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Dual-Layered Interfacial Evolution of Lithium Metal Anode: SEI

Analysis via TOF-SIMS Technology
Chengwei Ma, Fan Xu, and Tinglu Song*

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ABSTRACT: Lithium metal battery has been considered as one of

Downloaded via BEIJING INST OF TECHNOLOGY on May 17, 2022 at 10:40:48 (UTC).

the most promising candidates for the next generation of energy

storage systems due to its high energy density. However, the
lithium metal may react with the electrolyte, resulting in the
instability of the solid/liquid interface. The solid electrolyte
interface (SEI) layer was found to affect the interface stability of
the lithium metal anode; the real structure of SEI couldn’t be
accurately analyzed so far. Time-of-flight secondary ion mass
spectrometry (TOF-SIMS) has been thought as a powerful tool to
carry out three-dimensional (3D) characterization and structural
reconstruction at a high-resolution nanoscale, as well as detect
ionized elements and molecule fragments at the ppb level due to its
excellent sensitivity. Herein, we employed TOF-SIMS to investigate the chemical composition of SEI at the surface of the lithium
metal anode after electrochemical cycles. We find that SEI is not a completely dense interface layer. The organic phase of SEI can
accommodate part of the electrolyte, enhancing the lithium-ion conductivity. Meanwhile, SEI is an interface layer that changes with
the state of the electrolyte, and this process of change is expressed by conventional characterization methods. However, the
distribution of lithium salt can be analyzed by TOF-SIMS to judge the change degree of SEI. Our work provides significant guidance
for accurately characterizing the SEI layer, as well as constructing a more realistic interface layer model.
KEYWORDS: lithium metal battery, SEI, TOF-SIMS, interfacial layer, excellent sensitivity

1. INTRODUCTION
With the rapid development of electric vehicles and electronic
equipment technology, it becomes imperative to develop
batteries with high energy density. Among various types of
batteries, lithium metal battery has been considered as one of
the most promising candidates for the next generation of
energy storage systems, due presumably to its low electrode
potential (−3.04 V vs SHE) and very high theoretical capacity
(3860 mAh g−1).1−4 Thus, the lithium metal electrode shows
great potential to be applied into new energy vehicles and
portable electronic devices. However, the thermodynamic
stability limit restricted its further applications, i.e., the
thermodynamic limit of electrolyte components will be
exceeded in the electrochemical reaction process regardless
of whether non-aqueous or solid electrolyte was employed,
resulting in undesired irreversible reactions.5−7 Due to the low
electrode potential of the lithium metal anode, the dense solid
products produced by the decomposition products will be
deposited on the surface of the lithium metal anode to form a
passivation layer. This passivation layer is the so-called solid
electrolyte interface (SEI) layer, which would insulate the long-
range electron transmission, but can still conduct lithium ions;
thus, it plays an important role in battery reaction.8−10 The SEI
could stabilize the lithium metal anode, since it can prevent the
substances in the electrolyte from continuous decomposition
at the surface of the lithium metal, enabling the electro-
chemical reaction to continue and regulating the deposition of
lithium ions.11−15
In recent years, various studies have been conducted to
investigate the chemistry, morphology, and mechanism of the
lithium metal anode SEI layer. According to the frontier orbital
theory,9,16 the electrochemical potential of the lithium metal
anode (μA) is greater than the reduction potential (ELUMO) of
most electrolytes, which means that electrons at the surface of
the lithium metal anode will be transferred to the unoccupied
orbit of the electrolyte, and the electrolyte will spontaneously
react with the lithium metal anode. The reaction product is
SEI, which can prevent further decomposition of the organic
electrolyte. Currently, the most-reported SEI model is the
Received: January 14, 2022
Accepted: April 18, 2022
Published: April 26, 2022

© 2022 American Chemical Society https://doi.org/10.1021/acsami.2c00842

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Figure 1. Li deposited on the surface of the Li metal anode based on EIS curves: (a) after 1 cycle, (b) after 25 cycles, (c) after 100 cycles, and (d)
200 cycles. The related morphological change of Li deposition by SEM: (e) after 1 cycle, (f) after 25 cycles, (g) after 100 cycles, and (h) 200 cycles.
mosaic structure,17 which reveals inhomogeneity in the
direction of the thickness. The inner layer close to the lithium
metal anode is composed of low-oxidation species such as
Li2O, Li3N, LiF, LiOH, and Li2CO3. The outer layer near the
electrolyte side consists of high-oxidation species such as
ROCO2Li, ROLi, and RCOO2Li (R is an organic group related
to the solvent).18−20 In addition, intermediate products may
also be formed during the reaction between the electrolyte and
the lithium metal anode. Therefore, characterizing the
composition and distribution of each SEI becomes the key
step to reveal the formation mechanism of the SEI film.
However, there still remain various ambiguous problems in the
SEI study, i.e., no final conclusion can be drawn regarding the
effect of the chemical composition distribution of SEI after a
long working time on the action mechanism of the lithium
metal battery.
Time-of-flight secondary ion mass spectrometry (TOF-
SIMS) has been considered as one of the few advanced
technologies that could provide nanoscale three-dimensional
chemical information.21−25 One of the prominent advantages
of TOF-SIMS is that it can detect all light and heavy elements,
which makes it a powerful tool to characterize a thin film-based
multilayer structure26,27 and is of great significance for the
characterization of component distributions in new micro-
devices (such as lithium metal batteries). Moreover, the
detected area of TOF-SIMS can be easily changed from 10−2
to 105 μm2, which would provide information about both local
and global sample composition.28−30 Meanwhile, conducting
TOF-SIMS measurements does not require sample pretreat-
ment, which reduces the cost and time of the experiment.
Both inorganic and organic components of the SEI could be
detected by TOF-SIMS, which is vital for investigating the
electrochemical deposition process on the Li metal anode.
Most reports about SEI structure only focus on the
conventional decomposition products in the electrolyte,
while other substances with the same element but different
chemical structure are ignored.
Herein, we combined both conventional characterization
methods and TOF-SIMS to investigate the change of SEI layer
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on the Li metal surface. The chemical composition of the
interface was determined by analyzing the excited charge
fragments of the SEI layer, and the distribution of chemical
components was restored by two-dimensional (2D) and two-
dimensional (3D) reconstruction techniques. The dual-layered
structure of SEI layer is further confirmed, and it was found
that the LiTFSI without decomposition existed in the interface
layer between the organic phase and the inorganic phase,
which demonstrates that the organic phase of the SEI layer
could store some electrolyte, leading to the lithium-ion
conduction characteristic of SEI in the case of inactive lithium
accumulation. Different from previous reports, the SEI is not a
completely dense interface layer and will change with the state
of the electrolyte. The amount of LiTFSI that is not
decomposed further indicates the change degree of SEI, i.e.,
the higher the degree of SEI change, the greater the amount of
electrolyte stored in the organic phase. The TOF-SIMS is used
to evaluate this process, which is difficult to capture, providing
an insightful guiding role in the analysis of the SEI layer. As a
result, a more realistic SEI interface layer model was
established through this accurate analysis technology.
2. EXPERIMENTAL DETAILS
2.1. Materials. The Li foil (China Energy Lithium Co., Ltd.), the
commercial ether electrolyte (denoted as DOL/DME electrolyte), is
composed of 1 M LiTFSI dissolved in 1,3-dioxolane (DOL)/1,2-
dimethoxyethane (DME) (1:1 v/v) with 2% LiNO3 (Suzhou Duoduo
Technology Co., Ltd.). All of these materials were used as received
without further purification.
2.2. Electrochemical Measurements. All coin cells were
assembled as standard 2025 coin-type cells with 50 μL of electrolyte
in an Ar-filled glove box (O2 <0.1 ppm, H2O <0.1 ppm). The
commercial ether-based electrolyte was used in this cell, the Celgard
2500 as the separator, and Li foil (400 μm in thickness) as the anode.
The Li||Li symmetric cells were tested at room temperature under
galvanostatic charging/discharging conditions using a LAND multi-
channel battery cycler (Wuhan LAND electronics Co., Ltd.) The
electrochemical impedance spectroscopy (EIS) measurements were
performed in a frequency range between 105 and 10−1 Hz with a
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Figure 2. Depth profile curves of TOF-SIMS in (a) negative mode and (b) positive mode. Mass spectrum collected at the (c) surface and (d) after
sputter in negative mode. Mass spectrum collected at the (e) surface and (f) after sputter in positive mode.
voltage amplitude of 10 mV using an electrochemical workstation
(Shanghai Chenhua, China).
2.3. Characterization. The scanning electron microscopy (SEM)
measurements were carried out on a Regulus 8230 (Hitachi Inc.,
Japan) instrument. TOF-SIMS measurements were conducted with a
PHI nano TOF II (ULVAC-PHI Inc., Japan). In the process of
sample transfer, a special transfer vessel is used, which can directly
transfer the sample from the glove box to the TOF-SIMS vacuum
chamber without being exposed to the ambient air. A Bi3++ beam (30
kV) was used as the primary beam to detect the samples, and the
sputter etching was performed using an Ar+ beam (3 kV 100 nA) to
obtain the desired depth profile. The area of analysis was 100 × 100
μm2, while the sputtering area was 400 × 400 μm2. XPS measurement
was carried out on a PHI QUANTERA-II SXM instrument (ULVAC-
PHI Inc., Japan) with a monochromatic X-ray source (Al Kα =
1,486.6 eV). The sputter etching was performed using Ar+ gun (2 kV
20 mA) to obtain the desired depth profile. The area of analysis was
200 × 200 μm2, while the sputtering area was 2 × 2 mm2.
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3. RESULTS AND DISCUSSION
3.1. Electrochemistry and Morphology of SEI Change
on the Li Metal Anode. Currently, the commercialized
electrolytes could be mainly classified into carbonate and ether.
In our previous work, the lithium metal was found to exhibit
better deposition/dissolution efficiency in ether electrolyte.11
Therefore, the SEI of the lithium metal anode in ether
electrolyte was discussed in this work. The electrochemical
process of the SEI layer change at the interface of the lithium
metal anode was characterized by performing Li||Li sym-
metrical electrochemical impedance spectroscopy after differ-
ent cycles. As shown in Figure 1a, after one cycle, the Nyquist
and Bode diagrams in OCV phase showed only one semicircle
at the intermediate frequency, which corresponds to the charge
transfer resistance (RCT), while the SEI component does not
respond during quiescence. After the Li||Li symmetrical cell
undergoes 25 cycles with a current density of 1 mA cm−2, the
signal of the SEI layer is still weak, despite the charge transfer
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Figure 3. Mapping distributions of the corresponding charged fragments in negative mode: (a, c) collected on the surface of the Li anode, (b, d)
collected by the depth profile (a layer after the 30 s sputter time).
impedance decreasing (Figure 1b). In addition, the slope of the
low-frequency region, which represents the diffusion of lithium
ions, showed similar patterns to that of one cycle, indicating
that the lithium metal anode exhibited continuous plating/
stripping. The formed SEI layer is conducive to the charge
transfer of the lithium ions. As shown in Figure 1c, when the
measurement of the Li||Li symmetrical cell exceeds 100 cycles,
the shape of the low-frequency curve changes from an
approximate level to a line segment with an obvious slope,
which indicates that the composition of the interfacial layer has
been changed and the charge transfer kinetics of the lithium
ions at the interfacial layer becomes faster, resulting in a much
lower charge transfer impedance than that of the 25 cycles’
result. Moreover, the interfacial layer became much dense after
200 cycles, with a small charge transfer impedance of less than
10 Ω (Figure 1d), which indicated that the kinetic rate of
charge exchange between the lithium ion and the interface has
been improved with the processing of the cyclic reaction.
However, due to the growth of the passivated interfacial layer,
the diffusion of lithium ions may also be hindered, as revealed
by the increased diffusion slope of lithium ions in the low-
frequency region. Moreover, the diffusion behavior of lithium
ions could not be observed even at the low frequency of 1Hz.
The morphology of the lithium deposition after different cycles
was further investigated via SEM. Figure 1e shows the
morphology of the anode after 1 cycle, which indicates that
the electrolyte would react with the lithium metal, forming a
passivation layer to prevent further possible reaction between
the lithium metal and the electrolyte. The interfacial layer
tends to be denser when rising it to 25 cycles (Figure 1f). After
reaching 100 cycles, the size of the sediment on the surface of
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the lithium metal anode becomes larger, and the particles tend
to agglomerate and form a more compact and denser structure
(Figures 1g,h), which may further vary the charge transfer
resistance of the lithium ion, as discussed in the above EIS
results. The results indicate that the electrochemical behavior
of the lithium metal anode is regulated by SEI. Lithium
deposition shows different morphologies after different cycles,
which reveals a continuous change of SEI.
3.2. SEI Analysis of Li Metal Anode via TOF-SIMS. To
further investigate the SEI, the Li||Li symmetrical cell in ether
electrolyte after 200 cycles was measured via the TOF-SIMS
technique. Figure 2 shows the mass spectra of positively and
negatively charged fragments of SEI on the Li metal anode. It
should be noted here that all SIMS data were measured as a
function of the mass charge ratio (m/z), which indicated that
the secondary ion with one single charge is required to observe
the correct mass. According to the depth analysis curve of the
lithium metal anode in its negative ion mode (Figure 2a), the
signal intensity of element C decreased with the increase of
analysis depth, while the intensities of F, O, and S increased
when increasing the depth, which indicated that the SEI of
lithium metal anode is a dual-layered structure, with the outer
and inner layers consisting of an organic phase and inorganic
phase, respectively. In addition, the relatively strong signals of
F and O further indicated that apart from the surface oxidation,
the decomposition of lithium salt i may also have occurred
during the circulation process. The depth profile curve of the
positive ion mode is demonstrated in Figure 2b. As can be
observed, when increasing the probing depth, the signal
intensities of the lithium salt decomposition products and
surface oxides, such as HCOLi (m/z = 36), CH3COLi2 (m/z =
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Figure 4. (a) 3D variation of the TOF-SIMS intensity related to the corresponding charged fragments. (b) 3D distribution overlay between LiF
and C2F6S2O4N, (c) 3D distribution overlay between LiF and C6O4H11. 3D distribution of C2F6S2O4N (fragment of LiTFSI) with various
interfaces: (d) SiO2-modified interface, (e) electrolyte-derived SEI, and (f) poly(trifluoroethyl methacrylate)-modified interface.

57), −CH2CH2OCH2OLi (m/z = 81), Li2O (m/z = 30), and
Li2OH (m/z = 31), tend to decrease, while inorganic phase
products from the reaction of LiTFSI and the lithium metal
anode, including Li2F (m/z = 33), LiNO (m/z = 37), Li2N2O
(m/z = 58), Li3F2 (m/z = 59), LiSO2N (m/z = 85), Li2S3 (m/z
= 110), and H2CFSO2N (m/z = 111), showed an enhanced
signal strength. These results further suggested that the SEI of
the lithium metal anode exhibited an organic/inorganic bilayer
structure, which is consistent with the previous results of the
negative ion mode. The negative ion modes of the mass
spectrum before and after sputtering are shown in Figure 2c,d,
which contain information regarding the negatively charged
fragments of SEI, such as carbon, oxygen, and fluorine.
However, the relative abundance of the charged fragments
collected by the depth profile was different from that on the
anode surface, which suggested that the charge fragments
mainly come from the decomposition of LiTFSI and DOL.
From the TOF-SIMS results, not only could the chemical
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variation and cation gradient be revealed, but also may any
phase segregation or product accumulation in the SEI layer be
probed by taking high-resolution images, which would possibly
provide deeper insights into their mechanism. The results of
the positive ion mass spectrum before and after sputtering
(Figure 2e,f) further indicated that the SEI mainly consisted of
lithium and sulfur, with their contents varied at different
depths. The above finding suggested that the multilayer
structure of the SEI might be composed of various electrolyte-
decomposed products.
To investigate the spatial distribution of these organic and
inorganic species, the mapping images of the negative ion
modes were measured. We can anticipate that the main source
would be the charged atoms or atomic clusters of the LiTFSI-
decomposed products that are excited by Bi ions. As can be
observed in Figure 3a,b, the ions with a mass charge ratios (m/
z) of 62, 78, and 147 exhibited a relatively high intensity at the
anode surface. All ion intensities decreased after sputtering,
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Figure 5. TOF-SIMS analysis by positive mode: (a) the mapping distribution of related elements by depth profile. The region of interest: (b) total
mapping distribution, (c, d) related mass spectrum. (e) 3D distribution of related charged fragments.

which indicated that the SEI surface component of the lithium
metal negative electrode is decomposed by the organic
electrolyte.31 To be more specific, m/z = 147 could be
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assigned to the segment [2MDOL−1]+ after the polymerization
of DOL, m/z = 62 represented the ion fragment (CH3−O−
CH2−O−H) after the loss of −CH3 during its ionization, and
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m/z = 78 could be ascribed to the SO2N fragment after the
decomposition of lithium salt LiTFSI. The dual-layered
structure of lithium metal anode SEI could be further
confirmed by the depth profile, where enhanced ion intensities
of O, F, S, and OH (m/z = 17), LiF (m/z = 26) and LiF2 (m/z
= 45) were observed when increasing the sputtering time
(Figure 3c,d), corresponding to the inorganic products of
lithium metal reacting with the electrolyte at the inner layer.
Next, the 3D tomography with a transverse resolution of 100
μm was measured to investigate the microstructure of the
interfacial layer, cation distribution, and the stability of SEI. As
illustrated in Figure 4a, the ion fragments with mass charge
ratios (m/z) of 62, 78, 147, and 280 were found to be
distributed only at the surface layer, which indicated that the
products generated during the reaction between the lithium
metal anode and electrolyte may form a passivation layer,8
thereby preventing any further reaction. Such a process could
be considered as a spontaneously occurring protective
mechanism of the lithium anode. On the other hand, other
fragments, including m/z = 62 (CH3−O−CH2−O−H), m/z =
147 (C6O4H11), and m/z = 78 (SO2N), m/z = 280
(C2F6S2O4N) were corresponded to the reaction products of
DOL and the decomposition products of LiTFSI, respectively.
The existence of unreacted LiTFSI in the outermost layer
further suggests the barrier effect of SEI, which could avoid its
decomposition. In contrast, the polymerized organic phase was
found to be located only at the surface layer, and could store
the electrolyte and conduct lithium ions. For example, the
inorganic phases of Li-F-based compounds, such as m/z = 26
(LiF), m/z = 45 (LiF2), m/z = 64 (LiF3), and m/z = 71
(Li2F3), were evenly distributed in the inner SEI layer.
Moreover, it seems that the SEI layer contained more than
one phase, as demonstrated in its 3D surface morphology. In
addition, the inorganic phase products showed a higher
content at the inner layer, which could be attributed to the
easier reduction processes of anions on the surface of the
lithium metal, leading to different distribution characteristics of
the surface and SEI layers. By overlaying the 3D distribution
results of m/z = 26 (LiF), m/z = 280 (C2F6S2O4N), and m/z =
147 (C6O4H11), it was found that the lithium salt was evenly
distributed at the outermost SEI layer (Figures 4b,c), which
completely covered the LiF product forming during the
decomposition of lithium salt and metal lithium; the results
indicate that SEI may not be a dense layer and the liquid
electrolyte can be stored between the organic phase and
inorganic phase.32 In contrast, the so-formed organic layer of
C6O4H11 due to the decomposition of the organic electrolyte
DOL exhibited a staggered distribution with LiF, which further
confirmed the dual-layered structure of SEI. Furthermore, the
state of the interface layer is related to the change degree of
SEI, which can be evaluated by the distribution of the lithium
salt. Based on our previous results, 33,34 the artificial
modification of the interface layer can effectively regulate the
change degree of SEI. As shown in Figure 4d−f, the LiTFSI
exhibits various distributions after 200 electrochemical cycles.
The SiO 2 -modified interface shows a thinner LiTFSI
distribution layer than the electrolyte-derived SEI, but the
poly(trifluoroethyl methacrylate)-modified interface represents
a thicker LiTFSI distribution layer than the electrolyte-derived
SEI. The results indicate that the change degree of SEI under
the external film layer is different. Since such a process is a
continuous change and cannot be revealed by conventional
tools, the change of SEI after the electrochemical cycle was
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measured by reconstructing the distribution of the lithium salt
via TOF-SIMS.
The distribution of the inorganic phase in the SEI layer of
the lithium metal anode was investigated by employing a
positive ion mode. Note that the unevenly distributed cations
may lead to a gradient at the inorganic phase interface in SEI,
which might affect the stability of the passivation layer. Figure
5a presents the 2D mapping results of the depth profile in
positive ion mode, where Li exhibited strong signals, and their
intensities tend to be higher when increasing the probing
depth. The m/z = 6 (6Li) and m/z = 7 (Li) correspond to ion
fragments from the lithium metal anode. By comparing the 2D
images of the ion fragments with mass charge ratios (m/z) of
32, 33, 58, 59, 85, 110, and 111, respectively, it was found that
despite their similar morphologies and structures, their element
compositions were different. These ion fragments are the
inorganic phase products obtained during the reaction between
LiTFSI and the lithium metal after decomposition, which
constituted the main components of SEI. In addition, areas
with bright and dark regions of the total ion distribution were
observed in the 2D mapping images. To investigate their
difference, the region of interest (ROI) function was adopted.
As shown in Figure 5b, two circles with equal area were
extracted from the mapping image to obtain their mass
spectrum. Compared to the light region (Figure 5c), the
intensities of the ion fragments with the mass charge ratios (m/
z) of 14, 33, 59, 85, and 111 decreased in the dark region
(Figure 5d). Such fragments may come from the inorganic
phase products formed by the strongly electronegative atoms
and metal lithium after the decomposition of LiTFSI, such as
N, Li2F, Li3F2, Li4F3 and Li5N2O3. The results show that the
distribution of the inorganic phase at the inner interface of the
lithium metal anode SEI is uneven, which indicated that
lithium ions may pass through the SEI layer with different
rates, as well as affected the morphology of the deposited
lithium, resulting in the formation of lithium dendrites in the
electrolyte-derived SEI layer after long-term cycling. The
graded distribution of inorganic phase was unraveled by
measuring the spatial three-dimensional distribution (Figure
5e). For instance, organic phases such as CH3COLi2 (m/z =
57) and −CH2CH2OCH2Oli (m/z = 81) that formed by the
combination of DME and DOL with metal lithium after
decomposition were only distributed on the surface of SEI.
The surface distribution showed a porous morphology, which
indicated the intersection and dislocation distribution with the
inorganic phase. In addition, Li2F (m/z = 33) and Li3F2 (m/z
= 59) exhibited the highest density, which suggested a strong
electronegativity of fluorine in LiTFSI. Its product is the main
component of the inorganic phase of the SEI layer. The
inorganic phase formed by N and S elements in LiTFSI was
also evenly distributed in the SEI layer. It is worth noting that
the quality resolution and lateral resolution of TOF-SIMS data
depend on the primary ion beam conditions. Although TOF-
SIMS is known for its high resolution, this occurs only when
the beam is operating in beam mode. This means that the main
ion beam pulse with a time scale of about 100 ns is compressed
to picoseconds, which allows much accurate determination of
the main ion’s flight time, resulting in excellent mass resolution
of LiNO (m/z = 37), Li2N2O (m/z = 58), Li3SO2 (m/z = 85),
and H2CFSO2N (m/z = 111). Such tomography can be quite
enlightening and used to reveal changes in the interface
chemistry that result in improved performance or stability.
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Figure 6. (a) XPS characterization of the Li||Li cell in the ether electrolytes after 200 cycles: (a) full spectrum scanning, (b) intensity of the related
element, (c) atom concentration of the related element; the surface analysis of the (d) C 1s spectrum, (e) F 1s spectrum, (f) N 1s spectrum, and
(g) S 2p spectrum.
3.3. SEI Composition on Li Metal Anode from XPS
Depth Profiles. To further verify the double-layered structure
of the SEI layer, the chemical components of the SEI layer at
different depths were investigated by XPS depth profiles.
Taking the negative electrode deposition state of metal lithium
as an example, the full XPS spectrum (Figure 6a) shows the
element composition of each layer of SEI. In the electrolyte of
1M LiTFSI in DOL/DME (volume ratio = 1:1), the main
elements of SEI are C, N, O, F, and S, which came from the
products of the reaction with metal lithium after electrolyte
decomposition. The depth analysis curve of the metal lithium-
negative electrode SEI from the inside of the surface is shown
in Figure 6b. The thickness of the interfacial layer can be
estimated through the changes of sputtering time and signal
intensity. It can be seen that with the increase of sputtering
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time, the signal of element F also increased, while the signal of
element C decreased sharply, which indicated that the SEI
mainly consists of inorganic phase from the surface to the inner
layer. Figure 6c shows the atomic concentration percentage of
different elements in each layer. The content of C at the
surface was about 17.5%. With the increase of sputtering time,
the content of C gradually decreased, while F exhibited an
increased content. At the same time, a slight decrease of N and
S was observed, which is basically the same as that at the
surface. The organic phase after the ring opening of cyclic
DOL in the electrolyte only exists on the surface of the SEI
layer. The chemical states of each layer were then studied by
XPS. As illustrated in Figure 6d−g, the binding energies of C
1s were 284.8, 286.1, 288.1, and 292.4 eV, corresponding to
C−C, C−O/C−S, CO, and C−F, respectively. The binding
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Figure 7. XPS depth profile of the Li anode: (a) C 1s spectrum, (b) F 1s spectrum, (c) N 1s spectrum, and (d) S 2p spectrum.

Table 1. Atom Concentration of Related Elements with Depth Profile

O 1s F 1s S 2p
atomic (%) Li 1s C 1s N 1s Li-O CO C-O Li-F C-F S-C SO
cycle1 (0s) 29.02 16.52 3.19 6.39 19.39 1.50 4.82 10.94 2.78 5.45
cycle2 (15s) 37.13 5.43 3.27 3.82 11.32 5.86 17.98 8.42 2.07 4.72
cycle3 (30s) 38.33 4.19 2.39 2.11 10.01 5.24 25.87 6.66 1.30 3.90
cycle4 (60s) 38.96 3.27 2.19 0.93 6.99 4.13 34.16 6.03 0.52 2.82
cycle5 (90s) 47.51 3.43 2.47 0.77 2.41 9.15 23.58 7.03 1.03 2.62
cycle6 (120s) 43.72 2.92 1.90 2.24 6.30 3.38 32.06 3.76 1.14 2.58
cycle7 (180s) 42.90 2.36 1.38 1.50 5.70 3.20 36.78 3.56 0.62 2.01
cycle8 (240s) 47.81 2.26 1.63 1.22 2.71 8.34 25.92 6.59 1.14 2.41

energies of 685.0 and 688.3 eV in the F 1s diagram represent
Li−F and C−F. The signal intensity of C−F on the surface is
higher than that of Li−F, which indicates that unreacted
LiTFSI existed on the surface. The other decomposition
products of LiTFSI also include N-O (∼399.3 eV), C−S
(∼149.4 and ∼150.6 eV), and SO (∼156.6 and ∼158.8 eV).
To gain more insight, XPS depth analysis was further
performed on C, F, N, and S. As shown in Figure 7a, the
content of C−C decreases with the increase of sputtering time,
indicating that the surface is mainly organic carbon and the
inner layer is mainly inorganic carbon decomposed by LiTFSI.
In Figure 7b, the signal intensity of Li−F increases with the
increase of sputtering time, and the signal intensity of C−F
decreases with the increase of sputtering time, indicating that
the unreacted LiTFSI or its decomposition products were
mainly distributed on the surface, and the inner layer is mainly
the dense LIF inorganic phase formed by defluorination
reaction of C−F and the lithium ion. As shown in Figure 7c,
the signal strength of N−O in N 1s diagram decreases with the
increase of sputtering time, and the signal strength of the C−S
bond and SO in the S 2p diagram (Figure 7d) decreases
with the increase of sputtering time, but the contents of N and
S after depth analysis are not different from those on the
surface, which indicates that there are decomposition products
20205
of LiTFSI in the whole SEI layer; the relevant information is
shown in Table 1.
4. CONCLUSIONS
In conclusion, TOF-SIMS was employed to obtain the
chemical information of all components from SEI at the
lithium metal anode. It can achieve 70 nm lateral resolution, as
well as sub-nanodepth resolution up to 3D, which could be
applied to understand the relationship between the distribution
of the organic/inorganic phase and change of the SEI layer. By
investigating the structure of SEI at the Li metal anode
interface in ether electrolyte, we studied the effects of SEI
composition and structure on the interface stability from the
surface to the inner layer via TOF-SIMS and XPS. The TOF-
SIMS depth profile of the dual-layered structure of lithium
metal anode could quantify the SEI thickness and reveal its
structure; 2D mapping images could directly reveal the
distribution of grain boundaries in the SEI layer of the Li
metal anode, and 3D tomography can provide information on
the gradient of each phase in the SEI film from a three-
dimensional perspective, which would connect the lithium
ion’s electrochemical deposition with the chemical change of
the SEI film. The results indicated that after several
electrochemical cycles, the outermost layer of SEI is mainly
composed of a very thin organic phase, while the organic phase
https://doi.org/10.1021/acsami.2c00842
ACS Appl. Mater. Interfaces 2022, 14, 20197−20207
ACS Applied Materials & Interfaces
can absorb and store part of the electrolyte, thus improving the
conduction of lithium ion regardless of the inactive lithium
accumulation. In addition, the amount of LiTFSI that is not
decomposed can be related to the change degree of SEI. Since
the SEI layer may change in varying degrees during the
electrochemical cycles, the greater the SEI change degree, the
more the electrolyte stored in the organic phase and the
thicker the distribution layer of lithium salt (LiTFSI) obtained.
The TOF-SIMS is used to reveal this process of continuous
change, which is difficult to be measured by other experimental
methods, thus providing a great guiding role in the analysis of
the SEI layer. Furthermore, through the XPS depth profile, the
chemical composition of the SEI layer at different depths was
analyzed in detail, which further verifies the excellent accuracy
of TOF-SIMS to detect the chemical properties of the SEI film
at both the surface and the interface.
■
AUTHOR INFORMATION
Corresponding Author
Tinglu Song − Experimental Center of Advanced Materials
School of Materials Science & Engineering, Beijing Institute of
Technology, Beijing 100081, P. R. China; Email: song@
bit.edu.cn
Authors
Chengwei Ma − Beijing Key Laboratory of Environmental
Science and Engineering, School of Materials Science and
Engineering, Beijing Institute of Technology, Beijing 100081,
P. R. China; orcid.org/0000-0002-3879-3531
Fan Xu − BTR New Material Group Co., Ltd., Shenzhen
518107, P. R. China; State Key Laboratory for Artificial
Microstructure and Mesoscopic Physics, School of Physics,
Peking University, Beijing 100871, P. R. China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.2c00842
Author Contributions
C.M. and T.S. conceptualized the idea, conceived the
experiments, and wrote the draft. C.M. synthesized the
materials and prepared the samples. C.M., F.X., and T.S.
carried out the materials’ characterization work and data
analysis. T.S. supervised the research. All authors discussed and
commented on the manuscript.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors acknowledge support from the National Natural
Science Foundation of China (No. 22075026), and the
Postdoctoral Research Foundation of China, grant number
2020M680374. The authors thank Defeng Lu from CoreTech
Integrated Limited (ULVAC-PHI) for the TOF-SIMS
technical support.
■
REFERENCES
(1) Cheng, X. B.; Zhang, R.; Zhao, C. Z.; Zhang, Q. Toward Safe
Lithium Metal Anode in Rechargeable Batteries: A Review. Chem. Rev.
2017, 117, 10403−10473.
(2) Lin, D.; Liu, Y.; Cui, Y. Reviving the Lithium Metal Anode for
High-energy Batteries. Nat. Nanotechnol. 2017, 12, 194−206.
(3) Goodenough, J. B.; Park, K. S. The Li-Ion Rechargeable Battery:
A Perspective. J. Am. Chem. Soc. 2013, 135, 1167−1176.
20206
www.acsami.org Research Article
(4) Liu, D.-H.; Bai, Z.; Li, M.; Yu, A.; Luo, D.; Liu, W.; Yang, L.; Lu,
J.; Amine, K.; Chen, Z. Developing High Safety Li-metal Anodes for
Future High-energy Li-metal Batteries: Strategies and Perspectives.
Chem. Soc. Rev. 2020, 49, 5407−5445.
(5) Suo, L.; Oh, D.; Lin, Y.; Zhuo, Z.; Borodin, O.; Gao, T.; Wang,
F.; Kushima, A.; Wang, Z.; Kim, H.-C.; Qi, Y.; Yang, W.; Pan, F.; Li,
J.; Xu, K.; Wang, C. How Solid-Electrolyte Interphase Forms in
Aqueous Electrolytes. J. Am. Chem. Soc. 2017, 139, 18670−18680.
(6) Zou, P.; Sui, Y.; Zhan, H.; Wang, C.; Xin, H. L.; Cheng, H.-M.;
Kang, F.; Yang, C. Polymorph Evolution Mechanisms and Regulation
Strategies of Lithium Metal Anode under Multiphysical Fields. Chem.
Rev. 2021, 121, 5986−6056.
(7) Wu, J.; Ihsan-Ul-Haq, M.; Chen, Y.; Kim, J.-K. Understanding
Solid Electrolyte Interphases: Advanced Characterization Techniques
and Theoretical Simulations. Nano Energy 2021, 89, No. 106489.
(8) Peled, E. The Electrochemical-behavior of Alkali and Alkaline-
Earth Metals in Non-Aqueous Battery Systems - The Solid Electrolyte
Interphase Model. J. Electrochem. Soc. 1979, 126, 2047−2051.
(9) Goodenough, J. B.; Kim, Y. Challenges for Rechargeable Li
Batteries. Chem. Mater. 2010, 22, 587−603.
(10) Choi, N. S.; Chen, Z.; Freunberger, S. A.; Ji, X.; Sun, Y. K.;
Amine, K.; Yushin, G.; Nazar, L. F.; Cho, J.; Bruce, P. G. Challenges
Facing Lithium Batteries and Electrical Double-layer Capacitors.
Angew. Chem., Int. Ed. 2012, 51, 9994−10024.
(11) Ma, C.; Mu, G.; Lv, H.; Liu, C.; Bi, J.; Fu, J.; Mu, D.; Wu, B.;
Wu, F. In Situ-Formed Flexible Three-dimensional Honeycomb-like
Film for a LiF/Li3N-enriched Hybrid Organic−inorganic Interphase
on the Li Metal Anode. Mater. Chem. Front. 2021, 5, 5082−5092.
(12) Zheng, J.; Kim, M. S.; Tu, Z.; Choudhury, S.; Tang, T.; Archer,
L. A. Regulating Electrodeposition Morphology of Lithium: Towards
Commercially Relevant Secondary Li Metal Batteries. Chem. Soc. Rev.
2020, 49, 2701−2750.
(13) Zhai, P. B.; Liu, L. X.; Gu, X. K.; Wang, T. S.; Gong, Y. J.
Interface Engineering for Lithium Metal Anodes in Liquid Electrolyte.
Adv. Energy Mater. 2020, 10, No. 2001257.
(14) Gao, Y.; Yan, Z.; Gray, J. L.; He, X.; Wang, D.; Chen, T.;
Huang, Q.; Li, Y. C.; Wang, H.; Kim, S. H.; Mallouk, T. E.; Wang, D.
Polymer-Inorganic Solid-Electrolyte Interphase for Stable Lithium
Metal Batteries Under Lean Electrolyte Conditions. Nat. Mater. 2019,
18, 384−389.
(15) Yu, Z.; Wang, H.; Kong, X.; Huang, W.; Tsao, Y.; Mackanic, D.
G.; Wang, K.; Wang, X.; Huang, W.; Choudhury, S.; Zheng, Y.;
Amanchukwu, C. V.; Hung, S. T.; Ma, Y.; Lomeli, E. G.; Qin, J.; Cui,
Y.; Bao, Z. Molecular Design for Electrolyte Solvents Enabling
Energy-Dense and Long-cycling Lithium Metal Batteries. Nat. Energy
2020, 5, 526−533.
(16) Zhang, W.; Zhang, S.; Fan, L.; Gao, L.; Kong, X.; Li, S.; Li, J.;
Hong, X.; Lu, Y. Tuning the LUMO Energy of an Organic Interphase
to Stabilize Lithium Metal Batteries. ACS Energy Lett. 2019, 4, 644−
650.
(17) Peled, E.; Menkin, S. Review-SEI: Past, Present and Future. J.
Electrochem. Soc. 2017, 164, A1703−A1719.
(18) Yan, C.; Cheng, X. B.; Tian, Y.; Chen, X.; Zhang, X. Q.; Li, W.
J.; Huang, J. Q.; Zhang, Q. Dual-Layered Film Protected Lithium
Metal Anode to Enable Dendrite-Free Lithium Deposition. Adv.
Mater. 2018, 30, No. e1707629.
(19) Yan, C.; Yao, Y. X.; Chen, X.; Cheng, X. B.; Zhang, X. Q.;
Huang, J. Q.; Zhang, Q. Lithium Nitrate Solvation Chemistry in
Carbonate Electrolyte Sustains High-Voltage Lithium Metal Batteries.
Angew. Chem., Int. Ed. 2018, 57, 14055−14059.
(20) Yan, C.; Cheng, X. B.; Yao, Y. X.; Shen, X.; Li, B. Q.; Li, W. J.;
Zhang, R.; Huang, J. Q.; Li, H.; Zhang, Q. An Armored Mixed
Conductor Interphase on a Dendrite-Free Lithium-Metal Anode. Adv.
Mater. 2018, 30, No. e1804461.
(21) Schroder, K. W.; Dylla, A. G.; Harris, S. J.; Webb, L. J.;
Stevenson, K. J. Role of Surface Oxides in the Formation of Solid−
Electrolyte Interphases at Silicon Electrodes for Lithium-Ion Batteries.
ACS Appl. Mater. Interfaces 2014, 6, 21510−21524.
https://doi.org/10.1021/acsami.2c00842
ACS Appl. Mater. Interfaces 2022, 14, 20197−20207
ACS Applied Materials & Interfaces www.acsami.org Research Article

(22) Harvey, S. P.; Li, Z.; Christians, J. A.; Zhu, K.; Luther, J. M.;
Berry, J. J. Probing Perovskite Inhomogeneity beyond the Surface:
TOF-SIMS Analysis of Halide Perovskite Photovoltaic Devices. ACS
Appl. Mater. Interfaces 2018, 10, 28541−28552.
(23) Dong, Y.; Xu, F.; Li, Y.; Song, T.; Tan, G. Component
distribution of nano-carbon materials assisted by Time of Flight-
Secondary Ion Mass Spectrometer. J. Phys.: Conf. Ser. 2021, 2011,
No. 012071.
(24) Song, T.; Zou, M.; Lu, D.; Chen, H.; Wang, B.; Wang, S.; Xu, F.
Probing Surface Information of Alloy by Time of Flight-Secondary
Ion Mass Spectrometer. Crystals 2021, 11, 1465.
(25) Hou, C.-H.; Hung, S.-H.; Jhang, L.-J.; Chou, K.-J.; Hu, Y.-K.;
Chou, P.-T.; Su, W.-F.; Tsai, F.-Y.; Shieh, J.; Shyue, J.-J. Validated
Analysis of Component Distribution Inside Perovskite Solar Cells and
Its Utility in Unveiling Factors of Device Performance and
Degradation. ACS Appl. Mater. Interfaces 2020, 12, 22730−22740.
(26) Seyeux, A.; Frankel, G. S.; Missert, N.; Unocic, K. A.; Klein, L.
H.; Galtayries, A.; Marcus, P. ToF-SIMS Imaging Study of the Early
Stages of Corrosion in Al-Cu Thin Films. J. Electrochem. Soc. 2011,
158, C165−C171.
(27) Mao, D.; Blatz, G.; Wickersham, C. E.; Gloeckler, M.
Correlative Impurity Distribution Analysis in Cadmium Telluride
(CdTe) Thin-film Solar Cells by ToF-SIMS 2D Imaging. Sol. Energy
Mater. Sol. Cells 2016, 157, 65−73.
(28) Zai, H.; Su, J.; Zhu, C.; Chen, Y.; Ma, Y.; Zhang, P.; Ma, S.;
Zhang, X.; Xie, H.; Fan, R.; Huang, Z.; Li, N.; Zhang, Y.; Li, Y.; Bai,
Y.; Gao, Z.; Wang, X.; Hong, J.; Sun, K.; Chang, J.; Zhou, H.; Chen,
Q. Sandwiched Electrode Buffer for Efficient and Stable Perovskite
Solar Cells with Dual Back Surface Fields. Joule 2021, 5, 2148−2163.
(29) Huo, H.; Gao, J.; Zhao, N.; Zhang, D.; Holmes, N. G.; Li, X.;
Sun, Y.; Fu, J.; Li, R.; Guo, X.; Sun, X. A Flexible Electron-Blocking
Interfacial Shield for Dendrite-free Solid Lithium Metal Batteries. Nat.
Commun. 2021, 12, No. 176.
(30) Priebe, A.; Huszar, E.; Nowicki, M.; Pethö, L.; Michler, J.
Mechanisms of Fluorine-Induced Separation of Mass Interference
during TOF-SIMS Analysis. Anal. Chem. 2021, 93, 10261−10271.
(31) Aurbach, D. Review of Selected Electrode-solution Interactions
Which Determine the Performance of Li and Li Ion Batteries. J. Power
Sources 2000, 89, 206−218.
(32) Zhang, Z. W.; Li, Y. Z.; Xu, R.; Zhou, W. J.; Li, Y. B.; Oyakhire,
S. T.; Wu, Y. C.; Xu, J. W.; Wang, H. S.; Yu, Z. A.; Boyle, D. T.;
Huang, W.; Ye, Y. S.; Chen, H.; Wan, J. Y.; Bao, Z. N.; Chiu, W.; Cui,
Y. Capturing the Swelling of Solid-electrolyte Interphase in Lithium
Metal Batteries. Science 2022, 375, 66.
(33) Ma, C.; Liu, C.; Zhang, Y.; Zhang, X.; Zhao, Z.; Song, T.; Wu,
B.; Mu, D. A dual lithiated alloy interphase layer for high-energy−
density lithium metal batteries. Chem. Eng. J. 2022, 434, No. 134637.
(34) Ma, C.; Zhang, X.; Liu, C.; Zhang, Y.; Wang, Y.; Liu, L.; Zhao,
Z.; Wu, B.; Mu, D. Nano silica aerogel-induced formation of an
organic/alloy biphasic interfacial layer enables construction of stable
high-energy lithium metal batteries. Green Energy and Environment
2022, DOI: 10.1016/j.gee.2021.12.006.

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ACS Appl. Mater. Interfaces 2022, 14, 20197−20207