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Superlattice-Stabilized WSe2 Cathode for Rechargeable
Aluminum Batteries
Fangyan Cui, Mingshan Han, Wenyuan Zhou, Chen Lai, Yanhui Chen, Jingwen Su,
Jinshu Wang, Hongyi Li,* and Yuxiang Hu*
F. Cui, M. Han, W. Zhou, C. Lai, Y. Chen, J. Su, J. Wang, H. Li, Y. Hu
Key Laboratory of Advanced Functional Materials
Faculty of Materials and Manufacturing
Beijing University of Technology
Beijing 100124, P. R. China
E-mail: lhy06@bjut.edu.cn; y.hu@bjut.edu.cn
DOI: 10.1002/smtd.202201281
density.[4] Amongst, traditional elec-
trodes stability, limited by the inherently
strong Coulombic forces between vulner-
able structures and high-charge-density
aluminum ions (Al3+, 364 C mm−3), is the
core challenge in RABs.[5]
To solve above-mentioned issues
in RABs, layered transition metal
dichalcogenides (TMDCs) with moderate
aluminum-selenium/sulfide bonding,
adjustable interlayer spacing, and theo-
retically abundant ions accommodations,
have received much attention in recent
years.[6] Amongst, tungsten selenide (WSe2)
is favorable in metal-ion batteries owing
to its theoretically high capacity, high
conductivity, broad interlayer space, and
moderate metal-selenium bonding interac-
tions, yet never been reported in RABs.[7]
Nevertheless, similar with previous reported
TMDCs in RABs, the strong electrostatic
interaction with inherently high-charge-
density Al3+ (derived from AlxCly− in ionic
liquid-based electrolyte) would still result
in irreversible destruction and active materials pulverization/
dissolution (Scheme 1a). Above all, in despite of the advantages
of high theoretical capacity, TMDCs cathodes still suer from
inferior cycling stability. Therefore, the development of a new
strategy to stabilize the WSe2 structure as a case study of TMDCs
is necessary to enhance RABs performance. Superlattice-type
compound, a class of laminated fine materials composed of two
(or more) alternate and periodic components, is especially suit-
able for accommodating high-charge-density active ions.[8] Pre-
viously, superlattice-based materials were proved as stable and
high-performance cathodes in monovalent-ion batteries, such
as LIBs and sodium-ion batteries (SIBs).[9] For example, ordered
superlattice layered oxide (Na3Ni2RuO6) had been applied in
SIBs with two times enhanced capacities in comparison with the
un-treated samples.[8c] The strong Coulombic forces with large
binding energy of multivalent ions make the electrode structure
more prone to irreversible pulverization during cycling than that
of alkali-metal batteries.[10] The superlattice-type materials are pro-
spective candidates for multivalent ions storage due to expanded
interlayer distances, multiple active sites, and improved diusion
kinetics process.[8d] Thus, the introduction of organic molecules
to form superlattice-type structures in TMDCs (such as WSe2)
would be promising to stabilize electrode structure during Al3+
de-intercalation, yet never been explored in RABs.
Rechargeable aluminum batteries (RABs), with abundant aluminum reserves,
low cost, and high safety, give them outstanding advantages in the post-
lithium batteries era. However, the high charge density (364 C mm−3) and
large binding energy of three-electron-charge aluminum ions (Al3+) de-
intercalation usually lead to irreversible structural deterioration and decayed
battery performance. Herein, to mitigate these inherent defects from Al3+,
an unexplored family of superlattice-type tungsten selenide-sodium dode-
cylbenzene sulfonate (SDBS) (S-WSe2) cathode in RABs with a stably crystal
structure, expanded interlayer, and enhanced Al-ion diusion kinetic process
is proposed. Benefiting from the unique advantage of superlattice-type struc-
ture, the anionic surfactant SDBS in S-WSe2 can eectively tune the interlayer
spacing of WSe2 with released crystal strain from high-charge-density Al3+
and achieve impressively long-term cycle stability (110 mAh g−1 over
1500 cycles at 2.0 A g−1). Meanwhile, the optimized S-WSe2 cathode with
intrinsic negative attraction of SDBS significantly accelerates the Al3+
diusion process with one of the best rate performances (165 mAh g−1 at
2.0 A g−1) in RABs. The findings of this study pave a new direction toward
durable and high-performance electrode materials for RABs.
ReseaRch aRticle
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/smtd.202201281.
1. Introduction
The growing demands for state-of-the-art batteries, especially lith-
ium-ion batteries (LIBs) and their large-scale applications raise
the ever-increasing concerns of limited lithium resources, high-
price, and safety issue.[1] In response to these encountered prob-
lems toward LIBs, rechargeable aluminum batteries (RABs) are
promising candidates due to their abundant reserves, low cost,
and high safety.[2] In particular, the aluminum metal anode has
a three-electron-charge transfer and a high volumetric specific
capacity of 8040 mAh cm−3 (versus the value of 2046 mAh cm−3
for lithium).[3] However, considerable crucial challenges of
RABs still need to be conquered, including electrode pulveri-
zation/solubility, insucient cyclic stability, and low energy
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Herein, we proposed a new family of superlattice-type WSe2-
sodium dodecylbenzene sulfonate (SDBS) (S-WSe2) as a model
cathode to overcome the intrinsic weakness in RABs, and sta-
bilize cathodes structure/performance. Benefiting from the
unique superlattice-type structure, the anionic surfactant SDBS
can eectively tune the interlayer spacing of WSe2, release
crystal strain from high-charge-density Al3+, and accelerate the
Al3+ kinetics process, which was further confirmed via theo-
retical calculations. In addition, SDBS as a structural stabilizer
eciently reduce the dissolution of active species in Lewis-acidic
electrolytes, and layered compounds agglomeration. Compared
with traditional WSe2, both superlattice-type and organic inter-
calation strategies could yield enhanced long-term stability.
The optimized S-WSe2 achieved prominent cycling stability
(175 mAh g−1 over 500 cycles at 500 mA g−1, and above
110 mAh g−1 after 1500 cycles at a high current density of
2.0 A g−1). Moreover, S-WSe2 cathode exhibited drastically
enhanced rate-capability (165 mAh g−1 at 2.0 A g−1), and impres-
sively high specific capacity (354 mAh g−1 at 100mA g−1). Simul-
taneously, in/ex situ characterizations not only revealed the
intercalation reaction mechanism of S-WSe2 but also corrobo-
rated that the facile superlattice-type and organic-intercalated
strategy eciently prevented the structural collapse after long-
term cycling in RABs. Overall, the superlattice-type S-WSe2
cathode would pave a promising direction to design stable and
high-performance electrodes in RABs.
2. Results and Discussions
2.1. Structural Characterization of S-WSe2
Previously, owing to the high-charge-density of Al3+, normal
TMDCs, such as WSe2 usually suered from layered-structure
pulverization and drastic performance reduction in RABs. On
the contrary, the superlattice structure cathodes, which own
inherently stable interfaces, expanded interlayer spacing, and
intercalated organics molecular, drastically stabilize revers-
ible de-intercalation of high-charge-density Al3+, which would
contribute to robust layered-structure and long-term stability
in RABs (Scheme 1b,c). The superlattice-type S-WSe2 was
prepared via a bottom-up one-pot solvothermal approach.
Under the action of a high temperature, high-pressure
transfer physical medium, the raw reactants were constantly
undergoing chemical transport to form new products with con-
trolled particle size, physical phase, and morphology.[11] After
solvothermal reaction at 200 °C for 48 h, the phase composi-
tion and structural information of S-WSe2 and pristine WSe2
are qualitatively identified by X-ray diraction (XRD) patterns
(Figure 1a). The characteristic diraction peaks of WSe2 exhib-
ited at 2θ= 13.42°, 31.29°, 34.32°, and 41.28°, corresponded to
the (002), (100), (102), and (006) crystal planes, respectively,
which were consistent with standard WSe2 phase (JCPDS Card
No. 38–1388).[12] Compared to the WSe2 sample, the XRD pat-
terns of S-WSe2 displayed that the diraction peaks clearly
shifted to a lower angle, with a d-spacing changing from 6.58 Å
in the WSe2 sample to 10.10 Å in the S-WSe2. Moreover, the dif-
fraction peaks of S-WSe2 at 8.74° and 17.03° corresponded to the
(002) and (004) crystal planes, respectively. The obtained results
revealed the intercalation of WSe2 through chain-like organic
molecules (such as sodium dodecylbenzene sulfonate (SDBS))
would eectively and eciently decouple the layers, allowing
for expanding interlayer distance.[13] These features coincided
with the XRD characteristics of the superlattice structure, indi-
cating the successful preparation of superlattice-type S-WSe2.[14]
Furthermore, the Raman spectrum, where the dominant peak
in the S-WSe2 sample appears blue-shifted in comparison with
pristine WSe2 around 250 cm−1 in Figure S1 (Supporting Infor-
mation),[15] further confirms the interlayer-expanded S-WSe2.
The content of SDBS in S-WSe2, obtains by thermogravimetric
analysis (TGA) (Figure S2, Supporting Information), is calcu-
lated to be 1.80%. Meanwhile, nitrogen adsorption/desorption
isotherms are conducted (Figure S3, Supporting Information).
The Brunauer–Emmett–Teller (BET) surface area of the S-WSe2
Scheme 1. Schematic evolution of a) traditional WSe2 and b) superlattice-type S-WSe2 electrode after long-term cycling. c) The proposed mechanism
of superlattice-type structure alleviating the pulverization with high-charge-density Al3+ de-intercalation.
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(16.44 m2 g−1) was higher than the WSe2 sample (12.96 m2 g−1),
and the BET value increased by around 25% after the interlay-
expansion treatment. This improvement was mainly ascribed
to the introduction of considerable SDBS, which would also be
beneficial for an enhanced kinetic process.
Furthermore, X-ray photoelectron spectroscopy (XPS) char-
acterization delivers insights into the surface elemental com-
positions and chemical states of superlattice-type S-WSe2,
showing the presence of W 4f, Se 3d, Na 2p, and S 2p peaks
(Figure 1b–d). Double strong and weak peaks are presented
in the 4f orbital of element W (Figure 1b). The strong peaks
belonged to W4+ of S-WSe2 at 32.68eV (W 4f7/2) and 34.63 eV
(W 4f5/2), while the appearance of the weak peaks was ascribed
to the oxidation of W4+ to W6+ (tungsten oxide), in line with
previous literature.[16] The Se 3d XPS spectrum shows the
major doublet peaks of Se2− at 54.50eV (Se 3d5/2) and 55.30eV
(Se 3d3/2) (Figure 1c). Compared with the pristine WSe2, the
presence of Na (Figure 1d) and S elements (Figure S4, Sup-
porting Information) in S-WSe2 originates from the ecacious
introduction of the negative-charged surfactant SDBS. In the
scanning electron microscopy (SEM) (Figure1e) and transmis-
sion electron microscopy (TEM) (Figure1f) images of the super-
lattice-type S-WSe2, there are sparse ultrathin lamellas, while
the morphology of the pure WSe2 exhibits dense nanoflower
patterns (Figure S5, Supporting Information). These results
implied that SDBS organic chained molecules were uniformly
intercalated into the interlayer of WSe2 and further decreased
interlamellar stacking. TEM-energy dispersive spectroscopy
(TEM-EDS, Figure 1i) and SEM-EDS (Figure S6, Supporting
Information) mapping images of S-WSe2 not only reflect that
the related elements exhibit homogeneous distributions but
also demonstrate that S-doping and Na-doping are derived
from electrochemical inertness SDBS. Both the high-resolution
TEM (HR-TEM) image (Figure 1g) and line intensity profiles
of S-WSe2 (Figure1h) results indicate that S-WSe2 layers alter-
nately stack together with the interlayer spacing profoundly
enlarging to 10.1 Å, which match with the XRD analysis. The
emergence of superlattice-type S-WSe2 and interlayer-expanded
structure would reduce the influence from high-charge-density
Al3+ and facilitate aluminum ions diusion with fast reaction
kinetics.[8d,17] Meanwhile, the traditionally TMDCs-optimized
strategy, that was compounding WSe2 with graphene oxide
(GO) (G-WSe2), was also prepared to explore and compare with
the superlattice-type strategy. The Raman, XRD, and TEM char-
acterizations demonstrate the successful introduction of GO
into the WSe2 matrix (Figure S7, Supporting Information), and
GO is partially reduced in G-WSe2 from the ID/IG values calcu-
lated of the Raman spectra.[4d] Typically, the introduction of GO
would alleviate the agglomeration of TMDCs during discharge–
charge cycles. Moreover, the flexible and curled sheet structure
can eectively lessen the volume expansion, thereby to some
extent maintaining the stability of electrode materials.[18]
To further reveal the eect of the amount of SDBS on the
formation of superlattice-type structure, controlled dosages of
SDBS (0, 0.05, 0.10, 0.20, 0.30g) were introduced to synthesize
S-WSe2, named S-WSe2-0, S-WSe2-0.05, S-WSe2-0.10, S-WSe2-
0.20, S-WSe2-0.30. The introduction of the anionic surfactant
SDBS selectively adsorbs onto the (002) crystalline plane of
Figure 1. Characterization of the superlattice-type S-WSe2. a) XRD patterns of S-WSe2 and pristine WSe2. XPS spectra of b) W 4f, c) Se 3d, and d) Na 2p
in S-WSe2. e) SEM image and f) TEM image. g) HR-TEM image of S-WSe2 with h) profile of the interlayer distance in (g). i) HAADF-STEM image and
corresponding elemental mapping of S-WSe2.
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WSe2, promoting the growth of the (002) crystalline plane
(Figure S8, Supporting Information). Due to the distinction in
the adsorption capability of SDBS on dierent crystal faces, the
growth rates were variable.[19] Notably, the strong low-angle dif-
fraction peaks appeared only under the optimized addition of
SDBS (0.10 g), indicating the formation of a superlattice-type
structure. Therefore, the S-WSe2-0.10 was optimized as repre-
sentative S-WSe2, while the electrochemical performance was
further conducted.
2.2. Electrochemical Performance of Prepared Samples
The electrochemical performance of WSe2 and S-WSe2 in RABs
was investigated via assembled Swagelok cells. The cyclic vol-
tammetry (CV) curves of the S-WSe2 cathode with voltages
ranging from 0.25V to 1.95V under a scan rate of 0.50mV s−1
(Figure 2a). After the formation of solid electrolyte inter-
phase film in the initial cycle,[20] the CV of S-WSe2 exhibited
oxidation and reduction peaks located at around 1.58/1.29
and 1.51/1.20 V, which were attributed to the trivalent Al3+
intercalation/de-intercalation.[21] Moreover, CV tests are car-
ried out at dierent scan rates ranging from 1.0 to 3.0mV s−1
(Figure S9, Supporting Information). As scan rates increased,
the CV curves showed similar anodic peak and cathodic
peak. Figure 2b shows the discharge/charge curves of un-
treated WSe2 and superlattice-like S-WSe2 at 100 mA g−1 at
room temperature. The initial discharge specific capacity of
S-WSe2 (354 mAh g−1) was significantly higher than that of
WSe2 (282 mAh g−1). Moreover, the SDBS shows negligible
specific capacity (around 16 mAh g−1 at 100 mA g−1) in this
system (Figure S10, Supporting Information). The optimized
S-WSe2 with intrinsic negative attraction of SDBS eectively
tuned the interlayer spacing of WSe2 with released crystal
strain from high-charge-density Al3+, and significantly accel-
erated the Al3+ diusion kinetic with enhanced capacity. Alu-
minum ion diusion coecients (D) of WSe2 and S-WSe2
were conducted by the galvanostatic intermittent titration
technique (GITT) test. Compared with the D (10−16.4 cm2 s−1)
of the WSe2 sample, the S-WSe2 exhibits an order of magni-
tude improvement (10−13.7 cm2 s−1) with enhanced diusion
kinetic (Figure 2c). The enhanced kinetics process is further
verified via rate capability (Figure 2d). The superlattice-type
S-WSe2 electrode exhibited high capacities of 354, 333, 320,
253, and 165 mAh g−1 at current densities of 0.10, 0.20, 0.50,
1.0, and 2.0 A g−1, respectively. To the best of our knowledge,
Figure 2. Electrochemical performance of S-WSe2 and WSe2. a) CV curves of S-WSe2 from 0.25 to 1.95V at a scan rate of 0.50mV s−1; b) discharge–
charge curves at a current density of 100mA g−1; c) galvanostatic intermittent titration technique (GITT) curves; d) comparison of S-WSe2, WSe2, and
other typically reported cathode materials for RABs; e) electrochemical impedance spectroscopy (EIS) curves with fitted curves; f) long-term cycling
stability of S-WSe2 at 500mA g−1; g) cycle stability of S-WSe2 at a high current density of 2.0 A g−1 and the inset in (g) demonstration of soft-package
RABs lighting LED.
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the rate capability of S-WSe2 was among the highest reported
metal-sulfides, small molecules organic, and graphite materials
in RABs, which was mainly ascribed to the certain attraction
to positively charged Al3+ via SDBS and the extended interlayer
for enhanced diusion kinetic.[9d,10a,22] On the contrary, pristine
WSe2 only delivered capacity of 282, 189, 130, and 94 mAh g−1 at
current densities of 0.10, 0.20, 0.50, and 1.0 A g−1, exhibiting a
much lower rate-performance than that of the superlattice-type
S-WSe2. The improvement of rate-capacity is more pronounced
with increasing current densities (Table S1, Supporting Infor-
mation). The discharge capacity was enhanced by a factor of
around 2.69 (from 94 to 253 mAh g−1) at the current density
of 1.0 A g−1. Electrochemical impedance spectroscopy (EIS) is
conducted, while experimental results are fitted using an equiv-
alent circuit diagram (Figure S11, Supporting Information) to
clarify the kinetic process of the electrode materials (Figure2e,
Table S2, Supporting Information). The lower Rct of S-WSe2
(298.6 Ω) than the pure sample (5313.0 Ω) played a vital role
in enhanced conductivity and electrochemical reaction kinetics,
which was consistent with GITT test results.[23] The reinforced
diusion and reaction kinetics would provide the possibility for
the application of high-performance RABs.
Compared with the drastical capacity decay of WSe2 after
20 cycles at a current density of 100mA g−1 (Figure S12, Supporting
Information), the S-WSe2 retains a high capacity of 175 mAh g−1
after 500 cycles at a current density of 500mA g−1 (Figure2f ).
Although traditionally TMDC-optimized sample, that is G-WSe2,
exhibits a high initial discharge specific capacity (377 mAh g−1)
at 100 mA g−1, the retention rate is only 20% after 300 cycles
(77 mAh g−1) in Figure S13 (Supporting Information). The inher-
ently unstable architecture of G-WSe2 leads to the collapse of
the structure after the long-term cycling (Figure S14, Supporting
Information). Further, based on XRD pattern and TEM analysis,
G-WSe2 electrode exhibited an amorphous structure after cycles.
The unstable structure leads to its inferior electrochemical
stability (Figure S15, Supporting Information). In particular, the
superlattice-type S-WSe2 could provide a stable crystalline struc-
ture. After 200 cycles, the glass fiber separator of S-WSe2 was still
clean. On the contrary, WSe2 electrode exists a large amount of
irreversible shedding (Figure S16, Supporting Information), and
this may be related to the high compatibility between the unstable
electrode and the Lewis-acidic electrolyte.[24] Furthermore, at
a high current density of 2.0 A g−1, the capacity of S-WSe2 still
maintains above 110 mAh g−1 even after 1500 cycles (Figure2g),
which is one of the best cycling stability among the high-perfor-
mance TMDCs cathodes in RABs. The inset of Figure2g shows
that the two assembled fully charged pouch cells could lighten
the light emitting diodes (LEDs) and typical discharge–charge
curves of Al/S-WSe2 pouch cells are collected (Figure S17, Sup-
porting Information). The comparison of reported representative
cathode materials in RABs is listed in Table S3 (Supporting
Information), proving the remarkable cycling stability of S-WSe2
cathode with superlattice-type robust structure.
2.3. Mechanism Investigation of Aluminum-storage in S-WSe2
Considering the substantially improved RABs performance of
S-WSe2, it is of great interest to explore the reaction mechanism
in RABs. Thus, a series of in/ex situ characterizations were con-
ducted toward S-WSe2 electrodes. The in situ XRD measure-
ments of the S-WSe2 cathode are conducted via a costumed in
situ testing device (Figure S18, Supporting Information) during
the first discharge–charge cycles (Figure 3a,b). The obtained
diraction peaks matched with the S-WSe2 structure, while
the weak superlattice peaks presented in the range of 8.0–9.0°.
The characteristic peak of the (002) crystal plane slightly shifted
to a lower 2θ value after discharge and backtracked to the initial
state upon charging. This phenomenon could be ascribed
to de-intercalation of active ions, which reflected the reliable
reversibility of the superlattice-type S-WSe2 electrode. More-
over, a shifted and reinstated peak was similar with previous
reported in other metal-ion batteries,[8c,25] which was mainly
ascribed to the robust superlattice-type structure. Meanwhile,
the structural evolution of S-WSe2 was clearly presented in the
enlarged contour maps. For un-treated WSe2, a similar trend of
reversible shift of (002) crystalline plane during the insertion
and extraction of Al-based active ions is observed (Figure S19,
Supporting Information). While, other characteristic peaks
exhibited a certain amorphization during discharge process
and recovered after charge. Consequently, the superlattice-type
S-WSe2 exhibited more stability structure than the pristine
WSe2 under the reaction with high-charge-density Al3+.
Ex situ XPS spectra of the S-WSe2 electrode were further
performed to demonstrate the changes of W, Se, Al, and Cl ele-
ments. The W 4f XPS spectra of the S-WSe2 electrode at the
pristine, fully discharged, and fully re-charged states are pre-
sented in Figure 3c. The main doublet strong peaks of W4+
(32.68 eV (4f7/2) and 34.63 eV (4f5/2)) became weaker and the
new peaks emerged in low binding energy (the emerging
peaks belonging to W2+ (32.13 eV (4f7/2) and 34.23 eV (4f5/2))
and nearing zero-valence W (31.58 eV (4f7/2) and 33.70 eV
(4f5/2), respectively) as the electrode was fully discharged to
0.25 V. The corresponding peaks shifted to low-valance were
ascribed to the partial reduction of tetravalent W (originate
from S-WSe2) and the insertion of aluminum-based active
ions into the S-WSe2.[6e,26] The similar phenomenon exists
for un-treated WSe2 after fully discharged (Figure S20, Sup-
porting Information). After fully charged, the new doublet
peaks of W 4f spectrum in the low binding energy strikingly
decreased, indicating that the low-valance W was oxidized
back to W4+. Note that, there still existed considerable doublet
peaks after fully charged, possibly originating from residual
discharged production. Meanwhile, the XPS spectra of Se 3d
have negligible variation at all three representative states, fur-
ther indicating that the Se element has limited contribution in
the electrochemical reaction (Figure S21, Supporting Informa-
tion). The intensity of Al 2p XPS spectra increases after fully
discharged and then decreases upon re-charging (Figure 3d),
the Cl element has limited variation (Figure S22, Supporting
Information). Meanwhile, there still exists Al 2p peaks in the
S-WSe2 electrode after in-depth XPS etching (Figure S23, Sup-
porting Information), which further reflects that the presence
of Al homogenously exists in the whole S-WSe2 electrode.
More importantly, a real-time transformation of the S-WSe2
cathode was monitored by in situ Raman spectroscopy. The
dominant peak detected at 243 cm−1 was ascribed to the W-Se
band of S-WSe2. Besides, other peaks at 349, 310, and 432 cm−1
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can be assigned to Al-Cl band of AlCl4−, Al2Cl7−, and Al2Cl7−,
respectively (Figure S24, Supporting Information).[2a] During
the discharge process, peaks around 243 cm−1 (WSe2 signal of
superlattice-type S-WSe2 electrode) are gradually attenuated
(Figure3e,f ). In the meanwhile, signal of Al2Cl7− decomposed
to AlCl4− and Al3+ (a slight decrease in the stretching vibration
of Al2Cl7− group at 310 and 432 cm−1 was accompanied by an
improved intensity of AlCl4− group at 349 cm−1), which indi-
cated that the engendered Al3+ participated in the intercalation
process of S-WSe2 cathode and form Alx(S-WSe2). Correspond-
ingly, HR-TEM with EDS was further collected to confirm the
Al3+ insertion and extraction process in the superlattice-type
S-WSe2 cathode. Compared to the discharged stage (Figure3i),
signals of Al present patchy distribution with feeblish den-
sity after fully charged (Figure 3j). These results indicated
that the residual discharged production of S-WSe2 existed
in the charging process, in consistent with the trend in XPS
spectra. Meanwhile, in the contour maps (Figure3g) and three-
dimensional line graphs (Figure3h) of Raman spectra, it can
be observed that WSe2 signals belonging to the S-WSe2 species
are enhanced (the intensity of Raman peaks located in 243 cm−1
in the initial re-charged state is low but still exits (Figure S25,
Supporting Information)), namely reversible transformations
between trivalent aluminum ions and S-WSe2. Moreover, we
proposed that the Al-ion storage mechanism in S-WSe2 can be
simplified and formulated as follows
xx
x
()
−++↔ −
+−
SW
Se Al 3e Al SWSe
2
3
2
(1)
Here the typical aluminum deposition/striping reactions are
delivered by Equation (1). During discharge stage, trivalent Al
ions were inserted into superlattice-type S-WSe2 and transformed
into Alx(S-WSe2), accompanied by the tetravalent tungsten posi-
tive ions undertaking as to the principal redox centers, which
was reversible through the conversion between S-WSe2 and
Alx(S-WSe2) and similar with previous reports in TMDCs.[6e,26]
Moreover, the elemental analysis of discharged S-WSe2 sample
is performed via inductively coupled plasma optical emission
spectrometry (ICP-OES) analysis (Table S4, Supporting Informa-
tion) and TEM-EDS characterization (Figure S26, Supporting
Information). However, due to the complexity of the Lewis-acidic
system in RABs, it was dicult to obtain an accurate x value.[27]
Further in-depth elaborate of the reaction process of TMDCs in
RABs was crucial to the development and application of multiva-
lent-ion batteries, whereas the de-intercalation of aluminum ion,
as verified via a series of in/ex situ characterization, confirmed
superlattice-type S-WSe2 electrode was a promising cathodes in
RABs. Furthermore, the unique long-term reversibility (stability)
of superlattice-type S-WSe2 was investigated in details in the
following part.
2.4. Structural Evolution and Theoretical Simulations
of Superlattice-Type S-WSe2
The superlattice-type materials were a family of promising
electrodes with optimized stability and capacity, which were
Figure 3. Mechanism characterizations of S-WSe2 in RABs. a) In situ XRD patterns of S-WSe2 sample during the initial discharge–charge cycle and
b) the corresponding contour images. Ex situ XPS spectra of c) W 4f and d) Al 2p for S-WSe2 cathode at the pristine, initial fully discharged (0.25V), and
fully charged (1.95V) stages. In situ Raman spectra of S-WSe2 electrode during e,f) the discharge process and g,h) the charge process. HAADF-STEM
image and corresponding elemental mapping images of S-WSe2 electrode after i) fully discharged to 0.25V and j) fully charged to 1.95V.
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confirmed and applied in other secondary batteries (alkaline-
metal batteries and two-electron ZIBs).[28] Thus, it was highly
desirable to deeply explore the influence of this property on
three-electron-charge Al-ion. To probe the structural evolution
of superlattice-type S-WSe2 and WSe2 cathode during long-term
cycling, ex situ XRD and TEM characterizations were executed.
Figure 4a exhibits the XRD patterns of S-WSe2 and WSe2 elec-
trodes after long-term cycling (200 cycles). Compared with the
amorphous WSe2 and disappeared characteristic peaks, the
cycled S-WSe2 electrode still retained characteristic diraction
peaks, in compliance with the WSe2 phase. Moreover, density
functional theory (DFT) simulations are conducted to investi-
gate the enhanced Al-storage performance of the superlattice-
like S-WSe2 (Figure4b–d). Simultaneously, TEM images show
that the superlattice-like S-WSe2 electrode retains a comparable
crystal morphology (Figure4f) even after 1000 cycles, while the
WSe2 has become an amorphous structure (Figure 4e) after
200 cycles. The decayed structure of WSe2 would be ascribed
to volume expansion caused by the irreversible transformation
between tetravalent W and divalent W during the charging/
discharging process (volume increased by 86.4%).[29] Moreover,
the deformable material of pristine TMDCs, such as WSe2
was insucient to withstand the insertion/extraction of high-
charge-density Al3+. Moreover, TEM-EDS images reveal that the
W, Se, S, Na, Al, and Cl elements of superlattice-type S-WSe2
cathode still exhibit uniform distribution over 1000 cycles
(Figure S27, Supporting Information), which also demonstrates
the robust structure of superlattice-like S-WSe2 electrode.
On the other hand, DFT simulations were further performed
to explore the energy barrier of superlattice-like S-WSe2 and
untreated WSe2. The electronic structure of S-WSe2 via den-
sity of states (DOS) (Figure S28, Supporting Information),
reflects the spin-up energy band of S-WSe2 crosses the Femi
surface. The S-WSe2 had ignorable bandgap, and its metallic
characteristic delivered high electronic conductivity. Compared
to pristine WSe2, the lower diusion energy barrier of Al atom
diusion in the S-WSe2 is presented (Figure4b). As can be seen
from the models (Figure 4c), aluminum atoms are extremely
easily confined between the upper and lower WSe2 layers.
Whereas, the expanded interlayer of S-WSe2 promotes the alu-
minum atoms to be biased to one side (Figure4d), weakening
the binding force on aluminum and making the de-intercalation
of aluminum ions easier than the original WSe2. Furthermore,
the AlSe bond length of superlattice-type S-WSe2 is longer
(2.71 Å) than that of WSe2 (2.60 Å) and the WSe bond length
has negligible change (Table S5, Supporting Information).
These obtained results signified the intercalation of SDBS has a
slight eect on the intrinsic properties of the active layer, yet sig-
nificantly weakened the binding energy of AlSe bond during
high-charge-density Al3+ intercalation process. The simulations
further confirmed the ultrafast Al storage capability and robust
structure of the superlattice-type S-WSe2 electrode.
3. Conclusion
To overcome the inherent weakness in RABs especially struc-
tural deterioration ascribed to intrinsic high-charge-density
Al3+, we proposed a previously unexplored family of superlat-
tice-type S-WSe2 as a model cathode with drastically improved
long-term stability. The newly introduced anionic organic layer
(typically SDBS) in S-WSe2 not only suppressed crystal strain
with enhanced stability and reduced active-materials dissolu-
tion but also expanded interlayer space with improved diu-
sion process and lower energy barrier, which verified via DFT
simulation. Correspondingly, S-WSe2 exhibited one of the
best cycling stability in TMDCs (110 mAh g−1 after 1500 cycles
at a high current density of 2.0 A g−1), impressively enhanced
rate performance (165 mAh g−1 at 2.0 A g−1), and high specific
capacity (354 mAh g−1 at 100mA g−1). Meanwhile, the reaction
Figure 4. Structural evolution and theoretical simulation of superlattice-type S-WSe2 and WSe2. a) XRD patterns of cycled S-WSe2 and WSe2 electrodes
after 200 cycles. b) Energy profiles of Al diusion on WSe2 and S-WSe2. Typical models of Al diusion path in the interlayer of cycled c) WSe2 and d)
S-WSe2. HR-TEM and the inset corresponding TEM images of e) WSe2 and f) S-WSe2 electrode after long-term cycling tests.
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mechanism of superlattice-type S-WSe2 electrode was revealed
in detail via various in/ex situ characterizations. Overall, this
newly superlattice-tuned and organic-intercalated strategy
paves a facile direction to overcome the inherent weakness and
develop high-stability electrodes in RABs.
4. Experimental Section
Materials: Aluminum trichloride (AlCl3, 99.999%) and selenious
acid (H2SeO3, 98%) were obtained from Sigma-Aldrich. 1-ethyl-3-
methylimidazolium chloride (EMICl, 99%) was purchased from
Shanghai Chengjie Chemical Co., Ltd, China. Glass fiber filters (GF/A)
were obtained from Whatman. Aluminum foil (0.25 mm, annealed,
99.99%) was supplied by Alfa Aesar. Sodium tungstate dihydrate
(Na2WO4·2H2O, AR), sodium dodecylbenzene sulfonate (SDBS, AR),
and N,N-Dimethylformamide (DMF, AR) were bought from Sinopharm
Chemical Reagent Co., Ltd, China. Graphene oxide (GO) was obtained
from 3Achem Co., Ltd, China.
Synthesis of WSe2 and G-WSe2: The WSe2 and G-WSe2 were prepared
via the solvothermal synthesis technique. Precisely 1.30g of H2SeO3 and
0.66g of Na2WO4·2H2O were weighed and dissolved in 60 mL of DMF
solution. After sonication and stirring until the mixture was completely
dissolved, then transferred to the polyphenylene reactor, sealed, and
heated at 200 °C for 24h. The obtained product was vacuum filtered and
washed with deionized water and ethanol, and finally dried in a vacuum
oven at 50 °C for 12 h. The G-WSe2 synthesis strategy was similar to
pristine WSe2, besides 10mg GO powders.
Preparation of Superlattice-Type S-WSe2 Nanosheets: The S-WSe2
was synthesized via a reliable bottom-up one-pot solvothermal
approach. Synthesis consists of heating a 5:1 molar ratio of H2SeO3
and Na2WO4·2H2O, and an additional small amount of organic anionic
surfactant SDBS (0.10mg) in a sealed stainless steel reactor at 200 °C
for 48 h to generate the solvothermal product—the S-WSe2 precursor.
The suspension was separated and the final yield of S-WSe2 was stored
in a vacuum drying tank for use.
Characterizations: The morphologies of products were characterized
via SEM (SU8020) and TEM (FEI Talos F200X-G2) characterizations. The
XRD (Bruker, D8 Advance diractometer, Cu Ka, λ= 1.54 Å) patterns of
samples were measured from 5° to 80° (2θ). The nitrogen adsorption-
desorption isotherms were measured via ASAP 2460 and calculated
based on BET analysis. The TGA was performed by a NETZSCH ST
449 F5/F3 Jupiter thermoanalyzer under argon from room temperature to
750 °C with a heating rate of 10 °C min−1. The XPS spectra were acquired
through a Thermo Fisher, ESCALAB 250 Xi, and S-WSe2 samples at fully
discharged and fully charged stages were ion-etched using 2000 eV
Argon ion with an etching rate of ≈0.5 nm s−1 under etching time of
25 s. While, Raman spectra were collected in point scan mode using the
Renishaw instrument with a 532nm laser.
Electrochemistry Measurements: All of the WSe2, G-WSe2, and S-WSe2
cathodes were prepared by making a slurry of active material, Ketjen
black, and sodium carboxymethyl cellulose (CMC) in a weight ratio of
6:3:1. Electrochemical measurements were performed using Swagelok
type cells, in which the WSe2, G-WSe2, and S-WSe2 samples were used
as cathodes, high-purity aluminum served as the anode, and Whatman
glass fiber filter acted as separator and conventional Lewis-acid was used
as the electrolyte (AlCl3/EMICl = 1.3:1 = M/M). Galvanostatic charge and
discharge tests were conducted using a Neware battery test station
with a voltage range from 0.25 to 1.95V (vs Al3+/Al). The galvanostatic
intermittent titration technique (GITT) was conducted with pulses
of 6 µA and interruption time for 1.0 h, respectively. Electrochemical
impedance spectroscopy (EIS) was carried out on a PARSTATMC
workstation under frequencies from 0.01 to 105Hz. The CV curves were
measured in a CHI660e electrochemical workstation.
DFT Simulations: The migration barrier energy of Al in WSe2 and
superlattice-type S-WSe2 were calculated using first-principles DFT
under the framework of projector-augmented wave method with
Vienna Ab-initio Simulation Package code. The generalized gradient
approximation of Perdew–Burke–Ernzerh function was used to describe
the exchange and correlation eects. The kinetic energy cuto for plane-
wave expansion was set at 500 eV. A Monkhorst–Pack scheme with
k-spacing of 2π× 0.030 Å−1 was used for Brillouin zone sampling. The
convergence criterion for total energy and force was set at 10−5 eV and
10−2 eV Å−1, respectively.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This work was financially supported by Beijing Municipal Great Wall
Scholar Training Plan Project (CIT&TCD20190307), Beijing Municipal
Commission of Education (KZ202210005003), National Natural Science
Foundation of China (U1607110 and 51621003), Beijing Natural Science
Foundation (Z210016), Beijing Hundred, Thousand and Ten Thousand
Talent Project (2020016), National Natural Science Foundation of
China (Nos. 52104292, 52130407, and Innovative Research Groups (No.
51621003).
Conflict of Interest
The authors declare no conflict of interest.
Data Availability Statement
The data that support the findings of this study are available from the
corresponding author upon reasonable request.
Keywords
electrode pulverization, long-term stability, rechargeable aluminum
batteries, superlattice-type cathodes, tungsten selenide
Received: October 6, 2022
Published online:
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