Local structure of amorphous sulfur in carbon–sulfur composites for all-solid-state lithium-sulfur batteries

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https://doi.org/10.1038/s42004-025-01408-2

# Local structure of amorphous sulfur in carbon–sulfur composites for all-solid- state lithium-sulfur batteries

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Hiroshi Yamaguchi 1,2, Yu Ishihara 2, Yamato Haniu 2, Atsushi Sakuda 3, Akitoshi Hayashi 3,
Kentaro Kobayashi 4, Satoshi Hiroi 1,4, Hiroki Yamada 4,5, Jo-chi Tseng 5, Seiya Shimono 5 &
Koji Ohara 1,4,5,6

All-solid-state (ASS) batteries are a promising solution to achieve carbon neutrality. ASS lithium–sulfur

(Li-S) batteries stand out due to their improved safety, achieved by replacing organic solvents, which
are prone to leakage and fire, with solid electrolytes. In addition, these batteries offer the benefits of

higher capacity and the absence of rare metals. However, the low electronic conductivity of sulfur

poses a major challenge for ASS Li-S batteries. To address this challenge, sulfur is often combined

with porous carbon. Despite this standard practice, the local structure of sulfur in these composites

remains unclear. Based on small-angle X-ray scattering and pair distribution function analysis, we
discovered that sulfur in carbon–sulfur composites formed via melt diffusion is amorphous and
primarily comprises S8 ring-shaped structures. The carbon–sulfur composite demonstrated a high
specific capacity of 1625 mAh g −1 (97% of the theoretical specific capacity of sulfur). This remarkable

performance is attributed to the extensive contact area between carbon and sulfur, which results in an

excellent interface formed through melt diffusion. The insights gained into the local structure of sulfur

and the analytical approaches employed enhanced our understanding of electrochemical reactions in

ASS Li-S batteries, thereby aiding in the optimization of material design.

Further development of rechargeable batteries for efficient energy use is
crucial for achieving carbon neutrality. Applications such as electric vehicles, stationary energy storage systems, drones, and high-altitude pseudosatellites require batteries with high safety, large capacity, lightweight construction, and high power output 1 . The advancement of lithium-ion batteries can be credited to the pioneering work of Whittingham et al., who
used TiS2 as an intercalation electrode material 2, Goodenough et al. 3, who
explored a high-capacity layered oxide (LiCoO2) as a cathode material, and
Yoshino et al. 4, who demonstrated the use of carbon as a safe and manageable anode material, leading to the practical implementation of lithiumion batteries in 1991. Currently, the theoretical specific capacity of an anode
based on graphite is 372 mAh g −1 5–7 while that of a cathode based on
LiCoO2 is relatively low (140 mAh g −1 ) 3,8 . Consequently, extensive research
efforts have focused on developing active cathode materials 9–14, aiming for
specific capacities exceeding 300 mAh g −115 .

Lithium–sulfur (Li-S) 16–21, lithium–air 22,23, all-solid-state (ASS) 24–29,
sodium 30, and fluoride 31 batteries have been studied as next-generation
batteries. Silicon-based alloys with a maximum theoretical specific capacity
of 4200 mAh g −1 are considered promising candidates for anodes 32–38 .
Meanwhile, the theoretical capacity of sulfur, which is the cathode material,
is 1672 mAh g −1 16,17 . Therefore, developing positive electrode materials is
crucial for next-generation batteries.

A major challenge in lithium-ion batteriesis the use of organic solvents
as electrolytes. Although these solvents offer excellent lithium-ion
conductivity 39, they pose safety risks such as leakage and fire hazards and
have a limited operating temperature range 40,41 . In Li-S batteries, The performance is hindered by the dissolution of reaction intermediates, such as
Li2Sx (x = 2–8), into the solvent. This has shuttle effects, leading to capacity
loss, cycle degradation, and increased resistance due to irreversible
reactions 18 . ASS Li-S batteries can address these challenges. Solid-state

1Graduate School of Natural Science and Technology, Shimane University, Nishikawatsu-cho, Matsue, Shimane, Japan. 2Advanced Technology Research
Laboratories, Idemitsu Kosan Co., Ltd., Sodegaura, Chiba, Japan. 3 Department of Applied Chemistry, Graduate School of Engineering, Osaka Metropolitan
University, 1-1 Gakuen-cho, Sakai, Osaka, Japan. 4 Faculty of Materials for Energy, Shimane University, Nishikawatsu-cho, Matsue, Shimane, Japan. 5 Diffraction
and Scattering Division, Japan Synchrotron Radiation Research Institute, Kouto, Sayo-cho, Sayo-gun, Hyogo, Japan. 6 RIKEN SPring-8 Center, Kouto, Sayo-cho,

Sayo-gun, Hyogo, Japan. [e-mail: ohara@mat.shimane-u.ac.jp](mailto:ohara@mat.shimane-u.ac.jp)

Fig. 1 | Electrochemical evaluations of ASS LiS cell. a Charge–discharge curves of ASS Li-S cell
(1st cycle, green solid line; 2nd cycle, blue solid line).
b Charge–discharge curves and rate performance of
the ASS Li-S cell samples. c The specific capacites for
sulfur during the discharge process. d Schematic of
ASS Li-S cell.

Table 1 | Samples

Num Sample C
Wt%

S
Wt%

SE
Wt%

Surface area/ Pore size 1/ Pore size 2/
m 2 /g a nm, RSD b nm, RSD b

1 CS_NoHeat 30 70 0 20 0.9, 45% 3.4, 35%

2 CS_Heat 30 70 0 8 0.5, 16% 4.3, 32%

3 CS_heat-SE 15 35 50 - -

4 Carbon (cf.) 100 0 0 2840 0.7, 66% 3.7, 66%

5 Sulfur (cf.) 0 100 0 -

aMeasured by N2 adsorption at −196 °C using the BET method from desorption data.

bMeasured by small-angle X-ray scattering (SAXS) using curve fitting.

electrolytes eliminate liquid leakage concerns and substantially reduce fire
risks. Specifically, sulfide-based solid electrolytes (SEs) exhibit a conductivity comparable to liquid electrolyte systems, a wide operating temperaturerange,andgoodcompatibilitywithsulfur 41–43 .Inaddition,sulfur,as
a cathode material, offers high theoretical capacity. It is lightweight 44,45, free
of rare metals, abundant, and eco-friendly, making it suitable for highperformance and sustainable next-generation batteries 1 .

The major challenges faced by ASS Li-S batteries include the low
electronic conductivity of sulfur (or Li2S) and the sluggish nature of redox
reactions. Researchers have investigated various techniques, such as the
formation of composites with carbon or metals 16,46,47, to address these
challenges. A particularly effective technique involves the impregnation of
sulfur into carbon pores via melt diffusion 48–50 . This technique enhances
batteryperformancebycreatinganoptimalreactionenvironmentforLiand
electrons as well as increasing the contact area. For instance, Ando et al. 51

reported a specific capacity of 1488 mAh g −1 (89% of the theoretical specific
capacityofsulfur)forASSLi-Sbatteriespreparedusingmeltdiffusion-based
composite formation of sulfur and porous carbon. This underscores the
significance of forming a composite of amorphous sulfur and porous carbon. Hakari et al. 52 achieved a specific capacity of 1100 mAh g −1 per Li2S
(95% of the theoretical specific capacity) by dopingLi-S with lithium halides
toenhanceitsreactivityinelectrochemicalreactions.Theyalsomaintaineda
specific capacity of 980 mAh g −1 (after 2000 cycles at 2 C), surpassing the
performance of both conventional liquid-state and ASS Li-S batteries in
terms of specific capacity and cycle life. Understanding the factors contributing to high-performance batteries and analyzing the structural changes before and after composite formation and charge–discharge cycles is
essential for advancing the development of materials suitable for real-world
applications.

The analysis of sulfur reactions in electrode materials poses a substantialchallengeinliquid-stateandASSsystems.Whensulfuriscrystalline,
it can be effectively evaluated using techniques such as in situ X-ray diffraction (XRD) 46,53 . However, the structure becomes unknown when sulfur
becomes amorphous due to composite formation 51,54 or when the reaction
intermediate Li2Sx is amorphous. Consequently, spectroscopic approaches
have been actively employed. For example, in situ Raman spectroscopy 55–57,
X-ray absorption spectroscopy 55,58, and X-ray photoelectron spectroscopy 59

have been used to estimate the transformation from S8 to Li2S. In addition,
the local structure of amorphous sulfur can vary depending on the carbon
material. For instance, sulfur can exist as S2 in nanopores 54 or Sn chains can
be observed by transmission electron microscopy in carbon nanotubes 60 .
More direct methods for determining the structure of amorphous sulfur are
required. In this study, we elucidated the local structure of sulfur in carbon
pores using pair distribution function (PDF) analysis, which is suitable for
both crystalline and amorphous phases.

Results and discussion
Charge–discharge results of ASS Li-S cell
Figure 1ashowsthe firstandsecondcharge–dischargecurvesoftheASSLi-S
cell samples. The specific capacity for sulfur was 1625 and 1658 mAh g −1

during the discharge process of the first and second cycles, respectively.
These values validate the theoretical specific capacity and replicate the
findings of a previous study 51 . This remarkable performance is attributed to
the extensive contact area created between the sulfur-based SE, sulfur, and
carbon with a large specific surface area (Table 1), as well as the effective
formation of lithium-ion and electron transport pathways using a sulfurbased SE with excellent processability. The specific capacity for cathode of
the ASS Li-S cell was 570 mAh g −1 .

Fig. 2 | SEM image and EDX mappings of
CS_Heat. a ×1000, b ×5000, c C mapping, d S
mapping.

TherateperformanceisshowninFig. 1b,c.TheASSLi-Scellshowsthe
capacityof1649,1610,1262,707,430,228,and 119 mAh g −1 at0.05,0.1,0.2,
0.33, 0.5, 1, and 2 C, respectively. For 10th cycle, the capacity was
1226 mAh g −1 at 0.1 C. The observed decrease in capacity is attributed to
charge transfer and diffusion resistance. Further improvements in rate
characteristics are anticipated through the enhancement of the electronic
conductivity of the cathode and the lithium-ion conductivity.

Sulfur impregnated
SEM-EDS was conducted to examine the dispersion of sulfur in the
carbon–sulfur composite. The SEM-EDS result of CS_Heat was shown in
Fig. 2.ThedistributionofC(Fig. 2c)andS(Fig. 2d)isconsistent,confirming
that S is not localized.

The BET-specific surface area was evaluated to assess the detailed state
of carbon pores in ASS Li-S cells, which achieved a specific capacity per
weight of sulfur close to the theoretical specific capacity. The specific surface
area of Carbon (cf.) alone was 2840 m 2 /g, while CS_NoHeat and CS_Heat
decreased to 20 and 8 m 2 /g, respectively, irrespective of the implementation
of melt diffusion (Table 1). This decrease is attributed to sulfur adhering to
the surface of carbon particles and obstructing the pore entrances, raising
concerns about the accuracy of BET-specific surface area measurements for
capturing the pore situation inside carbon materials.

SAXS measurements were performed to nondestructively evaluate the
internal pore state of carbon particles. The results are shown in Fig. 3. Based
on wide-angle X-ray scattering (WAXS), scattering below and above
5.0 × 10 –2 Å –1 primarily originated from particle scattering and pores,
respectively 61 . CS_Heat, subjected to melt diffusion, exhibited a reduction in
the shoulder between 5.0 × 10 –2 and 0.5 × 10 –1 Å –1, indicating sulfur infiltration into pores.Notably, differentiatingbetween nanopore scattering and
WAXS was challenging. However, the scattering intensity ratio (the proportionofscatteringintensityotherthandummyscattering)fromporeswas
74.3%, 31.7%, and 4.2% for Carbon (cf.), CS_NoHeat, and CS_Heat,
respectively (Fig. S1, Table S1). The primary factors affecting carbon and
CS_NoHeat were a decrease in the contribution from carbon pores due to
sulfur content and changes in the pore quantity and shape due to tumbling
mill processing. The significant difference between CS_NoHeat and
CS_Heat was the marked decrease in scattering intensity due to sulfur
infiltrating the carbon pores via melt diffusion, resulting in a smallerdensity
difference. The 4.2% scattering intensity for CS_Heat indicates remaining
pores, attributable to the density difference between the carbon and sulfur

Fig. 3 | SAXS curves. Dotted line, carbon; dashed line, CS_NoHeat; and yellow solid
line, CS_Heat.

materials. The quantitative analysis can be enhanced by refining the analysis model.

Regarding the carbon pore state of carbon–sulfur composites, BET
evaluation is challenging because sulfur attaches to the carbon material
surface and conventional morphology observation was limited to local
observations 47 . However, SAXS enabled the quantification of sulfur infiltration into carbon pores, offering a novel method.

Local structure of sulfur in carbon pores
Based on the results of 3–2, sulfur exists within the carbon pores. XRD
measurements were conducted to confirm the sulfur structure (Fig. 4).
CS_Heat was verified to be amorphous because no crystalline Bragg peaks
were observed.This findingisconsistent withthoseof previousstudies 49,51,56 .

To investigate the thermal behavior, thermogravimetric–differential
thermal analysis (TG-DTA) was performed on Sulfur (cf.) and CS_Heat
(Fig. 5). The phase transition peaks of sulfur (109 °C, 122 °C, 183 °C) 62 were
not observed in CS_Heat (Fig. 5a). This indicates that sulfur exists in an
amorphous state within the carbon pores or is adsorbed on the surface of
carbon particles (consistent with XRD patterns in Fig. 4), and the structure
remains intact until the onset of vaporization at ~200 °C (Fig. 5b). The

Fig. 4 | XRD patterns. Blue solid line, sulfur (cf.); purple solid line, CS_Heat.

completiontemperatureofsulfurvaporization,asindicatedbytheTG-DTA
curve, increased from ~320 °C in Sulfur (cf.) to 460 °C in CS_Heat (Fig. 5b).
This finding corroborates a previous study 51 and signifies the influence of
sulfur adsorption on the carbon walls in the samples. In addition, the C:S
ratio calculated from the weight loss ratio was ~29:71, close to the
initial ratio.

Based on the findings, we confirmedthat sulfur infiltratescarbon pores
and remains in an amorphous phase through melt diffusion.

The chemical state of Sulfur in CS_Heat was confirmed by XPS.
Figure 6 presentsthe normalized S 2p peaks whichsplit to S 2p3/2 (164.1 eV)
and S 2p1/2 (165.3 eV) dual peaks with an area ratio ~2:1 causing by spinorbit splitting 55 . The lone dual peaks at high binding energies (169 eV) are
attributed to the sulfonate 63 . Compared to Sulfur(cf.), CS_Heat exhibited
enhanced intensity for the S 2p1/2 and sulfonate peaks. This enhancement is
attributedtovariationsintheconformationofsulfurorinteractionswiththe
carbon surface.

Figure 7 shows the PDF patterns of Sulfur (cf.), CS_Heat, and Carbon
(cf.). Sulfur (cf.) exhibited peaks at 2.1, 3.4, and 4.5 Å, indicating intramolecular correlations stemming from the S8 ring-shaped molecules 64 . Peaks
were also observed at 4.0, 5.5, 7.2, and 8.4 Å, representing intermolecular
correlations derived from the crystalline structures. Meanwhile, CS_Heat
exhibited peaks at 2.1, 3.4, and 4.5 Å, similar to those of Sulfur (cf), indicating the presence of S8 ring-shaped molecular structures. However, no
distinct correlation peaks were noted beyond 5.0 Å, implying that the
molecular size isunder5.0 Å.This observationisconsistent with the overlap
of thepeaksat2.1,3.4,and 4.5 Åwiththoseof Sulfur(cf.).Thepresenceof S8
was further confirmed through thermal decomposition GC–MS, which
detected a peak corresponding to S8 (Fig. S2).

Besides, CS_Heat exhibitedpeaks at 1.4, 2.5, and 2.8 Å, identified as inplane correlations of graphene, and a peak at 3.8 Å, recognized as interplane correlations of graphene. These findings were based on Carbon (cf.)
measurements and corroborated by previous studies 65 . The absence of
graphite correlation peaks beyond 4.0 Å is attributable to the lower

Fig. 5 | Thermal behaviors. a DTA. b TG: light blue solid line, Sulfur (cf.); Black solid
line, CS_Heat.

Fig. 6 | Chemical state of sulfur. XPS spectra of S 2p: Light blue solid line, Sulfur
(cf.); Black solid line, CS_Heat. PDF analysis was conducted to comprehensively
investigate the local structure of sulfur within the carbon pores.

scattering ability of carbon than sulfur and the challenge of detecting longrange correlation peaks due to the amorphous nature of carbon.

To explore possibilitiesbeyond the proposed S8 ring-shaped molecules
in Sulfur (cf.), theoretical calculations were performed by applying the
Gaussian method to the S8 ring-shaped model, linear model, and linear
model with intermolecular correlations. A comparison between the PDFs
and the experimental PDF data (Fig. 7: yellow solid line) as total correlation
functions, T(r) = G(r) + 4 πrρ0 where ρ0 is the number density, is presented
in Fig. 8. The results for the S8 monomolecular structure (ring model 1)

agreed with the experimental data (SC_Heat). The open-ring model 1 and 2
exhibited peaks at 6.2 and 5.7 Å, respectively, and did not match the
experimental data. In addition, a crown-shaped S8 ring model (ring moel 2)
showed a peak at 4.8 Å, which did not match the experimental data. Given
theheattreatment,thisindicatesthatthesulfurinthecarbonporeshasanS8
ring-shaped structure (Fig. 9). The temperature for melt diffusion is 300 °C,
a temperature at which sulfur can become a rubber-like linear form.
Interactions with the carbon walls likely maintain the presence of the S8
ring-shaped structure. Although the S8 ring-shaped structure was the predominant average molecular structure in this study, the pore size and the
type of carbon may result in different molecular structures 58 .

Conclusions
We fabricated an ASS Li-S cell using a carbon–sulfur composite obtained via
melt diffusion. We confirmed that the specific capacity per sulfur weight is
close to the theoretical specific capacity. The presence of sulfur in carbon
pores in the carbon–sulfur composite (CS_Heat) was quantitatively
demonstrated by SAXS, supporting the concept of melt diffusion. SAXS
provides an alternative or complementary evaluation to techniques such as
BET and local evaluations for particles with blocked entrances, contributing
tomaterialdesignoptimizationbyconfirmingthematerialquality.Thesulfur
in the carbon pores was directly evaluated as amorphous S8 through PDF
analysis and thermal decomposition GC–MS. This provides fundamental
and crucial structural information for theoretical calculations and serves as
primarydataforunderstandingthestructureofamorphoussulfurindifferent

Fig. 7 | Differences in local structure. Comparison between the PDFs: upper dashed
line, Carbon (cf.); yellow solid line, carbon–sulfur composites (CS_heat); lower
detted line, Sulfur (cf.).

compositiontechniques(suchassolventimpregnation)andcarbonmaterials
with varying properties (such as carbon nanotubes and highly amorphous
carbon materials). Further, this method has the potential for application
development, such as controlling the pore size by varying the sulfur content
and evaluating the resulting structure as well as assessing intermediate
structures of amorphous sulfur during charge–discharge processes.

This study makes industrial and academical substantial contributions
by accelerating the development and societal implementation of highcapacityandrare-metal-freenext-generationASSLi-Sbatteries.Inaddition,
it directly and fundamentally elucidated the local structure.

Methods
Composite electrode preparation
The raw materials used were sulfur (S; FUJIFILM Wako Pure Chemical
Corporation, 98.0%), porous carbon (MSC-30; Kansai Coke and Chemicals
Co.,Ltd.),andaLi3PS4-basedsulfideSE(IdemitsuKosanCo.,Ltd.).MSC-30/S
mixtures were prepared with a 3:7 weight ratio using a tumbling mill
(CS_NoHeat). The estimated sulfur pore occupancy, based on the pore
volume of the carbon material (1.58 ml/g) and the density of elemental sulfur
(2.07 g/cm 3 ), was 71.3%. This mixture was placed in a sealed stainless-steel
container and heated at 150 °C for 6 h, followed by heating at ~300 °C for 3 h
(CS_Heat). CS_Heat was then mixed with SE in a 1:1 weight ratio and 0.9 g of
the mixture processed using a ZrO2 pot (45 mL in volume) and 30 g of ZrO2
balls (10 mm in diameter) with a planetary ball mill apparatus (Pulverisette 7,
Fritsch) at 370 rpm for 20 h (CS_Heat-SE). All samples were prepared in an
argon-filled glovebox. The prepared samples are listed in Table 1.

Cell assembly and electrochemical testing
CS_Heat-SE (5 mg) was loaded into a cylindrical mold made of Macor with
a 10 mm diameter. Next, 100 mg sulfide-based SE (Idemitsu Kosan Co.,
Ltd.) was added and compressed to form the SE layer. Indium foil (thickness: 0.3 mm, diameter: 9.5 mm) and lithium foil (thickness: 0.2 mm, diameter: 9.5 mm) were subsequently added and compressed to form a threelayer structure comprising the cathode, SE layer, and anode. The three-layer
pellet was then sandwiched between two stainless-steel disks as a current
collector. Finally, an ASS Li-S cell (Fig. 1d) was obtained by cold-pressing.

Charge–discharge tests of the prepared ASS Li-S cells were conducted
using a potentiostat and galvanostat (TOSCAT) from the Toyo System. The
test voltage range was 0.8–2.2 V (vs. Li-In). Discharging was performed
using the constant current (CC) method, whereas charging was performed
using the constant current constant voltage (CCCV) method. The first and
secondcycleswerechargedanddischargedat0.146 mA/cm 2 (0.05 C)forthe
CC mode under room temperature (25 °C) and the cut off current for CV
mode was set to 0.059 mA/cm 2 (0.02 C). For cycles 3 to 10, charging was
performed at 0.1 C while discharging was conducted at varying rates. The
capacity was calculated from the weight of sulfur.

Fig. 8 | S8 model structures calculated using the Gaussian method and their total correlation functions, T(r). a comparison of T(r) among these models and experimental
data, b S8 ring model 1, c S8 ring model 2, d S8 open-ring model 1, and e S8 open-ring model 2.

Fig. 9 | Image of carbon–sulfur composites. Sulfur forms the ring structure of S8,
which is indicated in yellow atoms, within the gray-shaded carbon pores.

Characterization
Scanning electron microscopy (SEM) was performed using a field-emission
scanning electron microscope (SU8220, HITACHI) equipped with an
energy-dispersive X-ray spectroscopy system (X Flash5060FQ, Burker).

Specific surface area was determined using Autosorb-3 (Quantachrome), which employs the Brunauer–Emmett–Teller (BET) multipoint
method based on nitrogen adsorption.

NANOPIX (Rigaku) was employed for small-angle X-ray scattering
(SAXS)measurements.CuKα radiation(wavelengthapproximately1.54 Å)
with a 40 kV voltage and 30 mA current served as the X-ray source. A
2-pinhole optical system was chosen for the incident beam. The camera
length was approximately 598 mm, and the calibration was executed using
the 1.513° peak of silver behenate. A HyPix-6000 2D semiconductor
detector was used to perform a 12-frame measurement (5 min per frame,
totaling 60 min) with a direct beam measurement of 10 s per frame (totaling
2 min).A1/100attenuatorwasemployedduringdirectbeammeasurement.
The sampleswere measured by sandwiching the powders betweenmending
tapes. The 1D spectrum of SAXS was analyzed using SmartLab Studio II
MRSAXS (Rigaku), and the scattering from the particle origin was fitted,
assuming dummy scattering with a 300 nm diameter and a 40% normalized
dispersion.

TG-DTAwasperformedusingSTA7200RV(HitachiHigh-Tech).The
mass was measured using a precise balance with ~10 mg samples placed in
an open aluminum pan with a 5 mm height. The temperature was increased
from 25 °C to 500 °C at a rate of 20 °C/min under N2 flow at 200 ml/min.

Synchrotron-based total X-ray scattering measurements with PDF
analysis were performed using the BL04B2 beamline in SPring-8, Japan,
with an incident X-ray energy of 61.4 keV 66 . The samples were hermetically
sealed in a 2.0 mm Φ borosilicate glass capillary of 0.01 mm wall thickness
within a glovebox under an argon atmosphere with a controlled dew point.
The data were collected using Ge and CdTe hybrid detectors. The reduced
PDF G(r) was obtained via the conventional Fourier transform of the
Faber–Ziman structure factor S(Q) extracted from the collected data 67 .

Structural optimization calculations were performed using the Gaussian method. The density functional theory calculations employed the
B3LYP functional and cc-pVDZ basis set.

For the thermal decomposition gas chromatography–mass spectrometry (GC–MS) measurements, an EGA/Py-3030D thermal decomposition apparatus (Frontier Laboratories) and an 8890 GC/5977B MSD
(Agilent Technologies) were used. The sample amount ranged from 130 to
170 μgwithtemperatureincreasefrom40 °Cto600 °Catarateof20 °C/min
under a helium gas flow rate of 11 ml/min. The column used was an Ultra
ALLOY with an inert deactivated tube (0.25 × 0.47 mm 2 ). The weight ratio
was 10:1, oven temperature of GC–MS was set to 300 °C, and ion source
temperature was set to 300 °C. The m/z range extended up to 300.

X-ray photoelectron spectroscopy (XPS, VersaProbeII, ULVAC-PHI)
using monochromatic Al Kα radiation (100 W) at room temperature.
Charge neutralization was required to minimize sample charging.

Data availability
The datasets generated and/or analyzed during the current study are
available from the corresponding author on reasonable request.

Received: 12 July 2024; Accepted: 6 January 2025;

References
1. Fan, E. et al. Sustainable recycling technology for Li-ion batteries and
beyond: challenges and future prospects. Chem. Rev. 120,
7020–7063 (2020).
2. Whittingham, M. S. Electrical energy storage and intercalation
chemistry. Science 192, 1126–1127 (1976).
3. Mizushima, K., Jones, P. C., Wiseman, P. J. & Goodenough, J. B.
LixCoO2 (01): a new cathode material for batteries of high energy
density. Mater. Res. Bull. 15, 783–789 (1980).
4. Yoshino, A., Sanechika, A. & Nakajima, T. Secondary battery. U.S.
Patent 4668595 (1987).
5. Zaghib, K., Nadeau, G. & Kinoshita, K. Effect of graphite particle size on
irreversible capacity loss. J. Electrochem. Soc. 147, 2110–2115 (2000).
6. Herold, A. Insertion compounds of graphite with bromine and the
alkali metals. Bull. Soc. Chim. Fr. 187, 999–1012 (1955).
7. Armand, M. & Touzain, P. Graphite intercalation compounds as
cathode materials. Mater. Sci. Eng. 31, 319–329 (1977).
8. Okubo, M. et al. Nanosize effect on high-rate Li-ion intercalation in
LiCoO2 electrode. J. Am. Chem. Soc. 129, 7444–7452 (2007).
9. Xu, D. et al. The progress and prospect of tunable organic molecules
for organic lithium-ion batteries. ACS Nano 15, 47–80 (2021).
10. Deng, Z. et al. Recent progress on advanced imaging techniques for
lithium-ion batteries. Adv. Energy Mater. 11, 2000806 (2021).
11. Dahn, J., Fuller, E., Obrovac, M. & Vonsacken, U. Thermal stability of
LixCoO2, LixNiO2and λ-MnO2 and consequences for the safety of Liion cells. Solid State Ion. 69, 265–270 (1994).
12. Yabuuchi, N. & Ohzuku, T. Novel lithium insertion material of
LiCo1/3Ni1/3Mn1/3O2 for advanced lithium-ion batteries. J. Power
Sources 119-121, 171–174 (2003).
13. Tarascon, J. M. et al. Synthesis conditions and oxygen stoichiometry
effects on Li insertion into the spinel LiMn2O4. J. Electrochem. Soc.
141, 1421–1431 (1994).
14. Padhi, A. K., Nanjundaswamy, K. S. & Goodenough, J. B. Phosphoolivines as positive-electrode materials for rechargeable lithium
batteries. J. Electrochem. Soc. 144, 1188–1194 (1997).
15. Yabuuchi, N. et al. Origin of stabilization and destabilization in solidstate redox reaction of oxide ions for lithium-ion batteries. Nat.
Commun. 7, 13814 (2016).
16. Zhou, L. et al. Sulfur reduction reaction in lithium–sulfur batteries:
mechanisms, catalysts, and characterization. Adv. Energy Mater. 12,
2270183 (2022).
17. Manthiram, A., Chung, S.-H. & Zu, C. Lithium-sulfur batteries:
progress and prospects. Adv. Mater. 27, 1980–2006 (2015).
18. Wang, T. et al. Strategies toward high-loading lithium–sulfur batteries.
ACS Energy Lett. 8, 116–150 (2023).
19. Shuang, X. et al. A separator with double coatings of Li4Ti5O12 and
conductive carbon for Li-S Battery of good electrochemical
performance. Adv. Sci. 10, 2301386 (2023).
20. Jinlei, Q. et al. Engineering cooperative catalysis in Li–S batteries.
Adv. Energy Mater. 13, 2300611 (2023).
21. Borui, L. et al. Balancing polysulfide containment and energy loss in
lithium–sulfur batteries. Energy Environ. Sci. 17, 1073 (2024).
22. Gao, Z. et al. Recent progress in developing a LiOH-based reversible
nonaqueous lithium–air battery. Adv. Mater. 35, e2201384 (2023).

23. Pan, K. et al. A leap by the rise of solid-state electrolytes for Li-air
batteries. Green. Energy Environ. 8, 939–944 (2023).
24. Murayama, M., Sonoyama, N., Yamada, A. & Kanno, R. Material
designof new lithium ionicconductor, thio-LISICON, in the Li2S−P2S5
system. Solid State Ion. 170, 173–180 (2004).
25. Seino, Y., Ota, T., Takada, K., Hayashi, A. & Tatsumisago, M. A
sulphide lithium super ion conductor is superior to liquid ion
conductors for use in rechargeable batteries. Energy Environ. Sci. 7,
627–631 (2014).
26. Kamaya, N. et al. A lithium superionic conductor. Nat. Mater. 10,
682–686 (2011).
27. Yamaguchi, H., Kobayashi, K., Hiroi, S., Utsuno, F. & Ohara, K.
Structural analysis and ionic conduction mechanism of sulfide-based
solid electrolytes doped with. Br. Sci. Rep. 13, 16063 (2023).
28. Masuda, N., Kobayashi, K., Utsuno, F., Uchikoshi, T. & Kuwata, N. Effects
of halogen and sulfur mixing on lithium-ion conductivity in Li7−x−y(PS4)
(S2–x–yClxBry) argyrodite and the mechanism for enhanced lithium
conduction. J. Phys. Chem. C. 126, 14067–14074 (2022).
29. Li, Y. et al. A lithium superionic conductor for millimeter-thick battery
electrode. Science 381, 50–53 (2023).
30. Guo, D., Wang, J., Lai, T., Henkelman, G. & Manthiram, A. Electrolytes
with solvating inner sheath engineering for practical Na–S batteries.
Adv. Mater. 35, e2300841 (2023).
31. Inoo, A., Inamoto, J. & Matsuo, Y. Electrochemical introduction/
extraction of fluoride ions into/from graphene-like graphitefor positive
electrode materials of fluoride-ion shuttle batteries. ACS Appl. Mater.
Interfaces 14, 56678–56684 (2022).
32. Jin, Y., Zhu, B., Lu, Z., Liu, N. & Zhu, J. Challenges and recent progress
in the development of si anodes for lithium-ion battery. Adv. Energy
Mater. 7, 1700715 (2017).
33. Winter,M.&Besenhard,J.O.Electrochemicallithiationoftinandtin-based
intermetallics and composites. Electrochim. Acta 45, 31–50 (1999).
34. Cabana, J., Monconduit, L., Larcher, D. & Palacín, M. R. Beyond
intercalation-basedLi-ion batteries: thestate of the art and challenges
of electrode materials reacting through conversion reactions. Adv.
Mater. 22, E170–E192 (2010).
35. Kasavajjula, U., Wang, C. & Appleby, A. J. Nano- and bulk-siliconbased insertion anodes for lithium-ion secondary cells. J. Power
Sources 163, 1003–1039 (2007).
36. Chan, C. K. et al. High-performance lithium battery anodes using
silicon nanowires. Nat. Nanotechnol. 3, 31–35 (2008).
37. Hochgatterer, N. S. et al. Silicon/graphite composite electrodes for
high-capacity anodes: influence of binder chemistry on cycling
stability. Electrochem. Solid State Lett. 11, A76 (2008).
38. Liu, G. et al. Polymers with tailored electronic structure for high
capacitylithium batteryelectrodes. Adv. Mater. 23, 4679–4683(2011).
39. Li, M., Wang, C., Chen, Z., Xu, K. & Lu, J. New concepts in electrolytes.
Chem. Rev. 120, 6783–6819 (2020).
40. Chen, S. et al. Sulfide solid electrolytes for all-solid-state lithium
batteries: Structure, conductivity, stability and application. Energy
Storage Mater. 14, 58–74 (2018).
41. Wang, D. et al. Realizing high-capacity all-solid-state lithium-sulfur
batteries using a low-density inorganic solid-state electrolyte. Nat.
Commun. 14, 1895 (2023).
42. Zhu, X., Wang, L., Bai, Z., Lu, J. & Wu, T. Sulfide-based all-solid-state
lithium–sulfur batteries: challenges and perspectives. Nano Micro
Lett. 15, 75 (2023).
43. Bhardwaj, R. K. & Zitoun, D. Recent progress in solid electrolytes for
all-solid-state metal(Li/Na)–sulfur batteries. Batteries 9, 110 (2023).
44. Wang, C., Kim, J. T., Wang, C. & Sun, X. Progress and prospects of
inorganic solid-state electrolyte-based all-solid-state pouch cells.
Adv. Mater. 35, e2209074 (2023).
45. Bandyopadhyay, S. & Nandan, B. A review on design of cathode,
anode and solid electrolyte for true all-solid-state lithium sulfur
batteries. Mater. Today Energy 31, 101201 (2023).

46. Wang, B. et al. Niobium diboride nanoparticles accelerating polysulfide
conversion and directing Li2S nucleation enabled high areal capacity
lithium-sulfur batteries. ACS Nano 16, 4947–4960 (2022).
47. Magdalena, F. et al. The role of nanoporous carbon materials for
thiophosphate-based all solid state lithium sulfur battery
performance. Carbon 227, 119252 (2024).
48. Liang, C., Dudley, N. J. & Howe, J. Y. Hierarchically structured sulfur/
carbon nanocomposite material for high-energy lithium battery.
Chem. Mater. 21, 4724–4730 (2009).
49. Guo, J., Xu, Y. & Wang, C. Sulfur-impregnated disordered carbon
nanotubes cathode for lithium-sulfur batteries. Nano Lett. 11,
4288–4294 (2011).
50. Jung, D. S. et al. Hierarchical porous carbon by ultrasonic spray
pyrolysis yields stable cycling in lithium-sulfur battery. Nano Lett. 14,
4418–4425 (2014).
51. Ando, T. et al. High-rate operation of sulfur/mesoporous activated
carbon composite electrode for all-solid-state lithium-sulfur batteries.
J. Ceram. Soc. Jpn. 128, 233–237 (2020).
52. Hakari, T., Hayashi, A. & Tatsumisago, M. Li2S‐based solid solutions
as positive electrodeswith full utilization and superlong cycle life in all‐
solid‐state Li/S batteries. Adv. Sustain. Syst. 1, 1700017 (2017).
53. He, J., Bhargav, A. & Manthiram, A. High-energy-density, longlife lithiumsulfurbatterieswithpracticallynecessaryparametersenabledbylow-cost
Fe-Ni nanoalloy catalysts. ACS Nano 15, 8583–8591 (2021).
54. Xu, Y. et al. Confined sulfur in microporous carbon renders superior
cyclingstabilityinLi/Sbatteries. Adv.Funct.Mater. 25,4312–4320(2015).
55. Luo, L., Li, J., Yaghoobnejad Asl, H. & Manthiram, A. In-situ
assembled VS4 as a polysulfide mediator for high-loading
lithium–sulfur batteries. ACS Energy Lett. 5, 1177–1185 (2020).
56. Ji, X., Lee, K. T. & Nazar, L. F. A highly ordered nanostructured
carbon–sulphur cathode for lithium–sulphur batteries. Nat. Mater. 8,
500–506 (2009).
57. Wu, H. L., Huff, L. A. & Gewirth, A. A. In situ Raman spectroscopy of
sulfur speciation in lithium–sulfur batteries. ACS Appl. Mater.
Interfaces 7, 1709–1719 (2015).
58. Torii, Y. et al. Preventing capacity fading in lithium–sulfur batteries using
sulfurconfinementinmesoporouscarbonand fluorinatedsolvent-based
electrolytes. J. Phys. Chem. C. 127, 15069–15077 (2023).
59. Cao, D. et al. Understanding electrochemical reaction mechanisms of
sulfur in all-solid-state batteries through operando and theoretical
studies. Angew. Chem. Int. Ed. 62, e202302363 (2023).
60. Fujimori, T. et al. Conducting linear chains of sulphur inside carbon
nanotubes. Nat. Commun. 4, 2162 (2013).
61. Saurel, D. et al. A SAXS outlook on disordered carbonaceous
materials for electrochemical energy storage. Energy Storage Mater.
21, 162–173 (2019).
62. Matsumura, S. & Akiba, M. The thermal behaviors of sulfur-containing
curing agents. J. Soc. Rubber Sci. Technol. Jpn. 73, 56–59 (2000).
63. Yunwen, W. et al. On-site chemical pre-lithiation of S cathode at room
temperature on a 3D nano-structured current. J. Power Sources 366,
65–71 (2017).
64. Rettig, S. J. & Trotter, J. Refinement of the structure of orthorhombic
sulfur, α-S8. Acta Crystallogr. C. 43, 2260–2262 (1987).
65. Song, J. et al. Strong lithium polysulfide chemisorption on
electroactive sites of nitrogen-doped carbon composites for highperformance lithium–sulfur battery cathodes. Angew. Chem. Int. Ed.
Engl. 54, 4325–4329 (2015).
66. Ohara, K. et al. Time-resolved pair distribution function analysis of
disordered materials on beamlines BL04B2 and BL08W at SPring-8.
J. Synchrotron Radiat. 25, 1627–1633 (2018).
67. Ohara, K., Onodera, Y., Murakami, M. & Kohara, S. Structure of
disordered materials under ambient to extreme conditions revealed
by synchrotron x-ray diffraction techniques at SPring-8-recent
instrumentation and synergic collaboration with modelling and
topological analyses. J. Phys. Condens. Matter 33, 383001 (2021).

Acknowledgements
WeexpressourgratitudetoHiroyukiHiguchi,MasahiroSekiguchi,YutaFujii,
Yosuke Harada, Hiroya Nakata, Hiroto Ida, and Ikuko Nakamura.
Synchrotron radiation experiments were performed with the approval of the
Japan Synchrotron Radiation Research Institute (JASRI) (Proposal Nos.
2022B1021, 2023A1001, and 2024A1019). This work was conducted as an
SDGs Research Project of Shimane University and was partially supported
by the Green Technologies of Excellence program (Grant Number
JPMJGX23S5) of the Japan Science and Technology Agency (GteX, JST).

Author contributions
All authors contributed to the study conception and design. Material
preparation was performed by H. Yamaguchi, Y.I., and Y.H. Data collection
was performed by H. Yamaguchi, K.K., S.H., H. Yamada, J.T., S.S., and K.O.
Data analysis were performed by H. Yamaguchi, Y.I., Y.H., A.S., A.H., K.K.,
S.H., H. Yamada, J.T., S.S., and K.O. The first draft of the manuscript was
written by H. Yamagcuhi and K.O. and all authors commented on the first
version of the manuscript. All authors read and approved the final
manuscript.

Competing interests
The authors declare no competing interests.

Additional information
Supplementary information The online version contains
supplementary material available at
[https://doi.org/10.1038/s42004-025-01408-2.](https://doi.org/10.1038/s42004-025-01408-2)

Correspondence and requests for materials should be addressed to
Koji Ohara.

Peer review information Communications Chemistry thanks the
anonymous reviewers for their contribution to the peer review of this work. A
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