changes in the chemical environment may result
from the formation of new bonds or the interaction of the two
components in the CSE. The Raman peak associated with the
PS43− group (418 cm–1) shows a broadening effect when LPSCl
is interpenetrated into the polymer network, suggesting that
the sulfide could be bonded with P(VDF-TrFE).
Figure 3b presents the 31P NMR spectra of the CSE and LPSCl
powder. A strong peak corresponding to PS43− at 85 ppm was
detected in both samples.[27] For the CSE, a new peak appears
at 119 ppm, which is ascribed to the P-(SR)x (R is a hydrocarbyl
group) and further proves that the sulfide and polymer are
bonded together.[28] The 13C NMR spectra of the two samples
are shown in Figure S13b (Supporting Information). The peaks
at 44, 86, 120 ppm are attributed to –CH2–, –CHF–, and –CF2–,
respectively.[29] A new peak at 160 ppm is observed in the spectra
of the CSE, which can be assigned to the formation of a new
CS bond.[30] For the 1H NMR spectra (Figure S13c, Supporting
Information), peak splitting occurs at 1.77 and 7.665 ppm when
the sulfide is added to the polymer network, while for the 19F
NMR spectra (Figure S13d, Supporting Information), a new
peak shows up at −163 ppm. These changes could also be attrib-
uted to the bonding between the sulfide and the P(VDF-TrFE).
Meanwhile, the C 1s XPS spectrum of the CSE in Figure 3c
also shows consistent results. The XPS peaks at 284.8, 288.6,
and 290.8 eV are assigned to C–C/C–H, H–C–F and F–C–F
of P(VDF-TrTE), respectively.[31] An additional peak appears at
285.6 eV, which is attributed to the CS bond.[32] XPS depth
profiling analysis was conducted on the CSE (Figure S14,
Supporting Information). The proportion of the CS bond
increases with the increase of the depth, demonstrating the
interaction between LPSCl and P(VDF-TrFE) in the CSE. In
addition, the S 2p XPS depth profiles of the CSE and LPSCl
are shown in Figure S15 (Supporting Information). Three sets
of doublet peaks at 161.3–162.6, 162.1–163.5, and 163.2–164.5 eV
are attributed to the boned sulfur in P–S–Li, P = S and P–S–C,
respectively. The signal of P–S–C appears on the surface and
inner part of the CSE, further confirming the interaction
between LPSCl and P(VDF-TrFE).[33] Figure 3d shows the
magic-angle spinning (MAS) 7Li NMR spectra of the CSE and
LPSCl powder. The strongest 7Li resonance in both the CSE
and LPSCl powder is at 2.8 ppm. For the CSE, two new reso-
nances appear at −1.04 and −48.5 ppm (see the two right panels
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of Figure 3d), indicating that the Li active sites are facilitated by
the combination of LPSCl and P(VDF-TrFE).
Density functional theory calculations and molecular
dynamic simulations (see the Experimental Section) were car-
ried out to further investigate the interaction between LPSCl
and P(VDF-TrFE). The possible complex structures in the
CSE based on our theoretical simulations are presented in
Figure 3e. In Figure S16 (Supporting Information), the pro-
cess for the combination of LPSCl and P(VDF-TrFE) is illus-
trated and the corresponding binding energy is calculated to
be −2.88 eV through density-functional-theory calculations.
Figure S17 (Supporting Information) shows the snapshot of
the LPSCl@P(VDF-TrFE) model after a molecular dynamic
simulation run of 100 ps. The calculated interaction energy for
the LPSCl@P(VDF-TrFE) model is −28.80 kcal mol−1, further
proving the combination of LPSCl and P(VDF-TrFE) (Table S1,
Supporting Information).
2.2. Electrochemical Performance of the ASSB Cells
with LPSCl@P(VDF-TrFE) CSEs
To demonstrate the advantages of the LPSCl@P(VDF-TrFE)
CSEs, the ASSB cells with LiNbO3-coated NCM (denoted as
NCM@LNO)-based composite cathode and a Li-In anode were
assembled (see the Experimental Section). LiNbO3-coating on
NCM enabled use of the active NCM with sulfide electrolytes.
First, to verify the electrochemical performance of our as-
prepared NCM@LNO active materials, normal LIB cells with
NCM@LNO mass loading of ≈3.1 mg cm−2 but with liquid
electrolyte was fabricated (see the Experimental Section). As
seen from Figure S18 (Supporting Information), specific capaci-
ties of 202, 178, and 120 mAh g–1 were obtained at 0.1 (0.16 C),
0.5 (0.81 C), and 1.0 mA cm–2 (1.61 C), respectively. Even at a
high rate of 5.0 mA cm2, a specific capacity of 63 mAh g–1 was
achieved. When the current density turned back to 0.1 mA cm2,
a large portion of the initial capacity was recovered, i.e.,
189 mAh g–1. At a current density of 1.0 mA cm2, a discharge
capacity of 99 mAh g–1 was still achieved after 3000 cycles
(Figure S18c, Supporting Information). These demonstrate
that our as-prepared NCM@LNO active powder keeps excellent
performance.
Now turn to our NCM@LNO||CSE||Li-In ASSB cells. The
cross-sectional SEM images (Figure S19, Supporting Informa-
tion) show a compact and clear interface between the com-
posite cathode and CSE layer in the NCM@LNO||CSE||Li-In
ASSB cell. As seen from Figure 4a, the ASSB cells with the
same amount of NCM@LNO (≈3.1 mg cm−2) as in the normal
LIB cells above present the discharge capacities of 189, 173,
and 114 mAh g–1 at 0.1 (0.16 C), 0.5 (0.81 C), and 1.0 mA cm–2
(1.61 C), respectively. When the current density returns to 0.1
from 5.0 mA cm–2, ≈92% of the initial capacity is recovered.
Figure 4b shows the charge–discharge curves of ASSB cells
at different rates. By comparison with the normal LIB cells
above (Figure S18, Supporting Information vs Figure 4), the
performance of the as-prepared NCM@LNO active powder
was basically developed in the ASSB cells. As expected, the
normal LIB cells have bit lower polarization and higher
discharge capacities than the ASSB cells, due to higher
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Figure 4. Electrochemical performances at room temperature for NCM@LNO||CSE||Li-In ASSB cells with NCM@LNO loading of ≈3.1 mg cm−2:
a) Rate performance. b) Charge–discharge curves at different rates. c) Cycling performance at a current density of 0.1 mA cm–2. d) Long-term cycling
performance at a current density of 1.0 mA cm–2.

ionic conductivity of the liquid electrolyte and lower inter- 123.1 mAh g–1, respectively. At the 500th cycle, the reversible
facial resistance in the liquid LIB cells compared with the capacities of 144.1, 120.5, and 97.1 mAh g–1, still remain, cor-
ASSB cells. The CV curves of the ASSB cells at a scan rate of responding to the capacity retention of 88%, 83%, and 79%,
0.2 mV s–1 (Figure S20a, Supporting Information) present a respectively.
pair of broad peaks at 3.67/3.95 V and these peaks at different Pouch-type ASSB cells with the same CSE and composite
cycles are overlapped, indicating reversible redox electro- cathode were also fabricated. Figure 6a and Figure S22a
chemical reaction of NCM (Ni2+/Ni4+ redox reaction).[34] The (Supporting Information) show the cyclic performance and
charge–discharge curves in Figure S20b (Supporting Informa- charge–discharge voltage profiles of the pouch-type cells at
tion) are consistent with the CV curves in Figure S20a (Sup- 0.1 mA cm–2, respectively. The pouch-type cells also show a
porting Information). high capacity and charge/discharge platforms similarly to those
At a low rate (e.g., 0.1 mA cm–2), the ASSB cells present of the coin-type cells (Figure 4), and present a high capacity
the excellent cycling performance. The ASSB cells exhibit a retention of 92% after 100 cycles. It also shows a high capacity
high initial discharge specific capacity of 168 mAh g–1 and a retention of 81% after 200 cycles at 1.0 mA cm–2 (Figure 6b and
capacity retention of 93% after 2000 cycles (Figure 4c). The cor- Figure S22b, Supporting Information). As seen, the pouch-type
responding Coulombic efficiency gradually increases to 100% ASSB cells can power a bulb (Figure 6c) or light an LED lamp
after a few cycles and then becomes stable. At a high rate (e.g., (Figure S23, Supporting Information).
1 mA cm–2 (1.61 C)), the ASSB cells also present the excellent
cycling performance, even much better than the liquid LIB
cells above. As shown in Figure 4d, the ASSB cells exhibit more
stable long-term cycling performance. They deliver the retained
capacity of 108 mAh g–1 and the capacity retention of 92% after
1000 cycles, which are higher than that of the LIBs (88% after
1000 cycles in Figure S18, Supporting Information). After 4500
cycles, the ASSB cells deliver discharge capacity of 103 mAh g–1
with the capacity retention of 88%, yet the LIB cells almost
become failure. In particular, the ASSB cells exhibit super
long-term cyclic stability with a retained capacity of 83 mAh g–1
even after 20 000 cycles, and the capacity retention is 71% at
the 20 000th cycles (see Figure S21, Supporting Information for
several representative charge–discharge profiles of the ASSB
cells).
Furthermore, the cyclic performance of the ASSB cells with
high NCM@LNO loadings in the composite cathode were
tested at 0.1 mA cm–2. As shown in Figure 5, the ASSB cells Figure 5. Cyclic performance of NCM@LNO||CSE||Li-In ASSB cells with
with NCM@LNO loadings of 12.39, 18.58, and 24.78 mg cm–2 different mass loadings of the NCM@LNO active material at 0.1 mA cm–2
exhibit initial discharge capacities of 168.6, 157.2, and and room temperature.

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Figure 6. a) Cyclic performance of a pouch-type cell at 0.1 mA cm–2. b) Cyclic performance of a pouch-type cell at 1.0 mA cm–2. c) Photographs of the
pouch-type batteries with the CSE used to power a bulb.
3. Conclusions
A flexible, compact LPSCl@P(VDF-TrFE) CSE membranes
with 30–40 µm in thickness have been successfully fabricated,
and the CSE possess a high ionic conductivity of 1.2 mS cm–1
and low electronic conductivity of 3.4 × 10–9 S cm−1 at room
temperature. By assembling the LPSCl@P(VDF-TrFE) CSE
with the composite cathode of NCM@LNO and LPSCl, the
NCM@LNO||CSE||Li-In ASSB cells present an outstanding
high-rate capability and ultra-long cycle life. The ASSB
cells are very stable with a 71% capacity retention even after
20 000 cycles at 1.0 mA cm–2 (1.61 C) and room temperature.
Such a stable cycling performance is much superior to that of
a corresponding liquid LIB cell. A pouch-type ASSB cells with
the same CSE and composite cathode also demonstrate good
performance and feasibility in future commercial applications.
4. Experimental Section
Preparation of Electrolyte Materials: Li6PS5Cl sulfide electrolyte was
synthesized as before.[10] Li2S (Alfa, 99.9%), P2S5 (Aladdin, 99%) and LiCl
(Aladdin, 99.9%) powders were mixed by ball milling. Then, the mixture
was calcined for 10 h at 550 °C in a quartz tube. The porous P(VDF-
TrFE) membrane was prepared via electrospinning method. P(VDF-TrFE)
copolymer powders (70/30 mol%, Piezotech) were thoroughly dissolved
in the mixed solvent of N,N-dimethylformamide (DMF) and acetone with
a volume ratio of 3:7 to get P(VDF-TrFE) precursor solution. The P(VDF-
TrFE) solution was then transferred into the syringe and electrospun
with an electric field of 1 kV cm–1 and flow rate of 1 mL h–1 for 3–4 h. To
prepare the Li6PS5Cl@P(VDF-TrFE) CSE, grinded Li6PS5Cl powder with a
particle size of 1–3 µm was suspended in methylbenzene (99.9%, Sigma-
Aldrich) by mechanical stirring at 30 °C for 1 h to obtain a homogeneous
slurry. Then, the slurry was injected into a P(VDF-TrFE) electrospun film
and casted with a doctor blade, following by drying on a thermostatic
heater at 120 °C for 2 h to remove the solvent. Upon solvent evaporation,
two films with Li6PS5Cl were stacked and hot-pressed at 200 °C for 2 h
under a pressure of 10 MPa. The preparation of the CSE was conducted
in an Ar-filled glovebox (O2 ≤ 0.1 ppm, H2O ≤ 0.1 ppm).
Fabrication of Composite Cathode: Commercial LiNi0.8Co0.1Mn0.1O2
(NCM) powder was heated at 90 °C for 12 h before use. LiOC2H5 and
Nb(OC2H5)5 were mixed homogeneously into anhydrous ethanol.
Subsequently, the dried NCM powder was added into the solution
above and stirred for 3 h. After that, the solution was dried at 150 °C
for 12 h and heated in a furnace at 400 °C under an oxygen flow for 1 h.
Thus, a LiNbO3 coating was formed on the NCM powder (denoted as
NCM@LNO). Raw multiwalled carbon nanotube powder was soaked
in concentrated nitric acid at 120 °C for 2 h and washed with distilled
water until the pH of the filtrate was 7.0. The modified multiwalled
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carbon nanotube powder was then dried at 70 °C in an oven overnight
for subsequent use. Then, the NCM@LNO-based composite cathode
for ASSB cells was obtained by grinding the mixture of the NCM@LNO,
Li6PS5Cl, multiwalled carbon nanotube powders with a weight ratio of
7:2:1 for 30 min.
Fabrication of Batteries: Coin-type and pouch-type ASSB cells were
fabricated by employing the above NCM@LNO-based composite
cathode, LPSCl@P(VDF-TrFE) CSE as the solid electrolyte separator,
and Li-In foil as the anode. The mass loadings of the active NCM@
LNO material in the composite cathode for the coin-type and pouch-type
ASSB cells were ≈3.1 and 7.4 mg cm–2, respectively. The coin-type cells
with a high NCM@LNO loading of 12–25 mg cm−2 were also prepared
for some tests. A pressure of 100 MPa was applied on the coin-type
ASSBs. For pouch-type ASSB cells, the composite cathode, the CSE
membrane and the anode were laminated in the polypropylene-coated
aluminum pouch, with a size of ≈6 × 6 cm2. A positive tab was welded
on the positive current collector and a negative tab was welded on the
negative current collector using a resistance welder. Aluminum and
nickel were used as the positive and negative tabs, respectively.
For comparison, normal liquid LIB cells were fabricated by employing
the same NCM@LNO with a mass loading of ≈3.1 mg cm−2 (NCM@
LNO, poly(vinylidene fluoride)(PVDF), multiwalled carbon nanotube
powders with a weight ratio of 7:2:1), 1 m LiPF6 in ethylene carbonate and
dimethyl carbonate (EC:DMC = 1:1, v:v) as liquid electrolyte, commercial
polypropylene separator, and a Li foil as the anode. All LIB cells were
CR2025-type coin cells.
Material Characterization: XRD was carried out using a Rigaku D/
max-2500 diffractometer with a Cu Kα radiation source to identify the
phases of the samples. SEM and EDS mapping images were obtained
with a Zeiss Merlin field-emission scanning electron microscope.
Raman spectra were taken using a Raman spectrometer (LabRAM HR
Evolution) at an excitation of 532 nm. FTIR spectra were acquired on a
VERTEX 70 spectrometer. The TG analysis was performed with nitrogen
flowing over the samples heated at a rate of 10 °C min–1 using a TA-Q800
instrument. XPS spectra was measured using an XPS system (PHI
Quantera II, Ulvac-Phi) with a monochromatic Al Kα X-ray source. The
depth profiling was done by Ar sputtering with an equivalent sputtering
rate of 26.4 nm min−1 on SiO2. For each sputter lay, the time of sputtering
was 7.5 s.
Computational Methods: Density-functional-theory calculations were
performed in the Perdew–Burke–Ernzerhof (PBE) generalized gradient
approximation (GGA), implemented in the Vienna Ab initio Simulation
Package (VASP).[35] The projector augmented-wave (PAW) potentials
were used for the treatment of the core electrons. Kohn–Sham single
electron wave functions were expanded in a plane-wave basis with a
kinetic energy cutoff of 650 eV to describe the valence electrons. The
Tkatchenko–Scheffler method was used to count for the long range
dispersion corrections. A vacuum layer was set to be 22 Å. Momentum
space integration was performed using a 1 × 1 × 1 Monkhorst–Pack
k-point mesh.[36]
Molecular dynamic simulations were performed in NVT (number,
volume, and temperature (298 K) are constant) using the Universal force
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field. LPSCl was cut along the crystal plane (311) and P(VDF-TrFE) was
built on the sulfide surface. All these simulations were performed using
Forcite program.
Electrochemical Measurements: Two stainless steel (SS) disks were
attached to the CSE membranes as current collectors to assemble the
SS||CSE||SS cells to measure the impedance. The alternating current
impedance measurement was conducted using an impedance analyzer
(ZAHNER-elektrik IM6) in a frequency range of 1 Hz to 1 MHz with an
applied voltage of 50 mV. The ionic conductivity σ was calculated by the
equation σ = L/(RS), where R was the total resistance of solid electrolyte,
L was the sample thickness, and S was the area of solid electrolyte.
The Li+ transference number TLi+ was obtained using a symmetric
Li cell by a chronoamperometry test with a DC voltage amplitude of
20 mV. The EIS tests with a 10 mV AC amplitude were taken before and
after DC polarization. The value of TLi+ can be calculated according to
TLi+ = Is(ΔV−R0I0)/[I0(ΔV−RsIs)], where I0 and Is are the initial and steady-
state DC current, respectively; R0 and Rs are the initial and steady-state
interfacial resistances, respectively; and ΔV is the applied voltage.
To evaluate the electrochemical stability of the CSE, LPSCl and
carbon were mixed in a weight ratio of 9:1 and manually ground in an
agate mortar for 15 min. The same process was then used to prepare
Li6PS5Cl@P(VDF-TrFE) CSE, except instead of Li6PS5Cl, a mixture of
LPSCl+carbon is used to prepare CSE+carbon layer. CV measurement
was performed on a CSE+carbon||CSE||In cell under a pressure of
100 MPa using a potentiostat (Biologic VMP3) at a scan rate of
0.2 mV s–1 from −0.6 to 3.6 V at room temperature.
Galvanostatic measurements were performed using a multichannel
battery testing system (LAND CT2001A) in a voltage range of 2.2–3.6 V
for coin-type and pouch-type ASSB cells and 2.8–4.2 V for liquid LIB cells
(1 C = 200 mA g–1). CV was tested by a potentiostat (Biologic VMP3).
Electrochemical impedance spectroscopy was conducted with an
impedance analyzer (ZAHNER-elektrik IM6).
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This work was supported by the Basic Science Center Program of
National Natural Science Foundation of China (Grant No. 51788104) and
Tsinghua-Foshan Innovation Special Fund (Grant No. 2018THFS0409).
Conflict of Interest
The authors declare no conflict of interest.
Data Availability Statement
The data that support the findings of this study are available in the
supplementary material of this article.
Keywords
ASSLBs, composite solid electrolytes, Li6PS5Cl, P(VDF-TrFE), sulfide
electrolytes
Received: February 24, 2022
Revised: April 8, 2022
Published online: May 6, 2022
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