pubs.acs.

org/JACS Article

Amorphous Chloride Solid Electrolytes with High Li-Ion

Conductivity for Stable Cycling of All-Solid-State High-Nickel
Cathodes
Feng Li,○ Xiaobin Cheng,○ Gongxun Lu, Yi-Chen Yin, Ye-Chao Wu, Ruijun Pan, Jin-Da Luo,
Fanyang Huang, Li-Zhe Feng, Lei-Lei Lu, Tao Ma, Lirong Zheng, Shuhong Jiao, Ruiguo Cao,
Zhi-Pan Liu, Hongmin Zhou, Xinyong Tao,* Cheng Shang,* and Hong-Bin Yao*
Cite This: J. Am. Chem. Soc. 2023, 145, 27774−27787 Read Online
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ACCESS Metrics & More Article Recommendations *

sı Supporting Information
Downloaded via CHONNAM NATL UNIV on January 6, 2024 at 09:43:31 (UTC).

ABSTRACT: Solid electrolytes (SEs) are central components that enable

high-performance, all-solid-state lithium batteries (ASSLBs). Amorphous
SEs hold great potential for ASSLBs because their grain-boundary-free
characteristics facilitate intact solid−solid contact and uniform Li-ion
conduction for high-performance cathodes. However, amorphous oxide
SEs with limited ionic conductivities and glassy sulfide SEs with narrow
electrochemical windows cannot sustain high-nickel cathodes. Herein, we
report a class of amorphous Li−Ta−Cl-based chloride SEs possessing high
Li-ion conductivity (up to 7.16 mS cm−1) and low Young’s modulus
(approximately 3 GPa) to enable excellent Li-ion conduction and intact
physical contact among rigid components in ASSLBs. We reveal that the
amorphous Li−Ta−Cl matrix is composed of LiCl43−, LiCl54−, LiCl65−
polyhedra, and TaCl6− octahedra via machine-learning simulation, solid-
state 7Li nuclear magnetic resonance, and X-ray absorption analysis. Attractively, our amorphous chloride SEs exhibit excellent
compatibility with high-nickel cathodes. We demonstrate that ASSLBs comprising amorphous chloride SEs and high-nickel single-
crystal cathodes (LiNi0.88Co0.07Mn0.05O2) exhibit ∼99% capacity retention after 800 cycles at ∼3 C under 1 mA h cm−2 and ∼80%
capacity retention after 75 cycles at 0.2 C under a high areal capacity of 5 mA h cm−2. Most importantly, a stable operation of up to
9800 cycles with a capacity retention of ∼77% at a high rate of 3.4 C can be achieved in a freezing environment of −10 °C. Our
amorphous chloride SEs will pave the way to realize high-performance high-nickel cathodes for high-energy-density ASSLBs.

■ INTRODUCTION
High-energy-density and safe rechargeable batteries are highly
desirable for the ever-increasing demand for sustainable energy
storage in smart grids and electric vehicles.1−3 All-solid-state
lithium batteries (ASSLBs) using nonflammable solid electro-
lytes (SEs) instead of liquid electrolytes are promising
candidates with improved energy/power density, safety, and
cycle life.4−6 Although the expected advantages of ASSLBs are
widely acknowledged, their practical applications are still
hindered by formidable obstacles stemming from the intrinsic
nature of employed SEs, including low ionic conductivity,
interface incompatibility, and inadequate solid−solid physical
contact.7,8
In recent decades, tremendous efforts have been made to
explore suitable SEs for ASSLBs by focusing on oxide, sulfide,
halide crystalline ceramic, sulfide glassy-ceramic composite,
and amorphous oxide and sulfide SEs.5,9−11 Crystalline ceramic
SEs with high ionic conductivities (10−4−10−2 S cm−1) have
been reported in the oxides (perovskites and garnets),4,12
sulfides (argyrodites, Li6PS5Cl, Li5.5PS4.5Cl1.5 Li10GeP2S12,
Li9.5Si1.74P1.44S11.7Cl0.3),11,13−15 and revived halides (Li-M-X,
M = non-Li cations, X = halogen anions).16−18 However,
incorporating these ceramic SEs in ASSLBs is still hindered by
battery failure due to rapid interface deterioration19−21 and
limited ionic conduction percolation in high mass loading
cathodes (with areal capacity >3 mA h cm−2).22,23
In contrast to ceramic SEs, amorphous SEs are promising
candidates for ASSLBs due to their inherent unique glassy
networks for intimate solid−solid contact and excellent
lithium-ion conduction percolation.24−27 Currently, amor-
phous lithium phosphorus oxynitride (LiPON)28 SEs are
being used in commercial thin-film ASSLBs. Nevertheless, the
energy/power density of LiPON-based thin-film ASSLBs is still
Received: September 27, 2023
Revised: November 17, 2023
Accepted: November 20, 2023
Published: December 11, 2023

© 2023 American Chemical Society https://doi.org/10.1021/jacs.3c10602

27774 J. Am. Chem. Soc. 2023, 145, 27774−27787
Journal of the American Chemical Society
inferior to that of current lithium-ion batteries (LIBs) due to
the low areal capacity of the thin-film cathode and poor ionic
conductivity (10−6 S cm−1) of LiPON.
To achieve high areal capacity and high voltage cathodes,
highly Li-ion-conductive amorphous SEs with good antiox-
idative capability are desirable. Presently, ductile sulfide and
oxysulfide-based amorphous SEs exhibit acceptable Li-ion
conductivities (10−4−10−3 S cm−1).29,30 Unfortunately, it
remains a great challenge to achieve high areal capacity and
high voltage cathodes based on oxide, sulfide, or oxysulfide
amorphous SEs due to the undesirable trade-off between ionic
conductivity and cathode interfacial compatibility.9,21,31 Aside
from previously explored oxide SEs, chloride SEs have been
recently proven to overcome the poor oxidative stability of
sulfide SEs.32 Excellent electrochemical performance up to
several thousand cycles has also been demonstrated for bulk-
type ASSLBs with crystalline halides in combination with bare
high-voltage cathodes.16−18,33,34 Recently, the ionic conductiv-
ity of the crystalline halide is further boosted by the
modulation of the framework35−37 and the formation of
glass-ceramic phase38−40 and glass phase,41,42 indicating its
potential in future application of practical ASSLBs. In addition,
unique halide-eutectic and clay-like fluoride-halides43,44 had
been revealed with glass phase and excellent ionic conductivity.
However, their integration into high-areal-capacity ASSLBs is
hindered by their viscous states. In this context, amorphous
chloride SEs with proper mechanical properties combining the
advantages of glass networks and antioxidation chemistry have
yet to be explored.
Herein, we report a class of amorphous Li−Ta−Cl-based
SEs with super Li-ion conductivity up to 7.16 mS cm−1 and
good compatibility with a high-nickel single-crystal Li-
Ni0.88Co0.07Mn0.05O2 (S-NCM88) cathode. Owing to the soft
network and high oxidative stability of amorphous Li−Ta−Cl-
based SEs, the ASSLB with S-NCM88 exhibits a high-rate
capability up to 4 C and good reversibility with a capacity
retention of 98.8% after 800 cycles at ∼3 C. Also, a well-
operated ASSLB with a high mass loading of S-NCM88 (25
mg cm−2) delivering an areal capacity of ∼5 mA h cm−2 is
demonstrated to retain 80% capacity after 75 cycles at 0.2 C.
Furthermore, the high-rate capability and life-span of over
9800 cycles of halide-based ASSLB in a freezing environment
were demonstrated. The present work opens a new avenue for
amorphous SE-based ASSLBs with high areal capacity and long
cycle life.
■ EXPERIMENTAL SECTION
Synthesis of A-LTC and Composite SEs. The starting materials
used for the synthesis of A-LTC (A represents amorphous, and LTC
represents LiTaCl6) and composite SEs are mixtures of LiCl
(anhydrous, Aladdin), TaCl5 (anhydrous, Aladdin), and other
inorganic lithium salts (LiF, Li2O, LiOH, anhydrous, Aladdin,
Li2O2, anhydrous, Sigma-Aldrich). LiCl and TaCl5 were weighed
and mixed in a molar ratio of LiCl/TaCl5 = 1−7/1 for the synthesis of
A-LTC·(x − 1)LiCl (1 ≤ x ≤ 7); LiF, LiCl, and TaCl5 were weighed
and mixed in a molar ratio of LiF/LiCl/TaCl5 = 0.5/1/1, 0.75/1/1,
and 1/1/1 for the synthesis of A-LTC·xLiF (x = 0.5, 0.75, 1); Li2O,
LiCl, and TaCl5 were weighed and mixed in a molar ratio of Li2O/
LiCl/TaCl5 = 0.5/1/1, 1/1/1, and 1.5/1/1 for the synthesis of A-
LTC·xLi2O (x = 0.5, 1, 1.5); LiOH, LiCl, and TaCl5 were weighed
and mixed in a molar ratio of LiOH/LiCl/TaCl5 = 0.5/1/1, 0.75/1/1,
and 1/1/1 for the synthesis of A-LTC·xLiOH (x = 0.5, 0.75, 1);
Li2O2, LiCl, and TaCl5 were weighed and mixed in a molar ratio of
Li2O2/LiCl/TaCl5 = 0.25/1/1, 0.5/1/1, and 0.75/1/1 for the
27775
pubs.acs.org/JACS Article
synthesis of A-LTC·xLi2O2 (x = 0.25, 0.5, 0.75). Desirable
stoichiometric amounts of LiCl and TaCl5 powders were mixed and
then loaded into tungsten carbide pots (100 mL) and ball-milled at
450 rpm (6 min of milling, followed by 3 min of rest) in a Planetary
ball mill (YXQM-1L, Changsha Miqi Instruments & Equipment Co.)
for 24−168 h. The mass ratio of tungsten carbide ball mill beads (10,
8, and 5 mm in diameter; 16, 42, and 52 g in mass) to the precursors
is 50:1. The pots were opened, and the precursors were ground
several times to ensure homogenization of the powder during the
milling process. The TaCl5-based composite SEs with other lithium
salts and NbCl5-based electrolytes were obtained by introducing
stoichiometric amounts of Li-X (X = Cl, F, O, OH, O2) in the
reaction precursors under the same mixing and ball milling conditions.
LiCl and NbCl5 were weighed and mixed in a molar ratio of LiCl/
NbCl5 = 1/1, 4/1 for the synthesis of LiCl-NbCl5 (A-LNC), and
4LiCl-NbCl5 (A-LNC·3LiCl), respectively. Li2O and NbCl5 were
weighed and mixed in a molar ratio of 1/1 Li2O/NbCl5 for the
synthesis of Li2O-NbCl5. The obtained fine SE powders were
collected and stored for further application and characterization. All
the procedures were conducted in an argon-filled glovebox (H2O, O2
< 0.1 ppm).
SSW-NN Method. All simulations based on G-NN potential were
conducted by using LASP code45 (Large-scale Atomic Simulation
with neural network Potential, www.lasphub.com) developed in Liu’s
group. The stochastic surface walking (SSW)46 method was utilized
for global optimization, which can automatically explore multidimen-
sional potential energy surfaces (PESs) and identify important
structures and pathways, as demonstrated in our previous work.47,48
The G-NN potential was generated by fitting the DFT global PES
data obtained from the SSW global PES sampling, also known as the
stochastic surface walking global optimization combined with global
neural network potential (SSW-NN) method, which typically speeds
up PES calculations by 3−4 orders of magnitude compared with DFT.
This allows for efficient PES exploration at an accuracy comparable
with that of DFT calculations. We generated the triple-element Li−
Ta−Cl G-NN potential via the iterative self-learning scheme of the
SSW-NN data set49 by learning LiTaCl6 crystals with atoms ranging
from 16 to 48. The training data set can be downloaded from (www.
lasphub.com/supportings/Trainfile_LiTaCl6.tar.gz). The final Li−
Ta−Cl training data set consists of 5060 structures, as detailed in
Table S1. The root-mean-square (rms) errors for the energy and force
of the G-NN potential are 1.821 meV/atom and 0.027 eV/Å,
respectively. The important low-energy structures from SSW-NN
calculations have been further examined by using DFT calculations,
and the benchmark results are detailed in Table S2, which shows that
the energy rms error is below 4 meV/atom for important minima. The
accuracy is good enough for the SSW global PES search to find low-
energy minima.
DFT Calculations. All DFT calculations were performed by using
the plane-wave VASP (Vienna Ab initio Simulation Package) code,50
where the electron−ion interaction is represented by the projector
augmented wave potential. The exchange−correlation function
utilized to train the neural network (NN) potential was the GGA-
PBE,51 and the kinetic energy cutoff was 450 eV. The first Brillouin
zone k-point sampling adopted the Monkhorst−Pack scheme with an
automated mesh determined by 25 times the reciprocal lattice vectors.
The energy and force criteria for convergence of the electron density
and structure optimization were set at 5 × 10−6 eV and 0.05 eV/Å,
respectively. The dispersion effect is considered by using Grimme’s
D3 correction (PBE-D3).52
Li-Ion Conduction Simulation. To identify the equilibrated
volume (lattice), the initial structure relaxation was always carried out
for 10 ps using an isothermal−isobaric (NPT) ensemble at 300 K for
Li−Ta−Cl systems. The Li+ motion was then simulated by the
canonical ensemble for A-LTC systems with 512 atoms per supercell
for 1 ns with a time step of 1 fs, where the first 0.2 ns is for thermal
equilibration. To identify the elementary steps of Li-ion migration, we
have optimized the snapshots of the three pathways to local minima
and located the transition states connecting those minima. The
Einstein relation was used to determine the Li+ diffusion coefficients
https://doi.org/10.1021/jacs.3c10602
J. Am. Chem. Soc. 2023, 145, 27774−27787
Journal of the American Chemical Society
(D) from the slopes of the mean square displacements of the Li atom
(Δr2) plotted versus simulation time (t)
r(t )2
D = lim
t 6t (1)
The activation energies for lithium diffusion (Ea) were computed
by fitting the calculated diffusion coefficients to the standard
Arrhenius form using the following relation
i Ea yz
D = D0 exp jjj zz
k RT { (2)
The Ea values obtained were used to characterize the dependence
of the averaged diffusion barriers of A-LTC. The conductivity of Li+
ions σ was finally derived from the Nernst−Einstein relation with the
diffusion coefficient D
q2DN ijj F 2 yzz
= j z
VNa jjk RT zz{ (3)
where Na is the Avogadro constant, q is the charge of the mobile ion
(1 for Li+), N is the number of Li atoms, and F is Faraday’s constant.
Ionic Conductivity and Activation Energy Measurements.
The obtained SE powders were cold-pressed into 10 mm diameter
pellets by a hydraulic press (YLJ-15T-LD, Hefei Kejing Materials
Technology Co., Ltd.) at 400 MPa for 3 min. Both sides of the pellets
were sputtered with the thin Au layers by a magnetron sputtering
apparatus (SD-900 M, Vision Precision Instruments) for the
alternating current (AC) impedance measurement. The impedance
was measured between −40 and 60 °C with an applied frequency of 1
Hz to 7 MHz and a constant voltage of 50 mV. The electrical
conductivities were investigated by the direct current (DC)
polarization method with externally applied voltages ranging from
100 to 500 mV. All electrochemical measurements were performed
using a Bio-Logic VMP3 frequency response analyzer in an argon-
filled glovebox (H2O, O2 < 0.1 ppm). A Neware high- and low-
temperature test chamber (MGDW-150-40) was applied to control
the temperature.
XAS Measurement and Analysis. The X-ray absorption fine
structure spectra (Ta L3-edges) were collected at the 1W1B station at
the Beijing Synchrotron Radiation Facility (BSRF). The storage rings
of BSRF were operated at 2.5 GeV with an average current of 250 mA.
Using a Si(111) double-crystal monochromator, data collection was
carried out in transmission/fluorescence mode using an ionization
chamber. All spectra were collected under ambient conditions with
the pellets sealed by Kapton film. The acquired EXAFS data were
processed according to standard procedures using the ATHENA
module implemented in the IFEFFIT software package.53−55 The k3-
weighted EXAFS spectra were obtained by subtracting the post edge
background from the overall absorption and then normalizing with
respect to the edge-jump step. Subsequently, k3-weighted χ(k) data of
the Ta L3-edge were Fourier transformed to real (R) space using a
hanging window (dk = 1.0 Å−1) to separate the EXAFS contributions
from different coordination shells. To obtain the quantitative
structural parameters around central atoms, least-squares curve
parameter fitting was performed by using the ARTEMIS module of
the IFEFFIT software packages. The k3 weighting, k-range of 3.4−
14.2 Å−1, and R range of 1.2−2.7 Å were used for the fitting. The four
parameters, coordination number, bond length, Debye−Waller factor,
and E0 shift (CN, R, σ2, ΔE0), were fitted without any being fixed,
constrained, or correlated.
Neutron Powder Diffraction Measurement and Analysis.
The neutron powder diffraction (NPD) experiment was carried out at
the multi-physics instrument, a high-intensity time-of-flight diffrac-
tometer, at the China Neutron Spallation Source (CSNS). The
powder sample of about 1.4 g was filled into a cylindrical sample
holder and sealed carefully by indium wires under an argon
atmosphere. Then the container was transferred to the scattering
chamber and measured at room temperature with a neutron
wavelength band from 0.1 to 4.5 Å. The diffraction patterns were
27776
pubs.acs.org/JACS Article
collected by 6 sets of detectors labeled as Bank 2−7 with 2θ range
from 12.5 to 170.0°.56 The diffuse scattering signal originating from
the amorphous component can be clearly observed at low-angle banks
(Bank 2−4) covering a wide d-range, while high-angle banks (Bank
5−7) possess higher resolution to show more details within a low d-
range.
Solid-State 7Li NMR Measurement. 7Li 1D magic-angle
spinning nuclear magnetic resonance (MAS NMR) measurements
were performed on Bruker AVANCE NEO 600 WB spectrometers
(B0 = 14.1 T, Larmor frequency ω0 = 233.24 MHz for 7Li) with a 3.2
mm HXY MAS probe at room temperature. All the powder specimens
were sealed in ZrO2 tubes with VESPEL caps, and the preparation was
conducted in an Ar-filled glovebox (H2O, O2 < 0.1 ppm) to avoid the
degradation of samples induced by moisture. MAS was applied to
obtain high-resolution spectra, with a spinning rate of 22 kHz for 1D
NMR experiments. All 7Li chemical shifts were calibrated with 1 M
LiCl (aq).
Electrochemical Measurements of All-Solid-State Batteries.
ASSLBs employing amorphous chloride-based SEs in combination
with single-crystal NCM88 (provided by Hefei Gotion High-tech
Power Energy Co., Ltd.) cathode and a Li−In alloy anode were
assembled in an argon-filled glovebox (H2O, O2 < 0.1 ppm). S-
NCM88 was mixed with composite SE (A-LTC·Li-X, X = Cl, F, O,
OH, O2, or NbCl5-based electrolytes) and polytetrafluoroethylene
(PTFE) powders (Guangdong Canrd New Energy Technology Co.,
Ltd.) at a mass ratio of 70:27:3. The mixtures were then hand-ground
for 30 min in an agate mortar and mixed with a miniature vibration
mixer (MSK-SFM-12 M, Hefei Kejing Materials Technology Co.,
Ltd.) for another 30 min as the final cathode composite powders.
Li6PS5Cl was employed as a separate layer to construct stable anode-
electrolyte interface. Approximately 90 mg of SE powder was first
placed into a poly(ether ether ketone) (PEEK) cylinder with a 10 mm
diameter and pressed at 1.5 tons for 2 min to form a separator layer,
and then the cathode composite powder (corresponding to an areal
capacity of 1−5 mA h cm−2) was spread over one side of the separator
layer and pressed at 2 tons for another 2 min. To improve the
reduction stability of the interface between the SE and anode,
approximately 40 mg of Li6PS5Cl (provided by Hefei Gotion High-
tech Power Energy Co., Ltd.) powder was dispersed evenly on the
other side of the separator layer and then pressed at 3 tons for 5 min.
Then, a piece of In foil (0.1 mm thickness, 10 mm diameter, 3A
Materials) was attached to the surface of Li6PS5Cl. A Li foil (6 mm
diameter, China Energy Lithium Co., Ltd.) with a weight ratio of Li/
In = 1:50 was subsequently attached to the In foil. Subsequently, the
ASSLB was pressed at 1 ton for another 1 min and then placed into a
custom-made stainless-steel casing (Ningbo Zhengli New Energy
Technology Co., Ltd.) with a constantly applied pressure of 100 MPa
for 24 h to form the Li−In alloy. All of the preparation processes were
conducted in an argon-filled glovebox (H2O, O2 < 0.1 ppm).
Galvanostatic cycling of the ASSLBs was conducted with a constantly
applied pressure of 100 MPa within the voltage range of 2.8−4.3 V
versus Li+/Li using a LAND-CT2001A (Wuhan, China) and Neware-
CT-4008T battery cycler (Shenzhen, China) at 30 and −10 °C,
respectively.
Characterizations. Powder X-ray diffraction (PXRD) patterns
were acquired by a Philips X’Pert PRO SUPER X-ray diffractometer
using Cu Kα radiation (λ = 1.54178 Å). To prepare the samples, SE
powders were sealed with a Kapton film in a designed test apparatus,
avoiding the effect of ambient humidity. For cryogenic transmission
electron microscopy (cryo-TEM) characterizations, the SE powders
were directly dispersed on a Cu grid and then transferred into the
cryo-TEM holder in an Ar-filled glovebox (H2O, O2 < 0.1 ppm).
Using a sealed container, the cryo-TEM holder was quickly inserted
into the FEI Talos-S TEM chamber, and then liquid nitrogen was
poured into the cryo-TEM holder until the sample temperature
dropped below −170 °C. All cryo-TEM images were taken at
cryogenic temperature (−170 °C). SEM images were obtained by a
JEOL-JSM-6700F scanning electron microscope with an acceleration
voltage of 10 kV. Atomic force microscopy (AFM, Dimension Icon,
BRUKER) in an argon-filled glovebox (H2O, O2 < 0.1 ppm) was used
https://doi.org/10.1021/jacs.3c10602
J. Am. Chem. Soc. 2023, 145, 27774−27787
Journal of the American Chemical Society pubs.acs.org/JACS Article

Figure 1. Synthesis and Li-ion conductivity evaluation of the obtained A-LTC. (a) PXRD patterns of amorphous LiTaCl6 (A-LTC, top), ball-
milled LiCl (Bm_LiCl, middle) and ball-milled TaCl5 (Bm_TaCl5, bottom), showing the amorphization reaction between LiCl and TaCl5. The
patterns of Bm_LiCl and Bm_TaCl5 are indexed as LiCl (ICSD no. 26909) and TaCl5 (ICSD no. 409433), respectively. (b) Nyquist plots of the
EIS measurement results of A-LTC and Bm_LiCl (inset) at 25 °C. (c) Arrhenius plot of ionic conductivities of the A-LTC together with those of
crystalline sulfide, organic polymer, glassy oxide/sulfide, halide SEs, and LiPF6-based liquid electrolyte with the data adapted with permission
from.13,14,28,29,41,42,44,60−64 The A-LTC possesses a low activation energy and superionic conductivity close to that of the state-of-the-art sulfide SEs.

to analyze the mechanical properties of cold-pressed SE pellets. The
modulus distribution of SE pellets was obtained using Dimension
Icon (Bruker) in the peak force quantitative nanomechanical mapping
mode.
Metal Chlorides Cost Estimation. The comparison of the large-
scale purchase cost of 1000 kg of metal chlorides was based on the
method proposed by Hart and Sommerfeld,57 following the following
formula
log10 P = log10 a + b × log10 Q
In this equation, a and b represent the constants for the given
materials, P represents the unit price in units of $ kg−1, and Q
represents the quantity in units of grams purchased. The prices of the
metal chlorides with different packing are obtained from the Web site
of Aladdin (https://www.aladdin-e.com/).
precursors revealed that ball-milled LiCl (Bm_LiCl) and
TaCl5 (Bm_TaCl5) under the same conditions were still
maintained in crystalline states (Figure 1a, gray and blue
patterns), which indicates that the mechanochemical reaction
between LiCl and TaCl5 is an amorphization process.
We performed temperature-dependent electrochemical
impedance spectroscopy (EIS) measurements to evaluate the
ionic conductivity of the obtained A-LTC. The EIS of A-LTC
displayed high bulk ionic conduction without the grain
boundary (GB) resistance response (Figure 1b, 25 °C).
Representative equivalent circuit model and fitted values are
shown in Figure S1a−c and Tables S3, S4. The calculated ionic
conductivity of A-LTC is 6.05 mS cm−1 (Figure S1a,b) at
room temperature (25 °C). The activation energy for ionic

■ RESULTS AND DISCUSSION

We synthesized amorphous chloride SEs via a mechanochem-
ical reaction of binary compound precursors LiCl and TaCl5
(Experimental Section). PXRD patterns of the obtained
product and precursors are shown in Figure 1a. The featureless
pattern (Figure 1a, red pattern) indicates the amorphization of
the precursors to yield an amorphous powder, namely,
amorphous LiTaCl 6 (A-LTC). The peak indexing of
27777
conduction of A-LTC is 0.23 eV based on the ionic
conductivity in the temperature range of −40−60 °C (Figures
1c and S1a−f). In addition, the electronic conductivity of A-
LTC measured by the direct-current (DC) polarization
method is ∼5 × 10−9 S cm−1 (Figure S1g,h), implying that
A-LTC can be regarded as almost insulating electron transport
compared to the fast Li-ion conduction. As a control, Bm_LiCl
displayed typical characteristics of poor Li-ion conductors with
a very low ionic conductivity of 6.14 × 10−8 S cm−1 (inset of
https://doi.org/10.1021/jacs.3c10602
J. Am. Chem. Soc. 2023, 145, 27774−27787
Journal of the American Chemical Society pubs.acs.org/JACS Article

Figure 2. SSW-NN simulation and corresponding structure characterizations of the A-LTC. (a) The global PES contour plot of A-LTC systems
containing 3864 distinct low energy minima. The x-axis is a distance-weighted Steinhart OP, the y-axis is the potential energy of A-LTC obtained
from DFT computation, and the color indicates the DOS for the minima. The global minima region is highlighted by a black dashed circle and an
arrow below. (b) Representative local configuration of A-LTC obtained by SSW-NN simulation. (c,d) One-dimensional (1D) 7Li MAS NMR
spectra of the obtained A-LTC (c) and LiCl (d). (e) Corresponding Li-ion proportion of amorphous and crystalline components determined by
the peak integral areas in (c). (f) Fourier transforms of k3-weighted Ta L3-edge EXAFS curves of Ta2O5, TaCl5, and A-LTC. Solid lines and hollow
circles represent raw data and fit results, respectively. (g−j) TEM images with different magnifications (g−i) and the corresponding FFT pattern (j)
of A-LTC.

Figure 1b) and a high activation energy of 0.72 eV (Figure S2).
The apparent difference in Li-ion conduction between A-LTC
and Bm_LiCl indicates the important role of TaCl5 in the
formation of the amorphous Li-ion conduction matrix. It
seems that all octahedra based on the dimeric structure (−
Ta2Cl10−) in pristine TaCl5 are decomposed into separate
octahedra (TaCl6−) and interacted with LiCl to sharing
common edges or corners within the amorphous matrix, which
is different from other metal chlorides (ZrCl4, HfCl4, YCl3,
InCl3, ScCl3 and LaCl3) with maintaining crystalline frame-
works.16−18,58,59
To compare the Li-ion conductivity of A-LTC with other
SEs, we summarized Arrhenius plots of the ionic conductivity
of the A-LTC together with typical polymer,62 glass-ceramic
27778
oxide/sulfide,28,29,60,61 halide,41,42,44,63 crystalline sulfide13,14
SEs, and liquid electrolyte64 in Figure 1c. The Li-ion
conductivities and activation energies are also summarized in
Table S5. The superionic conductivity of A-LTC is slightly
lower than that of the liquid electrolyte and sulfide crystalline
SEs but outclasses the Li-ion conductivity of polymer, glass-
ceramic oxide/sulfide, and halide SEs. Furthermore, A-LTC
possesses a low activation energy of 0.23 eV, which should
endow it with the capability to operate at a wide range of
temperatures and exhibit acceptable Li-ion conductivity at low
temperatures (0.76 mS cm−1 at −30 °C and 0.44 mS cm−1 at
−40 °C, Figure S1a,c).
To reveal the atomic arrangement of A-LTC and the
corresponding Li-ion conduction mechanism, we employed
https://doi.org/10.1021/jacs.3c10602
J. Am. Chem. Soc. 2023, 145, 27774−27787
Journal of the American Chemical Society
SSW-NN45,46,65 simulation to determine the A-LTC glassy
structure. A Li−Ta−Cl NN potential with a fixed component
ratio of Li/Ta/Cl = 1:1:6 was first trained based on 5060
configurations (Table S1) and utilized to determine the
thermodynamics of LiTaCl6. A total of 30,000 minima are
visited with up to 32 atoms in the unit cell, where 3864 distinct
minima in total are collected. Based on those minima, the
global PES is shown in Figure 2a by plotting the energy against
a distance-weighted Steinhart order parameter (OP).66 The
global minimum (GM) phase, which corresponds to the
perfect single crystal phase, has a space group P1̅(#2) (Figure
S3a) with the structure composed of LiCl65− and TaCl6−
octahedra sharing a common edge, extending in one dimension
while packing stick-by-stick along the other two dimensions.
Due to the weak van der Waals interaction between sticks,
many low-energy minima are energetically degenerated. For
example, the lowest energy region highlighted by a black
dashed circle in Figure 2a corresponds to 11 different
metastable configurations with subtle differences in their
packing patterns. Such a phenomenon is generally observed
in molecular crystals where the packing motif is also mainly
determined by the van der Waals interaction.67 Comparatively,
the most stable phases of ionic crystals generally have distinct
local configurations and relatively large energy differences.68
Another important feature is that the highest density of states
(h-DOS) region in Figure 2a (purple region), which represents
the amorphous phase of the material, is rather close to the GM
phase.
To show a typical structure of A-LTC, we choose the
configuration that corresponds to the central point of the h-
DOS region in Figure 2a, and the corresponding typical atomic
spatial arrangement consisting of separated vacancies and free
space is shown in Figures 2b and S3b−e. The amorphous
matrix is composed of LiCl43−, LiCl54−, LiCl65− polyhedra, and
TaCl6− octahedra sharing a common edge or corner. All Ta
atoms remain in the octahedral voids of Cl ions, while the Li
atoms are now in the octahedral, rectangular pyramid, and
tetrahedral voids. The statistically average pair correlation
function g(r) and the number of neighboring Cl atoms around
the Li and Ta atoms, respectively, of the global PES, are
plotted in Figure S4. Both Li atoms and Ta atoms tend to be
uniformly distributed in amorphous structures, as shown by
the first peak at 3.57 and 6.24 Å, respectively (Figure S4a,b),
which is consistent with the arrangement model of edge- or
corner-sharing Li−Cl polyhedra and isolated Ta−Cl octahedra
(Figure 2b). Meanwhile, in the amorphous matrix, most Li and
Ta atoms are nearest neighbors with Cl atoms, showing
predominantly by the first peak of Li−Ta, Li−Cl, and Ta−Cl
at 3.69 2.47, and 2.3 Å, respectively, as shown in Figure S4c−e.
Furthermore, the number of neighboring Cl atoms around the
Li and Ta atoms is extracted to reveal the coordination mode
of metal cations in the amorphous matrix. In the range of
∼2.57−3.87 Å around the Li atoms, the number of
neighboring Cl atoms fluctuates between 4 and 6 (Figure
S4f), which corresponds to the Li−Cl tetrahedron, pentahe-
dron, and octahedron of the amorphous structure, as shown in
Figure 2b. In contrast, the number of Cl atoms around the Ta
atoms does not fluctuate with distance in the range of ∼2.57−
4.37 Å (Figure S4g), indicating that Ta atoms simply exist as
Ta−Cl octahedra in the amorphous matrix.
Furthermore, NPD was also performed to confirm the
consistency of bulk structure between experimental and
simulation of A-LTC. As shown in Figure S5, experimental
27779
pubs.acs.org/JACS Article
results revealed that A-LTC consists of trace crystalline LiCl
and an amorphous matrix (diffuse peak region), which is
consistent with PXRD patterns. The diffuse peaks were
obtained by broadening based on long-range ordered peaks.
Also, the main simulated peak located at 2.4−3.1 Å
corresponds to the main diffuse peak at 2.6−3.3 Å of the
experimental observation, the corresponding crystallographic
planes were extracted and shown in Figure S6, indicating the
reliability of representative local configurations obtained by the
SSW-NN method (detailed discussion can be found in Note
S1).
By taking the above representative configurations of the
amorphous phases as the starting points, we performed 1 ns
molecular dynamics (MD) simulation for each configuration at
300 K to reveal the mechanisms of Li-ion conduction (details
can be found in the Experimental Section). From the MD
trajectories, we have captured three representative migration
pathways. As shown in Figure S7, the energy barriers of the
three migration paths of Li-ion are around 0.13 to 0.21 eV,
where the Li-ion moves from octahedral and tetrahedral voids
to the nearby octahedral and tetrahedral voids. In Movies S1−
S3 we can also see one efficient Li-ion migration that
contributes to the conductivity may contain several such
movements. The hopping of Li-ion happens within the
interspace between Li−Ta−Cl sticks (Figure S7a, Movie S1),
within the sticks (Figure S7b, Movie S2), or perpendicular to
the sticks (Figure S7c, Movie S3). Such a migration
mechanism is similar to that in our recently reported
Li2ZrCl658 with three different migration channels, except
that the pathways in Li−Ta−Cl involve more intermediates
and all energy barriers are lower than that in Li2ZrCl6. The
computed ionic conductivities of five MD trajectories vary
within 2.8−10.4 mS cm−1 and the average conductivity is 6.6
mS cm−1 at 300 K (Figure S8), which is close to the
experimental ionic conductivity, identifying the reliability of
the SSW-NN simulation.
To probe the coordination and local environment of Li
atoms in A-LTC, we collected the 7Li 1D MAS NMR spectrum
of the A-LTC powder. As shown in Figure 2c, the spectrum
displays two peaks, including a broad peak and a sharp peak
located at −0.62 and −1.11 ppm, respectively. The presence of
the peak at −1.11 ppm is recognized from residual LiCl by the
comparison of NMR spectroscopy of LiCl powders, as shown
in Figure 2d. The assignment of the broad peak at −0.62 ppm
to amorphous Li−Ta−Cl was further confirmed by the 7Li
NMR spectrum of the Li0.5TaCl5.5 powder by decreasing the
amount of LiCl in the precursors (Figure S9). The broad peak
at −0.62 ppm indicates various coordination types of Li with
Cl in the A-LTC that are consistent with the simulated local
configurations (Figure 2b). These two peaks of A-LTC were
further deconvoluted with two partially overlapped Lorentz−
Gaussian peaks (Figure 2c) to quantify the relative proportions
of Li atoms in the amorphous Li−Ta−Cl matrix and residual
LiCl, which were determined to be 92.9 and 7.1% (Figure 2e
and Table S6), respectively. It is worth noting that residual
LiCl was not detected by PXRD (Figure 1a) owing to the small
proportion, as revealed by NMR.
Furthermore, we performed synchrotron X-ray absorption
spectroscopy (XAS) to examine the local Ta atomic structure
of the A-LTC matrix. The quite similar Ta L3-edge XANES
spectra of A-LTC, TaCl5, and Ta2O5 (Figure S10) confirm the
pentavalent oxidation state of Ta in the obtained A-LTC
matrix. Also, the presence of Ta−O signals in A-LTC and
https://doi.org/10.1021/jacs.3c10602
J. Am. Chem. Soc. 2023, 145, 27774−27787
Journal of the American Chemical Society pubs.acs.org/JACS Article

Figure 3. Characterizations of the obtained ALTC·(x − 1)LiCl (2 ≤ x ≤ 7) composite SEs. (a) PXRD patterns of the obtained ALTC·(x − 1)LiCl
(2 ≤ x ≤ 7). The crystalline phase of LiCl is marked with red pentagrams. (b) Ionic conductivity at 25 °C and activation energy of ALTC·(x −
1)LiCl (2 ≤ x ≤ 7). (c) Proposed mosaic model for LiCl-poor and LiCl-rich amorphous matrix-encapsulated nanocrystalline LiCl composite SEs.
The purple irregular geometry, beige rectangle, and purple arrow represent the LiCl nanocrystals, amorphous matrix, and Li-ion migration pathway,
respectively. (d−f) 1D 7Li MAS NMR spectra and deconvolution analysis results corresponding to A-LTC·LiCl (d), A-LTC·3LiCl (e), and A-LTC·
6LiCl (f). (g−k) HRTEM image (g), corresponding FFT result (h) of the selected area (region 1) in (g), magnified HRTEM images (i,j) of the
selected area (regions 2, 3) in (g), and HAADF-STEM combined elemental mapping images (k) of A-LTC·3LiCl. Note: the interface (g) of the
amorphous matrix and nanocrystalline LiCl is selected from the area indicated by the red arrow as presented in (k).

TaCl5 may originate from impurities, including trace Ta2O5
and TaOCl3, generated in the synthesis of A-LTC, and the
transfer process for characterizations. The corresponding
extended EXAFS spectra of A-LTC and TaCl5 at the Ta L3-
edge show an identical dominant peak for the shortest Ta−Cl
coordination (Figure 2f and Table S7), revealing the same
octahedral coordination of Ta (TaCl6−) in both A-LTC and
TaCl5, which is also in agreement with the local TaCl6−
configuration of both distance and coordination numbers
obtained by the SSW-NN simulation (Figure S4).
To reveal the microstructure of the A-LTC matrix, we
performed cryo-TEM characterizations of the obtained
powders. As shown in Figure 2g, an irregular agglomerate of
particles was observed, indicating the random formation of an
amorphous matrix under mechanochemical reactions. High-
resolution TEM (HRTEM) images in Figure 2h,i further
revealed the disordered lattice structure with the absence of
27780
crystalline lattice fringes, which is consistent with the absence
of diffraction peaks in the PXRD pattern and in Figure 1a, the
red pattern. The amorphous matrix feature of A-LTC can be
further characterized by the corresponding fast Fourier
transform (FFT) pattern with only slight diffraction spots
(Figure 2j), representing the lattice distance of the (111) and
(200) planes of cubic LiCl (referring to ICSD 26909), which is
consistent with the residual LiCl detected by NMR (Figure
2c). Furthermore, high-angle annular dark-field scanning TEM
(HAADF-STEM) combined with energy-dispersive X-ray
spectroscopy mapping, backscattered electron (BSE) images,
and elemental mapping indicate the homogeneous incorpo-
ration of Ta and Cl into the amorphous matrix (Figure S11).
The amorphous matrix and high polarizability of chlorides
also lead to excellent deformability of the synthesized A-LTC.
As shown in Figures S12a−c and S13, intimate contacts
without GBs are observed in the cold-pressed A-LTC pellet.
https://doi.org/10.1021/jacs.3c10602
J. Am. Chem. Soc. 2023, 145, 27774−27787
Journal of the American Chemical Society pubs.acs.org/JACS Article

Figure 4. Electrochemical performance characterization of the A-LTC·Li-X (X = F, Cl, O, OH, O2). (a) Optimal ball mill time and ionic
conductivity of A-LTC·Li-X (X = F, Cl, O, OH, O2) electrolytes. (b) LSV curves of A-LTC·Li-X (X = F, Cl, O, OH, O2) electrolyte-based cells.
Testing cell setup: Li−In|Li6PS5Cl|A-LTC·Li-X|A-LTC·Li-X + VGCF. (c) Initial charge/discharge voltage-capacity profiles of ASSLB-Cl, ASSLB-F,
ASSLB-O, AASLB-OH, and ASSLB-O2 operated at current densities of 0.191 mA cm−2 (red profiles) and 1.5 mA cm−2 (blue profiles). (d)
Corresponding mass-normalized dQ/dV curves of ASSLBs. (e) Cycling stability evaluation of ASSLB-Cl, ASSLB-F, ASSLB-O, AASLB-OH, and
ASSLB-O2 at a current density of 1.5 mA cm−2. The filled and hollow symbols represent the capacity and Coulombic efficiency, respectively. The
temperature for all cycling tests is 30 °C.

The smooth surface and excellent ductility of the A-LTC pellet
endowed by the nature of the amorphous chloride matrix were
further confirmed by AFM measurements, showing a low rms
roughness of 1.66 nm (Figure S12d) and a low average
Young’s modulus of 2.91 ± 0.32 GPa (Figure S12e−i and
Table S8).
To show the superionic conduction and deformability of A-
LTC, we prepared a series of A-LTC matrix-encapsulated LiCl
composite SEs by introducing excessive LiCl in the reaction
precursors. The obtained xLiCl-TaCl5 was denoted as A-LTC·
(x − 1)LiCl. The PXRD patterns of the obtained products
reveal the existence of the LiCl phase in the range 2 ≤ x ≤ 7
without other crystalline phases (Figure 3a), indicating that
TaCl5 completely reacted with LiCl to form A-LTC. The ionic
conductivity and activation energy of A-LTC·(x − 1)LiCl (2 ≤
x ≤ 7) were obtained by temperature-dependent EIS
measurements and error bar analysis (Figures S14−S17).
27781
The calculated ionic conductivity and activation energy of A-
LTC·(x − 1)LiCl (2 ≤ x ≤ 7) are summarized in Figures 3b,
S14, and Table S9. All ALTC·(x − 1)LiCl (2 ≤ x ≤ 7) SEs
exhibit high ionic conductivity between 1.07 and 7.16 mS cm−1
with a low activation energy of 0.21 ± 0.04 eV. The electronic
conductivity of ALTC·(x − 1)LiCl (2 ≤ x ≤ 7) is in the range
of 4.5 × 10−10−1.0 × 10−9 S cm−1 (Figures S18, S19 and Table
S10). It is worth noting that the 7.16 mS cm−1 of room
temperature ionic conductivity of the A-LTC·LiCl composite
SE is a record-high value reported thus far for advanced
chloride SEs32 (Figure S20). The high Li-ion conductivity of
ALTC·(x − 1)LiCl (2 ≤ x ≤ 7) composite SEs can be
attributed to excellent Li-ion migration in the A-LTC matrix
and at the interface of the matrix/LiCl particles. Specifically, a
moderate amount of LiCl nanocrystals in the amorphous
matrix can boost the Li-ion conduction by releasing the mobile
Li-ion, which is also observed in the recently reported eutectic
https://doi.org/10.1021/jacs.3c10602
J. Am. Chem. Soc. 2023, 145, 27774−27787
Journal of the American Chemical Society
halides.43 Besides, the space charge effect69 widely exists in
composites is beneficial for Li-ion conduction70,71 in the case
of a high conduction matrix as the crucial factor for overall
conductivity of composite SEs. However, with the introduction
of more LiCl into the composite SEs, the tortuosity of the Li-
ion transport pathways increases due to the blocking effect of
crystalline LiCl (Figure 3c), which results in a decrease in the
Li-ion conduction in the composite SEs.
We further employed 7Li 1D NMR to probe the local
environment of Li atoms in the A-LTC·LiCl, A-LTC·3LiCl,
and A-LTC·6LiCl composite SEs. As shown in Figure 3d−f
and Table S6, the resonance chemical shifts of 7Li for the
amorphous matrix in ALTC·LiCl, ALTC·3LiCl, and ALTC·
6LiCl are centered at −0.59, −0.41, and −0.32 ppm,
respectively, which are offset by more positive ppm values
relative to the A-LTC (−0.62 ppm), indicating the changed
surrounding chemical environments of Li atoms in the
amorphous matrix. It is assumed that the total number of
Ta5+ ions in the matrix is constant, whereas the average
number of Ta5+ ions surrounding Li+ ions decreases with the
introduction of more LiCl, which results in more positive shifts
of the resonance peaks of 7Li. This is consistent with a recent
result that the more positive resonance chemical shift for 7Li of
the halide electrolyte with stacking faults is correlated with a
greater number of surrounding Li+ ions.72 Furthermore, the
insets in Figure 3d−f clearly show that with increasing LiCl
precursor content the proportion of residual LiCl increased
from 50.9 to 86.1%.
Despite the increase in the amount of residual LiCl in the
composite SEs, the deformability of A-LTC is still well
maintained. SEM, AFM, and BSE results (Figures S21−S25
and Table S8), including the intimate contact GB-free surface,
low rms roughness (1.83−2.00 nm), and low average modulus
(3.1−3.58 GPa), which is lower than those of oxides and
sulfides (Figure S26), demonstrate the ductility of A-LTC·
LiCl, A-LTC·3LiCl, and A-LTC·6LiCl stemming from the soft
A-LTC matrix. In this scenario, the underlying origin of the
exceptional superionic conduction of A-LTC·(x − 1)LiCl (2 ≤
x ≤ 7) composite SEs lies in their intrinsic high ductility and
many isotropic migration pathways in the amorphous matrix
(Figure 3c). Besides, the densities of the cold-pressed A-LTC,
A-LTC·LiCl, A-LTC·3LiCl, and A-LTC·6LiCl pellets are 3.10,
2.90, 2.61. 2.23 g cm−3, respectively, which is similar to that of
typical crystalline halides (Figure S27, Note S2, and Table
S11).
To reveal the microstructure of the composite SE, we
performed cryo-TEM on A-LTC·3LiCl. The A-LTC matrix-
encapsulated LiCl composite structure can be confirmed by
selected area electron diffraction (Figure S28). We highlighted
three regions in Figure 3g to show the typical microstructure of
the composite SE. The thick amorphous matrix (Figure 3g,
region 1) was revealed by the FFT pattern, as shown in Figure
3h. At the interface of the amorphous matrix and nanocrystal-
line LiCl (Figure 3g, region 2), distortion of lattice fringes is
observed (Figure 3i), which corresponds to the incomplete
lattice period caused by local strain and defects at the interface.
The nanocrystalline LiCl (Figure 3g, region 3) was confirmed
by the clear lattice with an interplanar spacing of 2.96 Å
(Figure 3j), which matches the crystal plane distance of the
(111) planes of cubic LiCl (referred to as ICSD no. 26909).
The LiCl nanoparticles attached on the surface of the A-LTC
aggregate were also revealed by HAADF-STEM and the
corresponding elemental mapping images (Figure 3k). The Ta
27782
pubs.acs.org/JACS Article
and Cl elements are distributed uniformly throughout the
amorphous matrix, while only the Cl element can be observed
in the LiCl nanoparticles. The TEM analysis of A-LTC·3LiCl
is consistent with the proposed mosaic model (Figure 3c) that
the nanocrystalline LiCl particles are dispersed in and around
the A-LTC matrix.
Using the A-LTC as the matrix, we can also prepare a series
of composite SEs by encapsulating various lithium salts such as
LiF, Li2O, LiOH, and Li2O2 (Note S3). We conducted PXRD
measurements (Figure S29a−d) of the obtained composite SEs
and found that all of the samples possess poor crystalline
features with tiny crystalline LiCl, indicating that the
amorphous matrix possesses good compatibility with different
types of anions. Additionally, the Li-ion conduction of the
obtained composite SEs at room temperature was evaluated by
EIS, and the Nyquist plots are shown in Figure S29e−h. The
calculated room-temperature ionic conductivities are summar-
ized in Figure S29i. All of the A-LTC·Li-X composite SEs
exhibit good ionic conductivities of 0.78, 4.72, 4.08, and 4.95
mS cm−1 when appropriate amounts of LiF, Li2O, LiOH, and
Li2O2 were introduced into the A-LTC matrix, respectively
(Figure 4a). These results highlighted the flexibility of A-LTC
glassy networks to enable a wide range of composite SE
options. However, the different effective ionic radii and
polarizability between halides and oxides resulted in different
deformabilities and solid−solid contact in the composite SEs
(Figures S30−S32). It is worth pointing out that the
introduction of O2−, OH−, and O22− can lead to shorter
optimal time for achieving the optimal conductivity compared
to Cl− and F−. As listed in Figure 4a and Table S12, the
optimal conductivities can be achieved in 24 h for A-LTC·Li-X
(X = O2−, OH−, and O22−) and over 144 h for A-LTC·Li-X (X
= F−, Cl−), respectively. However, the synthesis of SE for up to
a week would decrease the efficiency and inevitably increase
the time cost of synthesis inevitably. The different synthesis
times may be related to the formation energy of raw materials,
as shown in Figure S33. During the reaction, the trend of
decomposition of raw materials is LiF < LiCl < Li2O < LiOH <
Li2O2. And Ta−O could be more stable than Ta−Cl bonding.
Thus, when the O2−, OH−, and O22− anions were introduced
into the reaction system, the amorphous matrix, consisting of
Li−Ta−O−Cl, may form rapidly, resulting in a shorter
synthesis time compared to that of Cl− and F−.
In addition, the effect of various anions on the electro-
chemical oxidation stability of the A-LTC-based composite SE
is also investigated by the linear sweep voltammetry (LSV)
measurement based on the Li−In|Li6PS5Cl|A-LTC·Li-X|A-
LTC·Li-X + VGCF cells. The onset oxidation potentials of A-
LTC, A-LTC·0.5LiF, A-LTC·LiCl, A-LTC·0.5Li2O, A-LTC·
0.75LiOH, and A-LTC·0.5Li2O2 were observed at 4.41, 4.36,
4.43, 4.30, 4.43, and 4.38 V, respectively (Figure 4b). A similar
oxidation stability may be determined by the characteristic of
amorphous chloride matrix not the various anions, implying
that all the A-LTC-based composite SEs are compatible with
high-voltage high-nickel cathode (>4 V). Motivated by the
superionic conductivity and desirable electrochemical stability,
we fabricated ASSLBs by employing A-LTC-based composite
SEs, S-NCM88 cathodes, and Li−In alloy anodes. Such
ASSLBs can be assembled by a feasible cold-pressing route due
to the excellent deformability of the A-LTC matrix. The
ASSLBs based on A-LTC·LiCl (7.16 mS cm−1), A-LTC·0.5LiF
(0.78 mS cm−1), A-LTC·0.5Li2O (4.72 mS cm−1), A-LTC·
0.75LiOH (4.08 mS cm−1), and A-LTC·0.5Li2O2 (4.95 mS
https://doi.org/10.1021/jacs.3c10602
J. Am. Chem. Soc. 2023, 145, 27774−27787
Journal of the American Chemical Society pubs.acs.org/JACS Article

Figure 5. Performance of the fabricated ASSLB-Cl in the ambient temperature of 30 °C and −10 °C. (a) Long-term cycling at ∼3 C (3 mA cm−2).
(b) Rate performance at various rates in the range from 0.2 to 4.0 C. (c) Cycling characteristics with a high mass loading of S-NCM88 (25.1 mg
cm−2) at 1.0 mA cm−2. (d) Rate performance at various rates in the range from 0.113 (0.25 mA cm−2) to 0.904 C (2 mA cm−2). (e) Discharge
voltage-capacity profiles at various rates in the range from 0.113 (0.25 mA cm−2) to 0.904 C (2 mA cm−2). (f) Discharge capacity retention at
various rates in the range from 0.113 (0.25 mA cm−2) to 0.904 C (2 mA cm−2). (g) Long-term cycling at ∼3.4 C (3 mA cm−2). The ambient
temperature for all cycling tests presented in (a−c,d−g) was 30 and −10 °C, respectively.

cm−1) SEs are denoted as ASSLB-Cl, ASSLB-F, ASSLB-O,
AASLB-OH, and ASSLB-O2, respectively. The charge and
discharge curves of the initial cycle of these ASSLBs are shown
in Figure 4c. The initial Coulombic efficiencies (CEs) are
94.47, 90.63, 91.13, 91.30, and 94.37% for ASSLB-Cl, ASSLB-
F, ASSLB-O, AASLB-OH, and ASSLB-O2, respectively, which
indicate that the A-LTC-based composite SEs are stable
against the S-NCM88 cathode with a limited interface side
27783
reaction. Meanwhile, the corresponding mass-normalized dQ/
dV curves also show typical redox peaks to demonstrate the
compatibility of A-LTC-based SEs toward S-NCM88 (Figure
4d). Typical redox reaction peaks are observed at 3.60, 4.01,
and 4.18 V, revealing that the S-NCM88 cathode underwent
three phase transformations, including H1 → M, M → H2, and
H2 → H3,73 respectively. In addition, the initial discharge
capacities of ASSLB-F are 172.48 and 106.15 mA h g−1 at
https://doi.org/10.1021/jacs.3c10602
J. Am. Chem. Soc. 2023, 145, 27774−27787
Journal of the American Chemical Society
0.191 and 1.50 mA cm−2, respectively, lower than that of ∼200
and ∼165 mA h g−1 for other ASSLBs (Figure 4c−e),
indicating lower utilization of S-NCM88 in ASSLB-F. Also, the
lower utilization is related to the limited percolating network of
ion-conduction in the composite cathode resulting from the
loose solid−solid contact and poorer Li-ion conductivity of A-
LTC·0.5LiF (Figure 4a), which led to poorer electrochemical
performance. In short, all the fabricated ASSLBs were cycled at
a current density of 0.191 mA cm−2 for the first three cycles
and the following cycles at 1.5 mA cm−2, all of which exhibited
a good capacity retention of >76% and a high average CE of
>99% over 100 cycles (Figure 4e).
We further evaluated the long-term cycling stability of
ASSLB-Cl due to its best performance among the fabricated
ASSLBs. As shown in Figure 5a, the ASSLB-Cl can achieve a
capacity retention of 100% over 800 cycles with an average CE
of ∼98.8%. Another ASSLB-Cl was fabricated and exhibited
analogical stable operation, in terms of capacity retention of
83.8 and 70% over 2000 and 3000 cycles (Figure S34), which
is the top-notch performance among recent reports. The
outstanding cycling performance indicates the realization of
virtually no capacity fading of ASSLB-Cl benefiting from the
deformability of A-LTC for constructing intimate solid−solid
contacts and buffering the volume change of the cathode
during cycling. The rate capability test result is presented in
Figure 5b, and the reversible capacities of ASSLB-Cl are
∼205.6, 190.2, 172.2, 149.6, and 132.8 mA h g−1 at rates of
∼0.2, 0.5, 1.0, 2.0, and 3.0 C, respectively. A reversible capacity
of 115.1 mA h g−1 can still be maintained even with a high rate
of ∼4.0 C. The discharge capacity can be recovered when the
current density returns from 4.0 to 0.2 C. These results
indicate the excellent rate capability of the fabricated ASSLB-
Cl, which is linked to the excellent electrochemical stability
and intimate physical contact enabled by the A-LTC matrix. In
addition, the cycling performance of ASSLB-Cl with a high
mass loading of S-NCM88 (∼25 mg cm−2) is shown in Figure
5c. The reversible phase transitions of S-NCM88 are
observable in the dQ/dV curves (Figure S35) at current
densities of 0.5 and 1 mA cm−2, indicating adequate Li-ion and
electron conduction in the thick cathode enabled by the
amorphous matrix. Moreover, ASSLB-Cl displays a remarkable
reversible areal capacity of 5.1 and 4.9 mA h cm −2
(corresponding to 205.2 and 195.7 mA h g−1) at 0.5 and 1
mA cm−2, respectively, which provides a competitive areal
capacity compared to that of commercial LIBs. Under
continuous cycling at 1 mA cm−2, ASSLB-Cl can exhibit a
capacity retention of 80% after 75 cycles and an average CE of
99.71%. Another two ASSLB-Cl with an S-NCM88 loading of
23 mg cm−2, corresponding to an areal capacity of ∼5 mA h
cm−2, also display reproducible performances in terms of
reversible phase transformations, capacity retention, and
average CE, as shown in Figure S36.
In order to verify the feasibility of the ASSLBs in a freezing
environment, we explored the cycling performance of ASSLBs
at a low temperature of −10 °C. The rate performance of the
ASSLB with an area capacity of 2.2 mA h cm−2 is presented in
Figure 5d. Discharge capacities are 172.5, 162.4, 154.3, 146.2,
128.3, and 114.7 mA h g−1 at current densities of 0.25, 0.5,
0.75, 1.0, 1.5, and 2.0 mA cm−2, respectively (Figure 5d,e).
Also, the discharge capacity can be recovered when the current
density returns from 2.0 to 0.5 mA cm−2. Up to 66.5% of the
capacity was retained at a high current density of 2.0 mA cm−2
compared to that of 0.25 mA cm−2 (Figure 5f), which
27784
pubs.acs.org/JACS Article
indicated effective conduction of Li-ions and intimate physical
solid−solid contact in the composite cathode enabled by the
amorphous matrix even at freezing temperature. To validate
the high-power capability of ASSLBs at a low temperature,
another ASSLB with an area capacity of 0.88 mA h cm−2 was
operated at a high current density of up to 3 mA cm−2 (3.37
C) for long-term cycling. The ASSLB achieved a capacity
retention of over ∼77% over 9000 cycles with an average CE of
∼99.98% (Figure 5g). The corresponding performances are
summarized in Table S13 and compared to those of recently
reported ASSLBs based on sulfide and halide SEs. The top-
notch performance of our ASSLB at a low temperature
demonstrated the potential of amorphous chloride SEs in
tackling the issue of sluggish kinetics of Li-ion migration in the
electrolyte and electrolyte−electrode at low temperatures.
In short, ASSLBs based on A-LTC·LiCl exhibit a high CE,
outstanding rate capability, and excellent cycling stability with
an areal capacity in the range of 1−5 mA h cm−2 in both
extreme and conventional environments, which represents the
state-of-the-art performance of recently reported ASSLBs
based on halide and sulfide SEs, as listed in Figure S37 and
Tables S13, S14. The amorphous chloride SEs can be
expanded to the cost-effective NbCl5 system, presenting a
similar capability of Li-ion conduction and a stable operation
of ASSLBs with an areal capacity of up to 6 mA h cm−2
(Figures S38, S39 and Tables S15, S16), detailed discussions
can be found in Note S4.
■ CONCLUSIONS
In summary, we reported a new type of amorphous chloride Li-
ion conductor, Li−Ta−Cl, which can enable the high areal
capacity of high-nickel cathodes, owing to its high conductivity,
superior mechanical deformability, and electrochemical
stability. Based on the A-LTC matrix, various composite SEs
can be obtained with high ionic conductivity in the range of
0.78−7.16 mS cm−1. The fabricated ASSLBs exhibit out-
standing electrochemical performance with a high CE
exceeding 99%, prominent rate capability up to 4 C, and
excellent capacity retention of 98.8% at 3 C for 800 cycles.
Most importantly, the ASSLBs with an areal capacity of up to 5
mA h cm−2 exhibited 80% capacity retention after 75 cycles at
a high current density of 1 mA cm−2. Besides, the high-rate
capability of ASSLBs in a freezing environment was
demonstrated with a stable operation up to 9800 cycles at a
high rate of ∼3.4 C. Our reported amorphous chloride SEs
with composition tunability, superionic conductivity, remark-
able deformability, and good high-nickel cathode compatibility
will pave the way to fabricating high-energy-density ASSLBs.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/jacs.3c10602.
Characterizations, electrochemical results, and additional
figures, notes, tables, and movies (PDF)
Crystallographic data of amorphous chloride SEs (ZIP)
Crystallographic data of the GM phase material (ZIP)
■ AUTHOR INFORMATION
Corresponding Authors
Xinyong Tao − College of Materials Science and Engineering,
Zhejiang University of Technology, Hangzhou 310014
https://doi.org/10.1021/jacs.3c10602
J. Am. Chem. Soc. 2023, 145, 27774−27787
Journal of the American Chemical Society
Zhejiang, China; orcid.org/0000-0003-4084-7743;
Email: tao@zjut.edu.cn
Cheng Shang − Collaborative Innovation Center of Chemistry
for Energy Material, Shanghai Key Laboratory of Molecular
Catalysis and Innovative Materials, Key Laboratory of
Computational Physical Science, Department of Chemistry,
Fudan University, Shanghai 200433, China; Shanghai Qi
Zhi Institute, Shanghai 200030, China; orcid.org/0000-
0001-7486-1514; Email: cshang@fudan.edu.cn
Hong-Bin Yao − Division of Nanomaterials and Chemistry,
Hefei National Research Center for Physical Sciences at the
Microscale, University of Science and Technology of China,
Hefei 230026 Anhui, China; Department of Applied
Chemistry, University of Science and Technology of China,
Hefei 230026 Anhui, China; orcid.org/0000-0002-2901-
0160; Email: yhb@ustc.edu.cn
Authors
Feng Li − Division of Nanomaterials and Chemistry, Hefei
National Research Center for Physical Sciences at the
Microscale, University of Science and Technology of China,
Hefei 230026 Anhui, China
Xiaobin Cheng − Department of Applied Chemistry,
University of Science and Technology of China, Hefei 230026
Anhui, China
Gongxun Lu − College of Materials Science and Engineering,
Zhejiang University of Technology, Hangzhou 310014
Zhejiang, China
Yi-Chen Yin − Department of Applied Chemistry, University
of Science and Technology of China, Hefei 230026 Anhui,
China
Ye-Chao Wu − Department of Applied Chemistry, University
of Science and Technology of China, Hefei 230026 Anhui,
China; Hefei Gotion High-tech Power Energy Co., Ltd., Hefei
230012 Anhui, China
Ruijun Pan − Hefei Gotion High-tech Power Energy Co., Ltd.,
Hefei 230012 Anhui, China
Jin-Da Luo − Department of Applied Chemistry, University of
Science and Technology of China, Hefei 230026 Anhui,
China
Fanyang Huang − Division of Nanomaterials and Chemistry,
Hefei National Research Center for Physical Sciences at the
Microscale, University of Science and Technology of China,
Hefei 230026 Anhui, China; Department of Materials
Science and Engineering, CAS Key Laboratory of Materials
for Energy Conversion, University of Science and Technology
of China, Hefei 230026 Anhui, China
Li-Zhe Feng − Department of Applied Chemistry, University
of Science and Technology of China, Hefei 230026 Anhui,
China
Lei-Lei Lu − Division of Nanomaterials and Chemistry, Hefei
National Research Center for Physical Sciences at the
Microscale, University of Science and Technology of China,
Hefei 230026 Anhui, China
Tao Ma − Division of Nanomaterials and Chemistry, Hefei
National Research Center for Physical Sciences at the
Microscale, University of Science and Technology of China,
Hefei 230026 Anhui, China
Lirong Zheng − Institute of High Energy Physics, the Chinese
Academy of Sciences, Beijing 100049, China
Shuhong Jiao − Division of Nanomaterials and Chemistry,
Hefei National Research Center for Physical Sciences at the
Microscale, University of Science and Technology of China,
27785
pubs.acs.org/JACS Article
Hefei 230026 Anhui, China; Department of Materials
Science and Engineering, CAS Key Laboratory of Materials
for Energy Conversion, University of Science and Technology
of China, Hefei 230026 Anhui, China; orcid.org/0000-
0003-0860-4151
Ruiguo Cao − Division of Nanomaterials and Chemistry,
Hefei National Research Center for Physical Sciences at the
Microscale, University of Science and Technology of China,
Hefei 230026 Anhui, China; Department of Materials
Science and Engineering, CAS Key Laboratory of Materials
for Energy Conversion, University of Science and Technology
of China, Hefei 230026 Anhui, China; orcid.org/0000-
0002-3177-3917
Zhi-Pan Liu − Collaborative Innovation Center of Chemistry
for Energy Material, Shanghai Key Laboratory of Molecular
Catalysis and Innovative Materials, Key Laboratory of
Computational Physical Science, Department of Chemistry,
Fudan University, Shanghai 200433, China; Shanghai Qi
Zhi Institute, Shanghai 200030, China; orcid.org/0000-
0002-2906-5217
Hongmin Zhou − Division of Nanomaterials and Chemistry,
Hefei National Research Center for Physical Sciences at the
Microscale, University of Science and Technology of China,
Hefei 230026 Anhui, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/jacs.3c10602
Author Contributions
○
F.L. and X.C. contributed equally to this work.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
We acknowledge the financial support from the National
Natural Science Foundation of China (grant nos. 22325505,
52073271, 52225208, 22161142004, 22033003, 92061112,
and 22122301), the National Key Research and Development
Program of China (grant no. 2018YFA0208600), the
Fundamental Research Funds from University of Science and
Technology of China (grant no. KY2060000207), the
Collaborative Innovation Program of Hefei Science Center,
CAS (grant no. 2022HSC-CIP018), and the Open Funds of
the State Key Laboratory of Rare Earth Resource Utilization
(grant no. RERU2022003). T.M. acknowledges the Shenzhen
Science and Technology Program (grant no.
JCYJ20190808143007479). We thank the beamline 1W1B
station of Beijing Synchrotron Radiation Facility (BSRF) for
providing the beam time. We greatly appreciate the neutron
beamtime granted from the CSNS and the technical assistance
from Juping Xu, Wen Yin, Zhongyuan Huang and Yinguo
Xiao. We thank the support from the USTC Center for Micro-
and Nanoscale Research and Fabrication. We also thank the
support from the Hefei Advanced Computing Center. We are
grateful to Dr. L.Z. from the Institute of High Energy Physics
for the analysis of EXAFS results. We are also grateful to Dr.
Ke Gong and Dr. Yu-Song Wang from the USTC Center for
Physical and Chemical Science Laboratory for the analysis of
NMR spectra.
■ REFERENCES
(1) Dunn, B.; Kamath, H.; Tarascon, J.-M. Electrical energy storage
for the grid: a battery of choices. Science 2011, 334 (6058), 928−935.
https://doi.org/10.1021/jacs.3c10602
J. Am. Chem. Soc. 2023, 145, 27774−27787
Journal of the American Chemical Society
(2) Lin, D.; Liu, Y.; Cui, Y. Reviving the lithium metal anode for
high-energy batteries. Nat. Nanotechnol. 2017, 12 (3), 194−206.
(3) Larcher, D.; Tarascon, J.-M. Towards greener and more
sustainable batteries for electrical energy storage. Nat. Chem. 2015,
7 (1), 19−29.
(4) Han, X.; Gong, Y.; Fu, K. K.; He, X.; Hitz, G. T.; Dai, J.; Pearse,
A.; Liu, B.; Wang, H.; Rubloff, G.; et al. Negating interfacial
impedance in garnet-based solid-state Li metal batteries. Nat. Mater.
2017, 16 (5), 572−579.
(5) Janek, J.; Zeier, W. G. A solid future for battery development.
Nat. Energy 2016, 1 (9), 16141.
(6) Hu, Y.-S. Batteries: getting solid. Nat. Energy 2016, 1 (4), 16042.
(7) Chen, R.; Li, Q.; Yu, X.; Chen, L.; Li, H. Approaching practically
accessible solid-state batteries: stability issues related to solid
electrolytes and interfaces. Chem. Rev. 2020, 120 (14), 6820−6877.
(8) Banerjee, A.; Wang, X.; Fang, C.; Wu, E. A.; Meng, Y. S.
Interfaces and interphases in all-solid-state batteries with inorganic
solid electrolytes. Chem. Rev. 2020, 120 (14), 6878−6933.
(9) Manthiram, A.; Yu, X.; Wang, S. Lithium battery chemistries
enabled by solid-state electrolytes. Nat. Rev. Mater. 2017, 2 (4),
16103.
(10) Zhao, Q.; Stalin, S.; Zhao, C.-Z.; Archer, L. A. Designing solid-
state electrolytes for safe, energy-dense batteries. Nat. Rev. Mater.
2020, 5 (3), 229−252.
(11) Wang, S.; Zhang, W.; Chen, X.; Das, D.; Ruess, R.; Gautam, A.;
Walther, F.; Ohno, S.; Koerver, R.; Zhang, Q.; et al. Influence of
crystallinity of lithium thiophosphate solid electrolytes on the
performance of solid-state batteries. Adv. Energy Mater. 2021, 11
(24), 2100654.
(12) Stramare, S.; Thangadurai, V.; Weppner, W. Lithium
lanthanum titanates: a review. Chem. Mater. 2003, 15 (21), 3974−
3990.
(13) Kamaya, N.; Homma, K.; Yamakawa, Y.; Hirayama, M.; Kanno,
R.; Yonemura, M.; Kamiyama, T.; Kato, Y.; Hama, S.; Kawamoto, K.;
et al. A lithium superionic conductor. Nat. Mater. 2011, 10 (9), 682−
686.
(14) Kato, Y.; Hori, S.; Saito, T.; Suzuki, K.; Hirayama, M.; Mitsui,
A.; Yonemura, M.; Iba, H.; Kanno, R. High-power all-solid-state
batteries using sulfide superionic conductors. Nat. Energy 2016, 1 (4),
16030.
(15) Adeli, P.; Bazak, J. D.; Park, K. H.; Kochetkov, I.; Huq, A.;
Goward, G. R.; Nazar, L. F. Boosting solid-state diffusivity and
conductivity in lithium superionic argyrodites by halide substitution.
Angew. Chem., Int. Ed. 2019, 58 (26), 8681−8686.
(16) Asano, T.; Sakai, A.; Ouchi, S.; Sakaida, M.; Miyazaki, A.;
Hasegawa, S. Solid halide electrolytes with high lithium-ion
conductivity for application in 4 V class bulk-type all-solid-state
batteries. Adv. Mater. 2018, 30 (44), 1803075.
(17) Liang, J.; Li, X.; Wang, S.; Adair, K. R.; Li, W.; Zhao, Y.; Wang,
C.; Hu, Y.; Zhang, L.; Zhao, S.; et al. Site-occupation-tuned superionic
LixScCl3+x halide solid electrolytes for all-solid-state batteries. J. Am.
Chem. Soc. 2020, 142 (15), 7012−7022.
(18) Li, X.; Liang, J.; Luo, J.; Norouzi Banis, M.; Wang, C.; Li, W.;
Deng, S.; Yu, C.; Zhao, F.; Hu, Y.; et al. Air-stable Li3InCl6 electrolyte
with high voltage compatibility for all-solid-state batteries. Energy
Environ. Sci. 2019, 12 (9), 2665−2671.
(19) Auvergniot, J.; Cassel, A.; Ledeuil, J.-B.; Viallet, V.; Seznec, V.;
Dedryvère, R. Interface stability of argyrodite Li6PS5Cl toward
LiCoO2, LiNi1/3Co1/3Mn1/3O2, and LiMn2O4 in bulk all-solid-state
batteries. Chem. Mater. 2017, 29 (9), 3883−3890.
(20) Yokokawa, H. Thermodynamic stability of sulfide electrolyte/
oxide electrode interface in solid-state lithium batteries. Solid State
Ionics 2016, 285, 126−135.
(21) Xu, S.; Hu, L. Towards a high-performance garnet-based solid-
state Li metal battery: A perspective on recent advances. J. Power
Sources 2020, 472, 228571.
(22) Kato, Y.; Shiotani, S.; Morita, K.; Suzuki, K.; Hirayama, M.;
Kanno, R. All-solid-state batteries with thick electrode configurations.
J. Phys. Chem. Lett. 2018, 9 (3), 607−613.
27786
pubs.acs.org/JACS Article
(23) Randau, S.; Weber, D. A.; Kötz, O.; Koerver, R.; Braun, P.;
Weber, A.; Ivers-Tiffée, E.; Adermann, T.; Kulisch, J.; Zeier, W. G.;
et al. Benchmarking the performance of all-solid-state lithium
batteries. Nat. Energy 2020, 5 (3), 259−270.
(24) Minami, T. Fast ion conducting glasses. J. Non Cryst. Solids
1985, 73 (1−3), 273−284.
(25) Minami, T. Recent progress in superionic conducting glasses. J.
Non-Cryst. Solids 1987, 95−96, 107−118.
(26) Minami, T.; Hayashi, A.; Tatsumisago, M. Recent progress of
glass and glass-ceramics as solid electrolytes for lithium secondary
batteries. Solid State Ionics 2006, 177 (26−32), 2715−2720.
(27) Tatsumisago, M.; Hayashi, A. Superionic glasses and glass-
ceramics in the Li2S-P2S5 system for all-solid-state lithium secondary
batteries. Solid State Ionics 2012, 225, 342−345.
(28) Yu, X.; Bates, J.; Jellison, G.; Hart, F. A stable thin-film lithium
electrolyte: lithium phosphorus oxynitride. J. Electrochem. Soc. 1997,
144 (2), 524−532.
(29) Mizuno, F.; Hayashi, A.; Tadanaga, K.; Tatsumisago, M. New,
highly ion-conductive crystals precipitated from Li2S-P2S5 glasses.
Adv. Mater. 2005, 17 (7), 918−921.
(30) Liu, Y.; Peng, H.; Su, H.; Zhong, Y.; Wang, X.; Xia, X.; Gu, C.;
Tu, J. Ultrafast Synthesis of I-Rich Lithium Argyrodite Glass-Ceramic
Electrolyte with High Ionic Conductivity. Adv. Mater. 2022, 34 (3),
2107346.
(31) Famprikis, T.; Canepa, P.; Dawson, J. A.; Islam, M. S.;
Masquelier, C. Fundamentals of inorganic solid-state electrolytes for
batteries. Nat. Mater. 2019, 18 (12), 1278−1291.
(32) Wang, C.; Liang, J.; Kim, J. T.; Sun, X. Prospects of halide-
based all-solid-state batteries: From material design to practical
application. Sci. Adv. 2022, 8 (36), No. eadc9516.
(33) Zhou, L.; Zuo, T.-T.; Kwok, C. Y.; Kim, S. Y.; Assoud, A.;
Zhang, Q.; Janek, J.; Nazar, L. F. High areal capacity, long cycle life 4
V ceramic all-solid-state Li-ion batteries enabled by chloride solid
electrolytes. Nat. Energy 2022, 7 (1), 83−93.
(34) Kwak, H.; Han, D.; Lyoo, J.; Park, J.; Jung, S. H.; Han, Y.;
Kwon, G.; Kim, H.; Hong, S. T.; Nam, K. W.; et al. New Cost-
Effective Halide Solid Electrolytes for All-Solid-State Batteries:
Mechanochemically Prepared Fe3+-Substituted Li2ZrCl6. Adv. Energy
Mater. 2021, 11 (12), 2003190.
(35) Fu, J.; Yang, S.; Hou, J.; Azhari, L.; Yao, Z.; Ma, X.; Liu, Y.;
Vanaphuti, P.; Meng, Z.; Yang, Z.; et al. Modeling assisted synthesis of
Zr-doped Li3‑xIn1‑xZrxCl6 with ultrahigh ionic conductivity for lithium-
ion batteries. J. Power Sources 2023, 556, 232465.
(36) Park, J.; Han, D.; Kwak, H.; Han, Y.; Choi, Y. J.; Nam, K.-W.;
Jung, Y. S. Heat treatment protocol for modulating ionic conductivity
via structural evolution of Li3‑xYb1‑xMxCl6 (M = Hf4+, Zr4+) new
halide superionic conductors for all-solid-state batteries. Chem. Eng. J.
2021, 425, 130630.
(37) Kwak, H.; Han, D.; Son, J. P.; Kim, J. S.; Park, J.; Nam, K.-W.;
Kim, H.; Jung, Y. S. Li+ conduction in aliovalent-substituted
monoclinic Li2ZrCl6 for all-solid-state batteries: Li2+xZr1‑xMxCl6
(M= In, Sc). Chem. Eng. J. 2022, 437, 135413.
(38) Chen, S.; Yu, C.; Chen, S.; Peng, L.; Liao, C.; Wei, C.; Wu, Z.;
Cheng, S.; Xie, J. Enabling ultrafast lithium-ion conductivity of
Li2ZrCl6 by indium doping. Chin. Chem. Lett. 2022, 33 (10), 4635−
4639.
(39) Hu, L.; Wang, J.; Wang, K.; Gu, Z.; Xi, Z.; Li, H.; Chen, F.;
Wang, Y.; Li, Z.; Ma, C. A cost-effective, ionically conductive and
compressible oxychloride solid-state electrolyte for stable all-solid-
state lithium-based batteries. Nat. Commun. 2023, 14 (1), 3807.
(40) Li, B.; Li, Y.; Zhang, H.-S.; Wu, T.-T.; Guo, S.; Cao, A.-M. Fast
Li+-conducting Zr4+-based oxychloride electrolyte with good thermal
and solvent stability. Sci. China Mater. 2023, 66, 3123−3128.
(41) Zhang, S.; Zhao, F.; Chen, J.; Fu, J.; Luo, J.; Alahakoon, S. H.;
Chang, L.-Y.; Feng, R.; Shakouri, M.; Liang, J.; et al. A family of
oxychloride amorphous solid electrolytes for long-cycling all-solid-
state lithium batteries. Nat. Commun. 2023, 14 (1), 3780.
(42) Ishiguro, Y.; Ueno, K.; Nishimura, S.; Iida, G.; Igarashib, Y.
TaCl5-glassified ultrafast lithium ion-conductive halide electrolytes for
https://doi.org/10.1021/jacs.3c10602
J. Am. Chem. Soc. 2023, 145, 27774−27787
Journal of the American Chemical Society pubs.acs.org/JACS Article

high-performance all-solid-state lithium batteries. Chem. Lett. 2023, 52 Conductivity > 10 mS cm−1 for All-Solid-State Batteries. Angew.
(4), 237−241. Chem., Int. Ed. 2023, 62 (13), No. e202217581.
(43) Xu, R.; Yao, J.; Zhang, Z.; Li, L.; Wang, Z.; Song, D.; Yan, X.; (64) Stallworth, P.; Fontanella, J.; Wintersgill, M.; Scheidler, C. D.;
Yu, C.; Zhang, L. Room Temperature Halide-Eutectic Solid Immel, J. J.; Greenbaum, S.; Gozdz, A. NMR, DSC and high pressure
Electrolytes with Viscous Feature and Ultrahigh Ionic Conductivity. electrical conductivity studies of liquid and hybrid electrolytes. J.
Adv. Sci. 2022, 9 (35), 2204633. Power Sources 1999, 81−82, 739−747.
(44) Jung, S.-K.; Gwon, H.; Yoon, G.; Miara, L. J.; Lacivita, V.; Kim, (65) Huang, S.-D.; Shang, C.; Kang, P.-L.; Liu, Z.-P. Atomic
J.-S. Pliable lithium superionic conductor for all-solid-state batteries. structure of boron resolved using machine learning and global
ACS Energy Lett. 2021, 6 (5), 2006−2015. sampling. Chem. Sci. 2018, 9 (46), 8644−8655.
(45) Huang, S. D.; Shang, C.; Kang, P. L.; Zhang, X. J.; Liu, Z. P. (66) Steinhardt, P. J.; Nelson, D. R.; Ronchetti, M. Bond-
LASP: Fast global potential energy surface exploration. WIRES orientational order in liquids and glasses. Phys. Rev. B 1983, 28 (2),
Comput. Mol. Sci. 2019, 9 (6), No. e1415. 784−805.
(46) Shang, C.; Liu, Z.-P. Stochastic surface walking method for (67) Shang, C.; Zhang, X. J.; Liu, Z. P. Crystal phase transition of
structure prediction and pathway searching. J. Chem. Theory Comput. urea: what governs the reaction kinetics in molecular crystal phase
2013, 9 (3), 1838−1845. transitions. Phys. Chem. Chem. Phys. 2017, 19 (47), 32125−32131.
(47) Peng, Y.; Shang, C.; Liu, Z.-P. The dome of gold nanolized for (68) Huang, S.-D.; Shang, C.; Zhang, X.-J.; Liu, Z.-P. Material
catalysis. Chem. Sci. 2021, 12 (15), 5664−5671. discovery by combining stochastic surface walking global optimization
(48) Ma, S.; Huang, S.-D.; Liu, Z.-P. Dynamic coordination of with a neural network. Chem. Sci. 2017, 8 (9), 6327−6337.
cations and catalytic selectivity on zinc-chromium oxide alloys during (69) Maier, J. Nanoionics: ion transport and electrochemical storage
syngas conversion. Nat. Catal. 2019, 2 (8), 671−677. in confined systems. Nat. Mater. 2005, 4 (11), 805−815.
(49) Kang, P.-l.; Shang, C.; Liu, Z.-p. Recent implementations in (70) Zeng, D.; Yao, J.; Zhang, L.; Xu, R.; Wang, S.; Yan, X.; Yu, C.;
LASP 3.0: Global neural network potential with multiple elements Wang, L. Promoting favorable interfacial properties in lithium-based
and better long-range description. Chin. J. Chem. Phys. 2021, 34 (5), batteries using chlorine-rich sulfide inorganic solid-state electrolytes.
583−590. Nat. Commun. 2022, 13 (1), 1909.
(50) Kresse, G.; Furthmüller, J. Efficient iterative schemes for ab (71) Arnold, W.; Buchberger, D. A.; Li, Y.; Sunkara, M.; Druffel, T.;
initio total-energy calculations using a plane-wave basis set. Phys. Rev. Wang, H. Halide doping effect on solvent-synthesized lithium
B 1996, 54 (16), 11169−11186. argyrodites Li6PS5X (X= Cl, Br, I) superionic conductors. J. Power
(51) Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient Sources 2020, 464, 228158.
approximation made simple. Phys. Rev. Lett. 1996, 77 (18), 3865− (72) Sebti, E.; Evans, H. A.; Chen, H.; Richardson, P. M.; White, K.
3868. M.; Giovine, R.; Koirala, K. P.; Xu, Y.; Gonzalez-Correa, E.; Wang, C.;
(52) Ehrlich, S.; Moellmann, J.; Reckien, W.; Bredow, T.; Grimme, et al. Stacking Faults Assist Lithium-Ion Conduction in a Halide-
S. System-dependent dispersion coefficients for the DFT-D3 Based Superionic Conductor. J. Am. Chem. Soc. 2022, 144 (13),
treatment of adsorption processes on ionic surfaces. ChemPhysChem 5795−5811.
2011, 12 (17), 3414−3420. (73) Sun, H.-H.; Manthiram, A. Impact of microcrack generation
(53) Ravel, B.; Newville, M. ATHENA, ARTEMIS, HEPHAESTUS: and surface degradation on a nickel-rich layered Li
data analysis for X-ray absorption spectroscopy using IFEFFIT. J. [Ni0. 9Co0.05Mn0.05]O2 cathode for lithium-ion batteries. Chem.
Synchrotron Radiat. 2005, 12 (4), 537−541. Mater. 2017, 29 (19), 8486−8493.
(54) Rehr, J. J.; Albers, R. C. Theoretical approaches to x-ray
absorption fine structure. Rev. Mod. Phys. 2000, 72 (3), 621−654.
(55) Koningsberger, D. C.; Prins, R. X-ray Absorption: Principles,
Applications, Techniques of EXAFS, SEXAFS and XANES; John Wiley
and Sons Inc.: New York, NY, United States, 1987.
(56) Xu, J.; Xia, Y.; Li, Z.; Chen, H.; Wang, X.; Sun, Z.; Yin, W.
Multi-physics instrument: Total scattering neutron time-of-flight
diffractometer at China Spallation Neutron Source. Nucl. Instrum.
Methods Phys. Res. Sect. A 2021, 1013, 165642.
(57) Hart, P. W.; Sommerfeld, J. T. Cost estimation of specialty
chemicals from laboratory-scale prices. Cost Eng. 1997, 39 (3), 31.
(58) Li, F.; Cheng, X.; Lu, L.-L.; Yin, Y.-C.; Luo, J.-D.; Lu, G.; Meng,
Y.-F.; Mo, H.; Tian, T.; Yang, J.-T.; et al. Stable All-Solid-State
Lithium Metal Batteries Enabled by Machine Learning Simulation
Designed Halide Electrolytes. Nano Lett. 2022, 22 (6), 2461−2469.
(59) Yin, Y.-C.; Yang, J.-T.; Luo, J.-D.; Lu, G.-X.; Huang, Z.; Wang,
J.-P.; Li, P.; Li, F.; Wu, Y.-C.; Tian, T.; et al. A LaCl3-based lithium
superionic conductor compatible with lithium metal. Nature 2023,
616 (7955), 77−83.
(60) Park, K. H.; Oh, D. Y.; Choi, Y. E.; Nam, Y. J.; Han, L.; Kim, J.
Y.; Xin, H.; Lin, F.; Oh, S. M.; Jung, Y. S. Solution-processable glass
LiI-Li4SnS4 superionic conductors for all-solid-state Li-ion batteries.
Adv. Mater. 2016, 28 (9), 1874−1883.
(61) Zhao, F.; Alahakoon, S. H.; Adair, K.; Zhang, S.; Xia, W.; Li,
W.; Yu, C.; Feng, R.; Hu, Y.; Liang, J.; et al. An air-stable and Li-
metal-compatible glass-ceramic electrolyte enabling high-performance
all-solid-state Li metal batteries. Adv. Mater. 2021, 33 (8), 2006577.
(62) Croce, F.; Appetecchi, G.; Persi, L.; Scrosati, B. Nanocomposite
polymer electrolytes for lithium batteries. Nature 1998, 394 (6692),
456−458.
(63) Tanaka, Y.; Ueno, K.; Mizuno, K.; Takeuchi, K.; Asano, T.;
Sakai, A. New Oxyhalide Solid Electrolytes with High Lithium Ionic

27787 https://doi.org/10.1021/jacs.3c10602
J. Am. Chem. Soc. 2023, 145, 27774−27787