Rubber-Derived Sulfur Composite as a High Capacity Anode for Li-ion Battery Using 5 V-Class LiNi_0.5Mn_1.5O₄ Cathode

Abstract

A much higher cell voltage of ca. 2.5 V than that of the typical Li-S battery was successfully achieved by combining the 5 V-class, spinel-type LiNi_0.5Mn_1.5O₄ (LNMO) as a cathode and the rubber-derived sulfur composite as an anode. The cycling performance of the cell was improved by the PVDF coating only the cathode and coating both the cathode and anode, in which the discharge capacity retention increased from ca. 45 % to ca. 60 %. On the other hand, there was no difference in the cycling performance between the cell with the PVDF coating only the anode and the cell without the PVDF coating both the cathode and anode. There was no difference between the cycling performance of the half-cell of the LNMO cathode with the PVDF coating and without the PVDF coating, indicating that the PVDF coating on the cathode side does not prevent degradation of the electrolyte solution on the cathode surface. These results suggest that the PVDF coatings of the cathode surface play an important role as a protective layer in preventing the direct contact and side reaction between the polysulfides and cathode surface, thus leading to improvement of the cycling performance.

1. Introduction

Lithium-ion batteries (LIBs) have been widely used as the most efficient energy storage devices due to their high volumetric and gravimetric energy densities, and applied not only for use in portable electronic devices but also in hybrid electric vehicles (HEVs), electric vehicles (EVs) and stationary energy storage systems in recent years. With the rapid development of these applications, the demands for higher energy density and power density batteries are increasing.

In recent years, lithium-sulfur (Li-S) batteries has received much attention as the promising next-generation battery due to their higher energy density, in which the sulfur as a cathode material has significant advantages of a higher theoretical specific capacity (1672 mAh g⁻¹), natural abundance, inexpensive cost and environmental friendliness than the conventional cathode material for LIBs.^1–4 However, sulfur cathodes still have several challenges for their practical use, because of the electrically insulating nature of the elemental sulfur (5 × 10⁻³⁰ S cm⁻¹ at 20 °C)⁵ and lithium sulfide, and the shuttle phenomenon of the Li-S battery caused by the dissolution of polysulfides into the electrolyte solution, leading to capacity fading during cycling.^6,7

Over the past decades, much effort has been devoted to overcoming these issues in which many kinds of sulfur-carbon composites, such as mesoporous carbon,^8,9 microporous carbon,^9,10 carbon nanotubes,^11,12 and graphene sheets,^13,14 and the sulfur-conductive polymer composites, such as the sulfurized-polyacrylonitrile,^15,16 were developed. Recently, our group developed a rubber-derived sulfur composite material that could be a promising cathode active material for the Li-S or LIBs by the vulcanization process of rubber as a polymer source and a larger amount of sulfur at the higher vulcanization temperature than the mass production process of the rubber. The rubber-derived sulfur composite cathode material has a thienoacene or thienoacene-like structure, which can ensure a good confinement of the sulfur species between and/or within the polymer network and prevent the dissolution of the polysulfides from the matrix during the charge-discharge, thus achieving a stable cycling performance with a high capacity of ca. 400 mAh g⁻¹.¹⁷

There are other obstacles for the practical use of Li-S batteries. The safety hazards associated with the employment of Li metal as an anode hinders its use in Li-S batteries for practical use. The Li metal can easily generate lithium dendrites during the charge-discharge which causes a short circuit of the batteries. Li metal also causes serious side reactions with the electrolyte solution, reducing the efficiency of using metallic lithium, and affecting the cycle life of the battery due to its large volume expansion during charging and discharging. In addition, although the Li-S batteries using sulfur or sulfur composite as the cathode have a high energy density, the cell voltage is much lower (ca. <2 V) than that of the conventional LIBs using the layered lithium transition metal oxide cathode (such as LiCoO₂, LiMn₂O₄, Li(Ni,Co,Mn)O₂, Li(Ni,Co,Al)O₂) and graphite anode (ca. 3.7 V).^1–4

There have been a few attempts to utilize the sulfur-based material as a high capacity anode for the LIBs instead of Li metal. Wu et al. utilized the sulfurized polyacrylonitrile (SPAN) composite as an anode and combined it with LiNi_1/3Co_1/3Mn_1/3O₂ (NCM) as the cathode,¹⁸ and Berhe et al. also developed the cell containing LiMn₂O₄ (LMO) as the cathode and SPAN composite as the anode,¹⁹ in which the discharge average voltage is ca. 1.8 V and ca. 2 V in the discharge curves, respectively. The energy density of these cells is higher than that of the Li₄Ti₅O₁₂ (LTO)-based LIBs, enabling its great competitiveness with conventional LIBs.

In the present study, we attempted to utilize the rubber-derived sulfur composite as a high capacity anode and develop the cell having a much higher voltage than the conventional Li-S cells by combining it with a higher voltage cathode, especially, the 5 V-class, spinel-type LiNi_0.5Mn_1.5O₄ (LNMO) than the 4 V-class cathode material such as NCM and LMO. Moreover, the effects of the PVDF coating of the electrodes on the cycling performance of the cell were investigated.

2. Experimental

2.1 Preparation of the electrodes and cells

For the preparation of the LiMn₂O₄ (LMO), LiNi_1/3Co_1/3Mn_1/3O₂ (NCM) and spinel type LiNi_0.5Mn_1.5O₄ (LNMO) cathodes, a slurry of mass composition, active material (LMO (Mitsui Mining & Smelting Co., Ltd.), NCM (Umicore S.A.), or LNMO (BASF TODA Battery Materials LLC.)) : acetylene black (AB) (Denka Black, Denka Company Limited) : vapor grown carbon fiber (VGCF) (VGCF-H, Showa Denko K.K.) : polyvinylidene fluoride (PVDF) (Kynar HSV 900, Arkema S.A.) = 86 : 4.5 : 4.5 : 5, was prepared, then spread onto carbon coated aluminum foil. The areal capacity of the cathodes was 1.9 mAh cm⁻² (calculated based on 110 mAh g⁻¹ of reversible capacity), 2.2 mAh cm⁻² (calculated based on 155 mAh g⁻¹ of reversible capacity) and 2.0 mAh cm⁻² (calculated based on 135 mAh g⁻¹ of reversible capacity) for the LMO, NCM and LNMO, respectively.

The rubber-derived sulfur composite was prepared by the following procedure in which the higher vulcanization temperature and a larger amount of sulfur were utilized to obtain the sulfur composite than the mass production process of the rubber. A high-cis butadiene rubber (UBEPOL, BR150L, weight average molecular weight: 5.2 × 10⁵, number average molecular weight: 2.1 × 10⁵, cis 1,4 bond content of 98 % by mass, Ube Industries, Ltd.) was used as the diene rubber, colloidal sulfur (purity: ≥99.9 %, Tsurumi Chemical Industry Co., Ltd.) was used as the sulfur, and zinc diethyldithiocarbamate (Nocceler EZ, Ouchi Shinko Chemical Industry Co., Ltd.) was used as the vulcanization accelerator. A rubber compound was obtained by kneading 100 parts by mass of the above high-cis butadiene rubber, 1000 parts by mass of the colloidal sulfur, and 25 parts by mass of the vulcanization accelerator using a kneading device (MIX-LABO, Moriyama Company, Ltd.) in which the excess amount of sulfur was used compared to that of vulcanizing the commercial rubber product. The mixed rubber compound was heated and vulcanized at 450 °C for 2 h under an argon atmosphere. The reaction product was pulverized and heated at 200 °C for 3 h in a vacuum in order to remove the unreacted sulfur, then the rubber-derived sulfur composite active material was obtained. The sulfur content in the obtained rubber-deriver sulfur composite active material was ca. 58 wt%.

For the preparation of the rubber-derived sulfur composite anodes, a slurry of mass composition, rubber-derived sulfur composite : AB : VGCF : polyacrylic acid binder (Aquacharge, Sumitomo Seika Chemicals Co., Ltd.) = 87 : 2 : 8 : 3, was prepared, then spread onto carbon coated aluminum foil. The areal capacity of the anodes was 1.1 mAh cm⁻² (calculated based on 500 mAh g⁻¹ of reversible capacity).

For the PVDF coating on the electrodes, the 2 wt% PVDF solution was obtained by dissolving the PVDF powder (Kynar HSV 900, Arkema) in acetone (FUJIFILM Wako Chemicals). The PVDF solution was spread onto the LNMO cathode and/or rubber-derived sulfur composite anode, then dried on a hotplate at 80 °C using the procedure shown in Fig. 1. Hereafter, the abbreviations PC-C, PC-A, NC-C and NC-A were used, which denote the PVDF-coated cathode, PVDF-coated anode, non-coated cathode, and non-coated anode, respectively. The cell consisting of the PVDF-coated cathode and PVDF-coated anode is denoted as PC-C/PC-A.

Figure 1.

Schematic of the PVDF coating procedure on the electrodes.

The CR2032-type coin cell or laminated-type cell including the half-cells and full-cells were fabricated to evaluate the electrochemical performance of the cells. For the half-cells, Li foil was used as the counter electrode. 1 mol L⁻¹ (1 M) LiPF₆ in EC/DEC (1/1, v/v) or 1 M LiTFSI in sulfolane were used as the electrolyte solutions. A glass filter and polyolefin microporous membrane were used as the separator.

2.2 Characterization of the electrodes

The changes in the surface morphology before and after the PVDF coating on the electrodes were observed using a scanning electron microscope (SEM) (JSM-6390, JEOL Ltd.).

2.3 Electrochemical measurement

The electrochemical performance of the cells was evaluated using a charge-discharge apparatus (BLS series, Keisokuki Center) at 30 °C. For the rubber-derived sulfur anode and LNMO cathode half-cells, the charge-discharge was carried out in the voltage range of 1.0–3.0 V and 3.5–4.8 V vs. Li/Li⁺, respectively. For the full-cells consisting of the rubber-derived sulfur composite anode and LMO cathode, NCM cathode or LNMO cathode, the charge-discharge was carried out in the voltage range of 0.5–3.3 V, 0.75–2.85 V, or 1.5–3.8 V, respectively.

3. Results and Discussion

3.1 Electrochemical performance of the half-cell using the rubber-derived sulfur composite

Figure 2 shows the electrochemical performance of the half-cell using the rubber-derived sulfur composite and Li metal as the counter electrode. The rubber-derived sulfur composite showed the discharge capacity of 830 mAh g⁻¹ and the charge capacity of 600 mAh g⁻¹ in the first cycle, in which the irreversible capacity was ca. 28 %. The discharge capacity and the irreversible capacity gradually decreased, then the charge-discharge capacity became stable and a good cycling stability with the charge-discharge capacity of ca. 450 mAh g⁻¹ after the 6th cycle. Although the rubber-derived sulfur composite has a high charge-discharge capacity, the average discharge voltage of the cell was limited to ca. 1.65 V (Fig. 2b), the same as the conventional Li-S batteries.^1–4 In the present study, we attempted to utilize the rubber-derived sulfur composite as a high capacity anode.

Figure 2.

The electrochemical performance of the half-cell using the rubber-derived sulfur composite and Li metal as the counter electrode. (a) The cycling performance and (b) charge-discharge curves of the cell. The 1 M LiPF₆ in EC/DEC was used as the electrolyte solution. The charge-discharge was conducted at the 0.5 C-rate. The 1 C-rate was defined as 1.5 mA.

3.2 Electrochemical performance of the cell using the 4 V-class LMO and NCM cathode and the rubber-derived sulfur composite anode

We initially developed a cell using the conventional 4 V-class LMO and NCM as the cathode and the rubber-derived sulfur composite as the anode in order to confirm whether the cell using the rubber-derived sulfur composite could be utilized as the anode. Figure 3 shows the electrochemical performance of the cell using the 4 V-class LMO and NCM as the cathode and the rubber-derived sulfur composite as the anode. The cells composed of the LMO and NCM cathode and the rubber-derived sulfur composite anode showed a slightly higher voltage than that of the Li-S cell displaying the discharge average voltage of ca. 1.9 V and ca. 1.6 V, respectively. In addition, these cells showed a stable cycling even when the rubber-derived sulfur composite was used as the anode. These results showed that the rubber-derived sulfur composites can be used as a high-capacity anode.

Figure 3.

The electrochemical performance of the cells composed of the LMO or NCM cathode, and the rubber-derived sulfur composite anode. (a) the cycling performance and (b) charge-discharge curves of the cell using the LMO cathode (coin-type cell), and (c) the cycling performance and (d) charge-discharge curves of the cell using the NCM cathode (670 mAh laminated-type pouch cell). The 1 M LiPF₆ in EC/DEC was used as the electrolyte solution. The 1 C-rate was defined as 2.5 mA and 67 mA for the cell using the LMO cathode and NCM cathode, respectively.

3.3 Electrochemical performance of the cell using the 5 V-class LNMO cathode and the rubber-derived sulfur composite anode

Based on these results, it can be expected that the cell having a stable cycling performance and a much higher cell voltage can be achieved by combining with a 5 V-class LNMO as the cathode. The cell design, charge-discharge capacity and cycling performance of the cell composed of the 5 V-class LNMO as the cathode and rubber-derived sulfur composite as the anode are shown in Fig. 4. When the rubber-derived sulfur composite as the anode is combined with the 5 V-class LNMO as the cathode, the expected discharge voltage is ca. 2.5 V as shown in Fig. 4a. In fact, the cell showed the much higher cell voltage of ca. 2.5 V than the conventional Li-S cells as well as the cell consisting of the LMO and NCM cathode and rubber-derived sulfur composite anode (Fig. 4b), and it was revealed that the rubber-derived sulfur composite can be utilized as a high-capacity anode even in the cell combined with the 5 V-class cathodes. However, the capacity significantly decreased with the increasing cycle number (Fig. 4c).

Figure 4.

The cell design and electrochemical performance of the cell composed of the 5 V-class LNMO as the cathode and rubber-derived sulfur composite as the anode. (a) Cell design (the charge-discharge curves were measured at the current of 0.26 mA and 0.74 mA for the LNMO cathode and rubber-derived sulfur composite anode, respectively), (b) charge-discharge curves and (c) cycling performance. The 1 M LiPF₆ in EC/DEC was used as the electrolyte solution. The charge-discharge was conducted at the 0.5 C-rate. The 1 C-rate was defined as 2.7 mA.

It is known that the capacity fading of the LNMO cathode is caused by the degradation of the electrolyte solution, i.e., the decomposition of the electrolyte solution by oxidation and side reaction, leading to the formation of an insulating layer at the interface between the electrode and electrolyte due to the high working voltage (∼4.7 V vs. Li/Li⁺) and the low oxidation stability of the common carbonate-based electrolytes.^20–23 The capacity fading is also caused by the dissolution of the transition metal (especially, Mn³⁺) and deposition at the anode, thus increasing the impedance of the cell.^24–26 There have been many attempts to develop high voltage electrolyte systems. Especially, the lithium imide salt, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), is a promising Li salt alternative to LiPF₆ due to its lower sensitivity to water and increased electrochemical stability, thus providing a good cycling performance using a high voltage cathode.²⁷ In addition, sulfolane having the sulfone structure is also a good candidate as a solvent due to its higher oxidation potential of over 5 V vs. Li/Li⁺ than the conventional carbonate-based solvent.²⁸ Therefore, the electrolyte solution of LiTFSI in sulfolane shows a higher oxidation potential than that of LiPF₆ in a carbonate-based solvent, which is suitable for the cell using a high voltage LNMO cathode.²⁹

On the other hand, it is known that the high viscosity of the electrolyte solution can suppress the polysulfide shuttle in the Li-S batteries.^30–34 The LiTFSI in the sulfolane solution has a much higher viscosity than the conventional carbonate-based electrolyte solution^35,36 in which the higher viscosity of the electrolyte solution would suppress the polysulfide shuttle and improve the cycling performance of the cell.

Thus, we attempted to utilize LiTFSI and sulfolane as a Li salt and solvent, respectively, instead of 1 M LiPF₆ in EC/DEC as the electrolyte solution, thus expecting the improved cyclability of the cell. Figure 5 shows the cycling performance of the cell consisting of the LNMO as the cathode and rubber-derived sulfur composite as the anode using 1 M LiTFSI in sulfolane. The cycling performance of the cell was improved by using LiTFSI in sulfolane as the electrolyte solution.

Figure 5.

The electrochemical performance of the cell composed of the 5 V-class LNMO as the cathode and rubber-derived sulfur composite as the anode using the electrolyte solution of 1 M LiTFSI in sulfolane. (a) The cycling performance and (b) charge-discharge curves of the cell. The charge-discharge was conducted at the 0.5 C-rate. The 1 C-rate was defined as 2.7 mA.

Many attempts have been made to prevent the decomposition of the electrolyte solution at the electrode/electrolyte interface and improve the cycling performance by surface coating of the cathode active materials using metal oxides, phosphates, fluoride, carbon and polymer, such as SiO₂,³⁷ ZrO₂,³⁸ ZnO,³⁹ TiO₂,⁴⁰ Al₂O₃,⁴¹ V₂O₅,⁴² CoAl₂O₃,⁴³ LiFePO₄,⁴⁴ Li₃AlF₆,⁴⁵ polypyrrole,⁴⁶ and polyacrylonitrile.⁴⁷ Recently, Zheng et al. reported that the PVDF coating of the LNMO cathode material reduced the decomposition of the electrolyte solution and suppressed the growth of the solid electrolyte interface (SEI) layer on the cathode as well as decreasing the Mn dissolution into the electrolyte solution effectively stabilizing the 5 V LNMO cathode and improving the electrochemical performance.⁴⁸

Hence, we attempted the PVDF coating of the surface of the electrodes, thus expecting the further improvement of the cycling performance by preventing the decomposition of the electrolyte solution on the cathode surface. The PVDF coating on the LNMO cathode and/or rubber-derived sulfur composite anode surface were conducted according to the procedure shown in Fig. 1. The changes in the weight of the electrodes after the PVDF coating of the electrodes were very low, which is only 0.2 wt% (0.044 mg cm⁻²) for the LNNMO cathode. Figure 6 shows SEM pictures of the surface and cross-section of the LNMO cathode before and after the PVDF coating. There were no changes in the morphology of the electrodes, which is considered to be due to the infiltration of the PVDF solution into the electrode or the very thin coating layer derived from the low concentration of the PVDF solution (2 wt%).

Figure 6.

SEM pictures of the surface and cross-section of the LNMO cathode (a) before and (b) after the PVDF coating.

Figure 7 shows the cycling performance and charge-discharge curves of the cell consisting of the LNMO cathode and rubber-derived sulfur composite anode with or without the PVDF coating on the electrodes. The cycling performance of the cell was improved by the PVDF coating only the cathode (PC-C/NC-A) and both the cathode and anode (PC-C/PC-A), in which the discharge capacity retention increased from ca. 45 % to ca. 60 % from the 5th cycle to 50th cycle by the PVDF coating. On the other hand, there was no difference in the cycling performance between the cell with the PVDF coating only the anode (NC-C/PC-A) and the cell without the PVDF coating both the cathode and anode (NC-C/NC-A). These results indicated that the PVDF coating on the cathode is effective in improving the cycling performance of the cell.

Figure 7.

The electrochemical performance of the cells composed of the LNMO cathode and rubber-derived sulfur composite anode with or without the PVDF coating on the electrodes. (a) The cycling performance and (b) charge-discharge curves of the cell. The 1 M LiTFSI in sulfolane was used as the electrolyte solution. The charge-discharge was conducted at the 0.5 C-rate. The 1 C-rate was defined as 2.7 mA.

We then investigated the effects of the PVDF coating of the 5 V LNMO cathode on the cycling performance of the cathode half-cell in order to clarify whether or not the PVDF coating plays a role in preventing the degradation of the electrolyte solution on the cathode surface. However, no major difference was observed between the cell with the PVDF coating and without the PVDF coating as shown in Fig. 8, in which the electrolyte solution of 1 M LiPF₆ in EC/DEC was used. This result indicated that the PVDF coating on the cathode does not prevent the degradation of the electrolyte solution on the cathode surface, and suggested the improvement of the cycling performance of the full-cell by the PVDF coating on the cathode surface was not due to prevention of the degradation of the electrolyte solution by the PVDF coating.

Figure 8.

The electrochemical performance of the half-cell composed of the LNMO cathode with or without the PVDF coating and Li metal anode. (a) The cycling performance and (b) charge-discharge curves at the 30th cycle of the cell. The 1 M LiPF₆ in EC/DEC was used as the electrolyte solution. The 1 C-rate was defined as 2.7 mA.

Furthermore, the result that the improvement of the cycling performance of the full-cells was not due to prevention of the degradation of the electrolyte solution on the cathode side suggested that the aforementioned improvement of the cycling performance of full-cells by using LiTFSI in sulfolane as the electrolyte solution is not due to preventing the degradation of the electrolyte solution on the cathode surface, but rather due to preventing the degradation of the rubber-derived sulfur composite anode, i.e., dissolution of polysulfides from the composite into the electrolyte.

Although the dissolution of polysulfide from the anode that actually occurs has not been analyzed and requires further investigation, based on these results, we propose the following hypothesis schematically shown in Fig. 9. The rubber-derived sulfur composite has a stable cycling performance as already mentioned, indicating that the sulfur is strongly confined within the matrix. However, the dissolution of an infinitesimal amount of polysulfide from the anode into the electrolyte solution might occur during the charge-discharge. Due to the concentration gradient, the dissolved polysulfide or lithium polysulfide can easily diffuse from the anode side toward the cathode side through the separator and react at a high oxidizing potential of the cathode surface causing the formation of a resistive layer on the cathode surface leading to the degradation of the cycling performance. Possibly, the concentration of the polysulfide in the electrolyte solution would decrease by consuming the dissolved polysulfide via a side reaction on the cathode side, accelerating the dissolution of polysulfide from the anode via the concentration gradient (Fig. 9a). The process sequence would continuously occur leading to the degradation of the cycling performance of the cell. The degradation of the cycling performance of the cell was higher for the cell using the 5 V-class LNMO cathode than the cell using the conventional cathode of the 4 V-class LMO and NCM (Figs. 3 and 4). Thus, it seems that the side reaction of polysulfide on the cathode side remarkably occurred at a higher potential. Therefore, the PVDF coating on the cathode surface is considered to serve as a protective layer that prevents direct contact and side reactions between the polysulfides and the cathode surface, which may have led to the improvement of the cycling performance of the cell (Fig. 9b).

Figure 9.

Schematic proposed mechanism preventing the cathode degradation and polysulfide dissolution with PVDF coating.

Although the PVDF coating has improved cycling performance of the full-cell, the full-cells still show a significant degradation. It is possible that the PVDF does not completely cover the surface of the cathode, therefore, the reaction between the cathode and polysulfides is not completely inhibited. The details of the reaction mechanism have not yet been revealed and further analyses are required to clarify the specific reaction mechanism. We believe that clarifying the specific reaction mechanism and optimizing the PVDF coating will improve the cycling performance of the full-cell. In addition, the degradation of the full-cell includes the degradation of each of the cathode half-cell and anode half-cell, and we believe that the degradation of the full-cell can be improved by reducing these degradations in the future.

4. Conclusions

We attempted to utilize the rubber-derived sulfur composite as a high capacity anode and developed a cell having a much higher voltage than the conventional Li-S cells by combining it with a high voltage cathode, especially, the 5 V-class, spinel-type LiNi_0.5Mn_1.5O₄ (LNMO). Moreover, the effects of the PVDF coating for the electrodes on the cycling performance of the cell were investigated. A much higher cell voltage of ca. 2.5 V than that of the typical Li-S battery was successfully achieved by combining the 5 V-class LNMO cathode and the rubber-derived sulfur composite as the anode.

The cycling performance of the cell was improved by using the electrolyte solution of LiTFSI in sulforane instead of LiPF₆ in EC/DEC. The improvement of the cycling performance was observed for the cell with the PVDF coating only the cathode (PC-C/NC-A) and both the cathode and anode (PC-C/PC-A), in which the discharge capacity retention increased from ca. 45 % to ca. 60 % from the 5th cycle to 50th cycle by the PVDF coating. On the other hand, there was no difference in the cycling performance between the cell with the PVDF coating only the anode (NC-C/PC-A) and the cell without the PVDF coating both the cathode and anode (NC-C/NC-A). There was no difference between the cycling performance of the half-cell of the 5 V-class LNMO cathode with the PVDF coating and without the PVDF coating, which indicated that the PVDF coating on the cathode side does not prevent the degradation of the electrolyte solution on the cathode surface. Therefore, these results suggested that the PVDF coatings of the cathode surface play an important role as a protective layer in preventing the direct contact and side reaction between the polysulfides and cathode surface, thus leading to the improvement of the cycling performance.

Thus, it was revealed that the rubber-derived sulfur composite can be utilized as a high capacity anode, and we believe that the cell composed of the high voltage cathode and the rubber-derived sulfur composite as the high capacity anode can be a promising candidate for the next-generation batteries.

CRediT Authorship Contribution Statement

Akihiro Yamano: Investigation (Lead), Writing – original draft (Lead)

Tatsuya Kubo: Investigation (Equal), Writing – review & editing (Equal)

Fumiya Chujo: Investigation (Equal)

Naoto Yamashita: Investigation (Equal)

Masanori Morishita: Investigation (Equal)

Masahiro Yanagida: Investigation (Equal), Writing – review & editing (Equal)

Satoshi Furusawa: Investigation (Equal)

Naohiko Kikuchi: Supervision (Lead)

Tetsuo Sakai: Supervision (Lead)

Conflict of Interest

The authors declare no conflict of interest in the manuscript.

Footnotes

A. Yamano, T. Kubo, M. Morishita, M. Yanagida, and T. Sakai: ECSJ Active Members

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