Energy Storage Materials 49 (2022) 246–254

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Energy Storage Materials

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

Stable all-solid-state lithium metal batteries enabled by ultrathin LiF/Li3 Sb

hybrid interface layer
Aonan Wang, Jie Li, Maoyi Yi, Yangyang Xie, Shilei Chang, Hongbing Shi, Liuyun Zhang,
Maohui Bai, Yangen Zhou, Yanqing Lai, Zhian Zhang∗
School of Metallurgy and Environment, Engineering Research Center of the Ministry of Education for Advanced Battery Materials, Hunan Provincial Key Laboratory of
Nonferrous Value-Added Metallurgy, Central South University, Changsha, 410083, P. R. China

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

Keywords: The PEO-LLZTO composite solid electrolyte is considered to be one of the most promising solid electrolytes.
Solid-state batteries However, there is still a heavily short circuit caused by dendrite penetration due to the uneven deposition of Li
Lithium on the solid electrolyte/Li anode interface. In this paper, the SbF3 is used as the precursor to treating commercial
Interface
Li foils by spray painting method, and an ultrathin LiF/Li3 Sb hybrid interface layer is constructed. The interface
Antimony(III) fluoride
layer can improve the deposition of Li and enhance the solid electrolyte/anode interface stability effectively
contributed by the high Li-ion conductivity of LiF and lithiophilic Li3 Sb. Using SbF3 @Li as the anode to assemble
solid symmetric cells, a high current density of 0.6 mA·cm–2 and an extended cycle life at 0.2 mA·cm–2 for 0.2
mAh·cm–2 are obtained. Moreover, assembling full cells with the LiFePO4 or single crystal LiNi0.6 Mn0.1 Co0.3 O2 , it
is found that the cycle stability and coulomb efficiency are greatly improved. The LiFePO4 |PEO-LLZTO|SbF3 @Li
cell delivers stable cycling at 0.2 C over 200 cycles (94.5% capacity retention), and it also exhibits a superior rate
capability of 127.9 mAh·g–1 at 1 C. These results demonstrate that the modified Li anode holds large potential
for all-solid-state lithium metal battery applications.

1. Introduction
Li metal anode is considered the ultimate choice for high energy bat-
teries due to its intrinsic high theoretical specific capacity and low re-
duction potential [1–3]. However, the liquid and flammable electrolytes
used in current commercial lithium-ion batteries are easily induced seri-
ous safety issues under harsh working conditions when comprised with
Li metal [4,5]. To get the energy density above 400 Wh·kg–1 cell-level
batteries with higher safety, all-solid-state batteries (ASSLBs) with lim-
ited Li metal as the anode have become the most attractive alternative
[6–9].
Solid electrolytes (SE), including inorganic solid electrolytes and
polymer-based electrolytes, are hard to burn and supposed to prevent
dendritic growth because of their high burning point and mechanical
strength compared with liquid electrolytes [10]. However, the general
issues of anode/solid electrolyte interface in solid-state Li metal bat-
teries lead to its low critical current density (CCD, which is defined as
the maximum available current density of a battery), and short cycle
life [11–13]. In which, the poor interface contact and the Li dendrite
formed by ununiform deposition on the anode are most prominent [14].
The polymer-based composite solid electrolytes have better interfacial
contact with Li metal than inorganic solid electrolytes [15], but the high
operating temperatures, poor mechanical strength, inhomogeneous in-
terface, and side reaction make composite solid electrolytes more sus-
ceptible to penetration by Li dendrites [16]. In addition, the short-circuit
caused by Li dendrites is particularly serious when practical thin Li foils
(≤ 100 μm) or quantitative Li metals are used in solid-state batteries
[17,18]. In summary, to improve the critical current density and cy-
cle life of solid-state batteries, it is important to construct a stable an-
ode/solid electrolyte interface and suppress the formation of Li den-
drites.
To improve the stability of interface and suppress Li dendrites in
solid batteries, varied efforts have been devoted including electrolyte
optimization [19,20], application of 3D collectors [21], and the em-
ployment of artificial interface layers [22,23]. Among them, the multi-
functional artificial interface layer can improve the behavior of Li de-
position and inhibit the penetration of Li dendrites, which is considered
as one of the most effective interface improvement methods [24,25].
Recently, some lithium compounds (LiF [26], Li3 N [27], etc.) are found
that have good compatibility with solid electrolytes and Li metal anodes
as the artificial interface layers, owing to their good mechanical prop-
erties, high lithium ion conductivity, and low electronic conductivity.

∗
Corresponding author.
E-mail address: zhangzhian@csu.edu.cn (Z. Zhang).

https://doi.org/10.1016/j.ensm.2022.04.023
Received 16 December 2021; Received in revised form 21 March 2022; Accepted 12 April 2022
Available online 14 April 2022
2405-8297/© 2022 Elsevier B.V. All rights reserved.
A. Wang, J. Li, M. Yi et al.
In addition, to improve the Li deposition more effectively, researchers
use some inorganic metal salts to undergo conversion reactions with Li
to form optimized composite interface layers containing lithium com-
pounds and lithiophilic sites [28,29]. For example, CuF2 is used to react
with Li to build an artificial interface layer composed of LiF and Cu in
solid batteries. Cu is found to be distributed in the interface layer and
acts as a lithiophilic site to make the Li deposition uniform [30]. Com-
pared with simple metals, some lithium alloys can improve the wettabil-
ity of lithium, with higher absorbing energy and lower diffusion barrier,
which allow Li ions to diffuse faster on the interface [31–35], resulting
in a more uniform deposition. Previous studies construct mixed artifi-
cial interface layers (thickness ≥10 μm) containing LiF and Li-Sn alloy
[36] or Li-Sb alloy [37] by immersing Li metals on precursor solutions,
and the liquid Li metal batteries use these modified Li anodes can catch
increased stable current densities supreme about 20 mA·cm–2 . However,
current research on LiF/Li-alloy mixed interface layer modified anodes
is mostly limited to liquid batteries, in which the modified layer is usu-
ally thick and infiltrated by the liquid electrolyte. And there are few
reports on the electrochemical performance and Li plating/stripping be-
haviors of these anodes in solid-state batteries. Therefore, further studies
are necessary for hybrid interface layers containing Li alloy and LiF in
solid batteries.
In our work, an in-situ constructing ultrathin LiF/Li3 Sb bifunctional
interface layer on thin Li foils is put forward for the polymer-based solid
batteries. Li foils (∼100 μm) are used as the anode and treated with
an organic solution containing SbF3 using a spraying method. Com-
bining the SbF3 -modified Li (SbF3 @Li) with the PEO-based compos-
ite electrolyte to assemble symmetric Li cells, which can cycle stably
at a high current density of 0.6 mA·cm–2 and show an extended cycle
life over 300 h at 0.2 mA·cm–2 for 0.2 mAh·cm–2 . The ASSLBs consist-
ing of Li foils, LiFePO4 cathode, and solid composite electrolyte show
good rate capability, excellent cycling stability, and high coulombic effi-
ciency (99.4% on average) over 200 cycles at 0.2 C. Moreover, the plat-
ing/stripping behaviors of modified Li foils are identified by the scan-
ning electron microscope and in situ optical microscopy. The enhanced
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Energy Storage Materials 49 (2022) 246–254
electrochemical performance and stability can be ascribed to the uni-
form deposition of Li on the surface and bottom of the hybrid interface
layer.
2. Results and discussion
The precursor solution including SbF3 is employed to pre-treat the
surface of Li foils. In-situ reaction against SbF3 with Li is the key to
obtaining good contact between the modified layer and Li foil. To en-
sure the integrity of the Li foil and the uniformity of the artificial layer,
the solvent of precursor solutions should be chemically stable against Li
while having solubility to SbF3 . The 1,2-Dimethoxyethane (DME), which
is commonly used in the commercial electrolyte, has been chosen as the
solvent of SbF3 [37], It has polarity and moderate boiling point, which
allows it to solve the commercial SbF3 particle and evaporate control-
lably. Herein, a widely used technology in the industry named “spray
painting” [38] is selected to build the wanted interface layer in Li foil.
Fig. 1a shows the in-situ modification process of Li foils. Firstly, the SbF3
particle is dissolved in DME at 60 ◦ C to obtain the precursor solution.
Then, the solution is sprayed by an airbrush to create some droplets
which easily disperse on the Li foil surface and evaporate rapidly to
make SbF3 recrystallize as crystallites and deposit uniformly. The re-
crystallization has been confirmed by X-ray diffraction (XRD) and shows
the phase-pure orthorhombic structure SbF3 (Figure S3, Supplementary
Information). After standing still for a few minutes, the silver surface of
Li metal gradually turns golden, which indicates that the Li foil sponta-
neously reacts with SbF3 depositing on its surface (Fig. 1b).
To confirm the formation, the XRD is used to examine the surface of
the bare Li and SbF3 @Li. And XRD patterns are shown in Fig. 2a. Com-
paring the spray painting processed Li foils with bare Li, only strong
characteristic peaks of the Li metal can be detected. It is due to that
the low thickness of the modified layer causing the weak diffraction
signal [39,40]. To enhance the diffraction signal, a bare Li foil is im-
mersed in the SbF3 precursor solution for about 5 min to build a thick
modified layer. The XRD pattern of the immerse processed Li foil shows
Fig. 1. Illustration of the interface design
of LiF/Li3 Sb interface layer using a spraying
method. a) The preparation of SbF3 @Li. b, c)
Optical images of the Li foil before and after
being processed.
A. Wang, J. Li, M. Yi et al.
Fig. 2. The structure and composition characterization of SbF3 @Li. a) The XRD of SbF3 @Li with different prepared methods. b) The top view and cross-section SEM
images of bare Li and SbF3 @Li (prepared by 10 mmol/L SbF3 precursor solution). c) The XPS of SbF3 @Li.
obvious diffraction peaks of crystalline phases LiF and Li3 Sb on the sur-
face, which shows metallic Li can spontaneously react with SbF3 . In
addition, the spray painting treated Li foil is analyzed by X-ray pho-
toelectron spectroscopy (XPS) using Ar+ sputtering (Fig. 2c), and it is
found that the surface of the SbF3 @Li foil is mainly coated by LiF ((Li
1 s in 55.50 eV, F 1 s in 684.90 eV), Li3 Sb (Li 1 s in 54.62 eV, Sb 3d
in 528.39 eV)and oxides (Li2 O and SbOx ) [37,41-43], where the forma-
tion of Li2 O might be related to the brief contact of the sample with
air during the testing. In addition, characteristic peaks of zero-value Sb
are also found in 525.2 and 534.8 eV, indicating that a small amount of
unreacted Sb metal remained on the surface of SbF3 @Li after the reac-
tion. Furthermore, full-spectrum results of the XPS test for bare Li and
SbF3 @Li before the cycle are shown in Figure S18a. Compared with bare
Li, obvious F and Sb elements are detected on the surface of SbF3 @Li.
The XRD and XPS results indicate a thin LiF/Li3 Sb hybrid interface layer
has been successfully prepared.
The concentration of the SbF3 precursor solution may affect the
thickness of the interface layer, which has a great influence on the inter-
face impedance and electrochemical performance in solid-state batteries
[44]. To examine its effect, different concentration precursor solutions
(10, 15, 20, 50 mmol/L SbF3 ) are used to treat Li foils, the color change
on the surface of Li foils after spraying by 10 mmol/L SbF3 and the sur-
face color of Li foils treated by different concentration SbF3 solutions are
shown in Figure S4 and Video S1. Scanning electron microscopy (SEM) is
used to view the morphological and structural features of SbF3 @Li foils.
The top view and cross-section SEM images of bare Li and SbF3 @Li foils
are shown in Fig. 2b and Figure S5. Comparing the bare Li with SbF3 @Li
prepared by 10 mmol/L SbF3 solutions, it is found that the surface of
the SbF3 @Li is uniformly and densely covered by some small particles,
and not any obvious pores are found, while the surface of bare Li is
rough. Moreover, the cross-section of SbF3 @Li shows its ultrathin in-
terface layer with a thickness of about 1∼2 μm. In addition, the energy
spectrum (EDS) images of the top view of SbF3 @Li indicate a uniform
distribution of Sb and F elements on its surface (Fig. 2b), which means
the uniform distribution of LiF and Li3 Sb. This is conducive to the uni-
form distribution of surface current and the uniform deposition of Li.
Furthermore, the top view of SbF3 @Li foils becomes more and more
rough and porous with the increased concentration of precursor solu-
tions, and the thickness also increases from about 1 μm to above 5 μm.
It confirms that the concentration of precursor solutions has a strong
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Energy Storage Materials 49 (2022) 246–254
influence on the morphology and structure of the interface layer. Fig-
ure S7 shows the EIS of the SS|SE|Li batteries assembled by different
SbF3 @Li foils. When the thickness of the interface layer varies from 1
to above 5 μm, the corresponding impedances increases. It is obvious
that the thin interface layer contributes to low interface impedances in
the solid-state battery (Table S1). Finally, a 10 mmol/L SbF3 solution
is selected to build the SbF3 @Li foil with the thickness of the interface
layer only about 1∼2 μm.
The symmetric SbF3 @Li|PEO-LLZTO|SbF3 @Li cells are assembled
to assess the interface stability and dendrite suppressing effect of the
SbF3 @Li electrode, and the rate capability of symmetric cells with
a fixed Li deposition time of 1 h is first measured at different cur-
rent densities. As shown in Fig. 3a-b , under the condition of fixed
charge/discharge time of 1 h, both bare Li and SbF3 @Li keep sta-
ble Li plating/stripping at current densities from 0.05 mA·cm–2 to 0.2
mA·cm–2 . However, bare Li symmetric cells show obviously short cir-
cuits at a current density of 0.3 mA·cm–2 when SbF3 @Li symmetric cells
remain roughly stable. Voltage profiles of symmetric cells at different
current densities show the similar polarization of bare Li and SbF3 @Li
about 25 to 150 mV from 0.05 mA·cm–2 to 0.2 mA·cm–2 , respectively,
which indicates the weak obstruction of the interface layer. And the
voltage polarization of bare Li symmetric cells appears suddenly drop
at 0.3 mA·cm–2 after plating 0.75 h Li, which is regarded as the signal
of a soft-short circuit in solid batteries [30]. Moreover, with the cur-
rent density increasing to 0.4 mA·cm–2 , the voltage polarization of bare
Li symmetric cells remains unchanged at 10 mV, which shows a com-
pletely short circuit. The soft-short circuit happens at 0.4 mA·cm–2 for
SbF3 @Li. In addition, the rate behavior of SbF3 @Li is also performed at
a fixed Li deposition capacity of 0.2 mAh·cm–2 (Fig. 3c). The SbF3 @Li
symmetric cell remains stable at 0.6 mA·cm–2 and shows good recovery
from 0.6 mA·cm–2 to 0.2 mA·cm–2 . The result indicates that PEO-LLZTO
hard to suppress the growth of Li dendrites at 60 ◦ C even in solid bat-
teries due to the uneven deposition of Li [45]. After being modified by
SbF3 , the in-situ formed LiF/Li3 Sb mixed interface layer integrates the
good Li-ion conductivity of LiF, the high Li-ion diffusion rate, and the
low Li-ion binding energy of Li3 Sb, which make the deposition behav-
ior of Li better and suppress the growth of dendrites. As a result, the
crucial current density and Li deposition capacity of the Li electrode are
improved.
A. Wang, J. Li, M. Yi et al. Energy Storage Materials 49 (2022) 246–254

Fig. 3. Electrochemical performances of SbF3 @Li anodes. a) The rate capability of SbF3 @Li and bare Li at a certain cycle time. b) Voltage profiles of the SbF3 @Li
and bare Li anodes at different current densities. c) the rate capability of SbF3 @Li and bare Li at 0.2 mAh·cm–2 . d) The cycling stability of SbF3 @Li and bare Li at
the current density of 0.2 mA·cm–2 . e) The electrochemical impedance spectroscopy of SbF3 @Li|PEO-LLZTO|SbF3 @Li cells after cycles.

The results above demonstrate that the SbF3 @Li can effectively sup-
press Li dendrites in symmetric cells with PEO-LLZTO electrolytes. Fig.
3d shows the cycle performance of Li||Li cells at 0.2 mA·cm–2 . The volt-
age polarization value of SbF3 @Li cells is similar to bare Li, which is
about 150 mV, and it remains stable with the increase of cycle times.
However, after cycling about 100 h, bare Li||Li cells experience obvious
short circuits, and the overpotential suddenly decreases to below 10 mV
[46], while SbF3 @Li|| SbF3 @Li cells still maintain stable cycles over
300 h. In addition, the cells keep excellent cycle stability over 700 h and
300 h at 0.1 mA·cm–2 and 0.3 mA·cm–2 , respectively (Figure S8a-b). The
stable voltage polarization and long cycle times at various current densi-
ties show the stable interface of SbF3 @Li. To further verify the stability
of the interface, the electrochemical impedance spectroscopy (EIS) are
evaluated and analyzed on Li||Li cells before and after cycles at a current
density of 0.2 mA·cm–2 (Fig. 3e, Figure S9). The SbF3 @Li||SbF3 @Li cells
show slightly increase interface resistance (Rint ) of about 32.7 Ω before
the cycle, and about 39.2 Ω, 50.3 Ω, 60.5 Ω at 10th, 50th, 100th cy-
cle, respectively. It indicates a stable evolution in the interface between
electrolyte and SbF3 @Li. In contrast, the bare Li||Li cells show Rint of
about 20.4 Ω before the cycle and drop to zero after 100 cycles because
of its hard-short circle [51].
The SbF3 @Li is proved to have a significant effect on improving the
interface stability and can inhibit the short circuit caused by Li den-
drites. Next, LiFePO4 (LFP) is used as the cathode to assemble ASSLBs
with PEO-LLZTO solid electrolyte to determine the performance of bare
Li and SbF3 @Li in solid batteries (Fig. 4a-b). At 0.1 C, the discharge
capacity of LFP||SbF3 @Li is essentially as same as that of LFP||Li, while
at 0.2 C, 0.5 C, and 1 C, LFP||SbF3 @Li has a higher discharge specific
capacity. The discharge specific capacities of LFP||SbF3 @Li cell at 0.1,
0.2, 0.5, and 1 C are 168.9 mAh·g–1 , 154.1 mAh·g–1 , 143.1 mAh·g–1 , and
127.9 mAh·g–1 , respectively, and the discharge specific capacity recov-
ered to 168.0 mAh·g–1 after returned to 0.1 C, showing an outstanding
capacity recovery [34]. Moreover, the LFP||Li cell has lower coulomb
efficiency (CE) than LFP||SbF3 @Li at all rates. Obviously, LFP||SbF3 @Li
has superior rate performance compared to LFP||bare Li.
The cycling performances of ASSLBs at 0.2, 0.5, and 1 C are shown in
Fig. 4(c-e) and Figure S10. Compared with LFP||bare Li, LFP||SbF3 @Li
full cells maintain good cycling stability and higher CE after 200 cycles
at 0.2 C. Its initial specific discharge capacity is 159.6 mAh·g–1 and main-
tains a high discharge capacity of 150.8 mAh·g–1 after 200 cycles, cor-
responding to high capacity retention about 94.5% (a capacity decrease
rate of 0.028%/cycle) and an average CE of 99.4%. In contrast, the ini-
tial discharge capacity of LFP||Li full cells is about 150.5 mAh·g–1 at 0.2
C, and the CE decreases sharply after about 30 cycles, indicating that a
soft short circuit occurs in this cell due to the growth of Li dendrites. The
results above indicate that the SbF3 @Li has a significant improvement
in cycling stability and can effectively inhibit the penetration of lithium
dendrites. The EIS has performed on LFP||Li and LFP||SbF3 @Li cells be-

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A. Wang, J. Li, M. Yi et al. Energy Storage Materials 49 (2022) 246–254

Fig. 4. Electrochemical performances of full cells with bare Li and SbF3 @Li anode. a, b) Rate capability at various charge/discharge rates (0.1–1 C) of
LiFePO4 ||SbF3 @Li and LiFePO4 ||bare Li. c-e) Discharge capacity, coulombic efficiencies and charge/discharge curves of LiFePO4 ||SbF3 @Li and LiFePO4 ||bare Li at
0.2 C (c, e), 0.5 C (d). f, g) Discharge capacity, coulombic efficiencies and charge/discharge curves of SC–NMC613||SbF3 @Li at 0.5C.

fore and after cycling, and it is found that the increase in impedance
of LFP||SbF3 @Li is much smaller than that of LFP||Li after the same
cycles, and the difference occurred mainly in the Rint , which indicated
that the modified interface is more stable after cycling (Figure S11). The
performances of the batteries used single crystal LiNi0.6 Mn0.1 Co0.3 O2
(SC–NMC613) as the cathode active materials also show in Fig. 4f-g. It
indicates good cycling stability and high CE above 99% after 100 cycles
at 0.5 C. The initial specific discharge capacity is about 157 mAh·g–1 ,
and the specific discharge capacity after 100 cycles is 120.5 mAh·g–1 ,
which leads to the capacity retention rate is about 76.8%. Compared

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A. Wang, J. Li, M. Yi et al.
Fig. 5. The top view SEM of SbF3 @Li electrodes in Li||Li symmetric cells with a-c)Li plating and d-e)Li stripping, bare Li electrodes with g-i)Li plating and j-l)Li
stripping after 50 cycles, at the Li deposition capacity of 0.2 mAh·cm–2 . m-p) The cross-section SEM of SbF3 @Li and bare Li electrode.
with LFP, the discharge capacity of SC–NMC613 decays faster. The rea-
son is that under a cut-off voltage of 4.2 V, the Co in NMC accelerates
the oxidation of PEO, and the surface structure of the NMC particle is
destroyed, resulting in a rapid decrease in its specific capacity [52].
In order to understand the reason why the SbF3 @Li can improve
the stability of the interface, inhibit dendrites and short circuits, and
investigate the plating/stripping behavior of Li on SbF3 @Li electrode,
the morphological evolution images of the Li electrode in Li||Li sym-
metric cells over cycling are observed by SEM (Fig. 5, Figure S12, 13).
The bare Li shows obvious cellular dendrites on the Li plating side and
some cracks on the Li stripping side after 50 cycles at 0.2 mAh·cm–2 Li
deposition capacity. With the increasing of Li deposition capacity to 0.4
mAh·cm–2 , the plating side of the bare Li electrode becomes rougher,
which indicated that the bare Li has severe deterioration due to the un-
even plating and stripping of Li and the stress generated by the volume
change after 50 cycles. In contrast, the surface of SbF3 @Li has no ob-
vious Li dendrites after cycles on both sides of plating and stripping at
0.2 mAh·cm–2 , and the deposited Li demonstrates a dense layer. Com-
paring the top view and cross-section images of the plating side with the
stripping side of SbF3 @Li, it’s found that the size of particle increases
from about 200 nm to over 500 nm after plating, and the interface be-
tween the interface layer and Li metal disappears, which indicates the Li
metal may deposit around the small particle formed the interface layer
preferentially. In addition, with the change of deposition capacity from
0.1 mAh·cm–2 to 1 mAh·cm–2 , the Li deposits with sheet-like structure,
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Energy Storage Materials 49 (2022) 246–254
which implies the homogenous plating process of Li and demonstrates
the effective suppression of formation of Li dendrites [47]. However, the
flaw becomes serious with high deposition capacity due to the interface
layer fully covered by Li metal or volume change of Li. It’s estimated
to the reason why the short circuit still happens after SbF3 is treated
[48]. Charge and discharge state LiFePO4 ||Li full cells after 50 cycles,
and liquid batteries deposited 0.4 mAh·cm–2 Li with SbF3 @Li electrode,
also are disassembled to observe the morphology of Li electrodes (Fig-
ure S14, 15). The SEM images show the same phenomenon about Li de-
position like Li||Li cells, which further verifies the preferential deposit
behavior of Li on SbF3 @Li.
Energy-dispersive X-ray spectroscopy (EDS) and XPS are used to fur-
ther determine the deposition behavior of Li on SbF3 @Li in ASSLBs
and confirm the composition of the surface of SbF3 @Li after 50 cycles.
The SEM top view and cross-section images of the Li plating/stripping
SbF3 @Li electrode above show obvious structural change. To determine
the major cause of this change, the line scans of chemical elements are
used to analyze Li plating and Li stripping SbF3 @Li electrodes, respec-
tively. Figure S16 shows that after 50 cycles, the contents of F and Sb ele-
ments are all evenly distributed both SbF3 @Li electrodes after Li plating
or stripping along with the interface layer in the cross-section direction,
which indicates that the structure of the LiF/Li3 Sb artificial interface
layer has not been destroyed by the structural change on the surface
of SbF3 @Li. It shows the excellent electrochemical reversibility of the
LiF/Li3 Sb artificial interface layer [49], and the apparent change on the
A. Wang, J. Li, M. Yi et al. Energy Storage Materials 49 (2022) 246–254

Fig. 6. a) The XPS results of SbF3 @Li electrodes with Li plated after 50 cycles. b) The optical evolution photos of bare Li and SbF3 @Li during Li deposition at about
4 mA cm−2 for 240 min. c) The schematic of speculated protective mechanism of SbF3 @Li.

surface (Fig. 5c,5f) of SbF3 @Li may be due to the deposition of Li firstly
occurring in the gaps between the particles which form the LiF/Li3 Sb
interface layer and finally covers its surface. On this basis, the elemen-
tal mappings are carried out to analyze the surface of SbF3 @Li after Li
plating (Figure S17). Obviously, the Sb and F elements are uniformly
distributed at 0.2 mAh·cm–2 . It further shows that Li is not deposited
directly after contacting the LiF/Li3 Sb interface layer, but firstly dif-
fuses on the particle surface quickly because of the high chemical diffu-
sion coefficient of Li3 Sb, and then obtains electrons in the gaps between
particles to deposit [32]. As the amount of Li deposition capacity in-
creases(0.4 mAh·cm–2 and 0.6 mAh·cm–2 ), after the inter-particle gaps
are filled, Li begins to be deposited on the surface of the LiF/Li3 Sb in-
terface layer. In addition, it is found that the distribution of F and Sb
elements can still be detected on the surface of SbF3 @Li under higher
Li deposition. The possible reason is that a part of Li will be deposited
on the bottom of the interface layer due to the high Li-ion conductiv-
ity of LiF and the potential difference between the artificial interface
layer and the Li bulk, which cause the surface of SbF3 @Li cannot be
completely covered by deposited Li. In addition, XPS is performed on
the SbF3 @Li after Li plating. Compared with fresh SbF3 @Li, the zero-
valence Sb is found to disappear on the surface after 50 cycles, which
may be completely alloyed with Li and form some Li3 Sb. After Li de-
posited, the components of the interface layer on SbF3 @Li are including
LiF (Li 1 s in 55.90 eV, F 1 s in 684.71 eV), Li3 Sb (Li 1 s in 55.26 eV, Sb
3d in 528.18 eV)and some metal oxide (Li2 O,SbOx ) [37,41–43]. Among
them, the peak intensity of Li3 Sb is smaller than fresh, which indicates

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A. Wang, J. Li, M. Yi et al.
that the exposed Li3 Sb on the surface is reduced [43]. The appearance
of the zero-valence Li(Li 1 s in 54.59 eV)indicates that there is some Li
deposited on the surface of the LiF/Li3 Sb interface layer, which is con-
sistent with the conjecture of Li deposition behavior above. The charac-
teristic peak of LiTFSI (F 1 s in 688.00 eV) is due to the residue of the
solid electrolyte that has not been cleaned completely. The full spectrum
results of the XPS test for bare Li and SbF3 @Li after cycle are shown in
Figure S18b. The new peak of the F element in bare Li shows the de-
compose of LiTFSI. And the La element is from LLZTO filler in the solid
electrolyte.
The optical observation is further conducted at room temperature
to observe the deposition behavior of Li on the SbF3 @Li electrode in
the solid-state batteries more intuitively through the in-situ optical de-
vice with bare Li|PEO-LLZTO|SbF3 @Li as illustrated in Figure S19, and
the employing current is 2 mA and the actual current density is over 4
mA·cm–2 . In this condition, both in-situ Li||Li and SbF3 @Li||SbF3 @Li
cells discharge normally within 240 min (Figure S20). The correspond-
ing cross-section images during the deposition are listed, in which the
Li electrode is bright and the solid electrolyte is dark, and the solid elec-
trolyte/electrode interface can be observed clearly. As shown in Fig. 6b,
the Li dendrites grow quickly after depositing on bare Li for 30 min, and
the interface of solid electrolyte/bare Li becomes roughly after Li plating
for 240 min. In contrast, Li is found uniformly deposited on the surface of
SbF3 @Li and the interface of solid electrolyte/SbF3 @Li keeps stable af-
ter Li plating for 240 min, and not any obvious Li dendrites are observed.
Moreover, both bare Li and SbF3 @Li have been observed an increase in
thickness and the deposition of Li on the bottom of the electrode, which
indicates that part of the Li can pass through the LiF/Li3 Sb interface
layer and be deposited on the bottom. It further confirms the deposition
behavior of Li on SbF3 @Li and the improvement of the LiF/Li3 Sb inter-
face layer on the solid electrolyte/Li electrode interface. In addition, the
videos of in-situ optical microscopy observation are provided as Video
S2, S3. According to the analysis above, the mechanism schematics are
described in Fig. 6c. Due to the low self-diffusion of Li on the bulk and
the local high current density, Li ions are preferentially deposited on
surface defects of the bare Li electrode, and accumulate during the cy-
cle [50], resulting in the uneven plating/stripping. Then, Li dendrites
grow and penetrate the solid electrolyte, causing the short circuit phe-
nomenon, which leads to a sudden drop in voltage and low CEs during
the cycle. For the SbF3 @Li, since the LiF/Li3 Sb interface layer has a
certain electronic conductivity, Li can get electrons and be deposited on
its surface. Profiting from the high chemical diffusion coefficient and Li
absorbing the energy of Li3 Sb, combined with LiF which has high Li-ion
and low electronic conductivity, Li tends to be uniformly transferred on
the surface and firstly be deposited in the gaps of the particles formed
the interface layer which has higher local current density [30,37,43].
Next, the surface of the interface layer will be covered by dense and
uniform Li. In addition, part of Li passes through the interface layer and
is deposited on its bottom, which makes the surface of the LiF/Li3 Sb
interface layer not completely covered by depositing Li. The exposed
Li3 Sb and LiF are great for more Li deposition. Thereby, the solid elec-
trolyte/Li electrode interface gets improved and the critical current den-
sity is increased, realizing the high coulombic efficiency and long cycle
life of ASSLBs.
3. Conclusions
In this work, an ultrathin LiF/Li3 Sb artificial interface layer is pre-
pared on the practical commercial Li foils surface by spraying method.,
The influence of the concentration of the SbF3 precursor solution is stud-
ied, which shows that the concentration has a significant effect on the
interfacial layer thickness and interfacial impedance. Using SbF3 @Li as
the anode to assemble solid Li||Li symmetric batteries, a current density
of 0.6 mA·cm–2 can be reached at the amount of Li deposition is 0.2
mAh·cm–2 , and the SbF3 @Li|| SbF3 @Li cell can cycle stably for more
than 300 h under the condition of 0.2 mA·cm–2 –0.2 mAh·cm–2 at 60 ◦ C.
253
Energy Storage Materials 49 (2022) 246–254
The LiFePO4 and single crystal NCM613 are assembled with SbF3 @Li
as the cathode activity materials, respectively, to construct the ASSLBs,
which showed high specific capacity and CEs, and achieved excellent cy-
cle life. In addition, the Li deposition behavior of SbF3 @Li in ASSLBs is
studied. It is found that Li should be preferentially deposited uniformly
in the gaps of particles on the LiF/Li3 Sb interface layer, and then gradu-
ally cover the interface layer to form a uniform and dense Li deposition
layer on the surface. A part of Li may pass through the artificial interface
layer and be deposited on its bottom. In summary, the uniform deposi-
tion of Li on SbF3 @Li improves the stability of the solid electrolyte/Li
electrode interface and alleviates the problems of dendrites and short
circuits. This strategy provides a new way for the improvement of the
anode interface in the practical solid-state Li metal battery and provides
a new reference for the study of the deposition behavior of Li in the in-
situ conversion artificial interface layer.
4. Author contributions
Zhian Zhang and Aonan Wang conceived this study. Aonan Wang
prepared the materials, assembled cells, conducted electrochemical
evaluations and obtained SEM images of Li metal anodes. Shilei Chang
and Hongbing Shi prepared the LLZTO powder. Maoyi Yi provided
SC–NMC613 cathode materials and studied the method to prepare PEO-
LLZTO solid electrolyte. Yangyang Xie and Liuyun Zhang provided the
method of Li metal characterizations and conducted the in-situ opti-
cal microscope study. All authors contributed to writing and revising
manuscript.
Declaration of Competing Interest
The authors declare no conflict of interest.
Data Availability
The authors do not have permission to share data.
Acknowledgments
This work was supported by Changsha Municipal Natural Science
Foundation (kq2202085) and the Innovation Program of Central South
University (No. 2020zzts087)
Supplementary materials
Supplementary material associated with this article can be found, in
the online version, at doi:10.1016/j.ensm.2022.04.023.
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