Solvent-Free Reaction for Unsymmetrical Organodisulfides with High Purity and Application as Cathode-Active Materials
Unsymmetrical disulfides, in which different organic groups are bonded to disulfide bonds, have been synthesized by cross-coupling reactions using thiols as substrates. However, due to the low-binding energy of unsymmetrical disulfides, its disproportionation occurs based on the side reactions with...
| Main Authors: | , , , , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2024-02-01
|
| Series: | Materials |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1996-1944/17/3/699 |
| _version_ | 1797318505942482944 |
|---|---|
| author | Yuta Tsukaguchi Kazuki Shinoda Yusei Noda Yui Hatta Kentaro Tsubouchi Naoko Shokura Fumiya Nakamura Hiromi Kimura-Suda Hirofumi Yoshikawa Takeshi Shimizu Naoki Tanifuji |
| author_facet | Yuta Tsukaguchi Kazuki Shinoda Yusei Noda Yui Hatta Kentaro Tsubouchi Naoko Shokura Fumiya Nakamura Hiromi Kimura-Suda Hirofumi Yoshikawa Takeshi Shimizu Naoki Tanifuji |
| author_sort | Yuta Tsukaguchi |
| collection | DOAJ |
| description | Unsymmetrical disulfides, in which different organic groups are bonded to disulfide bonds, have been synthesized by cross-coupling reactions using thiols as substrates. However, due to the low-binding energy of unsymmetrical disulfides, its disproportionation occurs based on the side reactions with nucleophilic thiols, resulting in the impurity of symmetric disulfides. In this study, we developed a solvent-free synthesis method for unsymmetrical disulfides using thiosulfonates, thiols, and a base. This synthetic method enabled us to obtain highly pure diaryl-substituted unsymmetrical disulfides with particularly low-binding energy without control over the nucleophilicity and elimination properties of the substrate. Furthermore, it was observed that the disproportionation of unsymmetrical disulfides occurred in the solvent. This means that solvent-free condition is one of the factors to obtain unsymmetrical disulfides. As a new application of unsymmetrical disulfides, we applied unsymmetrical disulfides to cathode active materials of lithium batteries based on the reversible multi-electron redox activity of S–S bonds. The batteries using unsymmetrical disulfide cathode-active materials with a carbon nanotube exhibited initial capacities of 127 and 158 Ah/kg, equal to 42 and 53% of their theoretical ones. We demonstrated that unsymmetrical disulfides could be used as cathode-active materials for rechargeable batteries. |
| first_indexed | 2024-03-08T03:52:26Z |
| format | Article |
| id | doaj.art-1ea2b99b940143f3bfd99f8506420732 |
| institution | Directory Open Access Journal |
| issn | 1996-1944 |
| language | English |
| last_indexed | 2024-03-08T03:52:26Z |
| publishDate | 2024-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Materials |
| spelling | doaj.art-1ea2b99b940143f3bfd99f85064207322024-02-09T15:17:46ZengMDPI AGMaterials1996-19442024-02-0117369910.3390/ma17030699Solvent-Free Reaction for Unsymmetrical Organodisulfides with High Purity and Application as Cathode-Active MaterialsYuta Tsukaguchi0Kazuki Shinoda1Yusei Noda2Yui Hatta3Kentaro Tsubouchi4Naoko Shokura5Fumiya Nakamura6Hiromi Kimura-Suda7Hirofumi Yoshikawa8Takeshi Shimizu9Naoki Tanifuji10Chemistry and Biochemistry Division, Department of Integrated Engineering, National Institute of Technology, Yonago College, 4448 Hikona-cho, Yonago 683-8502, JapanChemistry and Biochemistry Division, Department of Integrated Engineering, National Institute of Technology, Yonago College, 4448 Hikona-cho, Yonago 683-8502, JapanChemistry and Biochemistry Division, Department of Integrated Engineering, National Institute of Technology, Yonago College, 4448 Hikona-cho, Yonago 683-8502, JapanChemistry and Biochemistry Division, Department of Integrated Engineering, National Institute of Technology, Yonago College, 4448 Hikona-cho, Yonago 683-8502, JapanChemistry and Biochemistry Division, Department of Integrated Engineering, National Institute of Technology, Yonago College, 4448 Hikona-cho, Yonago 683-8502, JapanChemistry and Biochemistry Division, Department of Integrated Engineering, National Institute of Technology, Yonago College, 4448 Hikona-cho, Yonago 683-8502, JapanChitose Institute of Science and Technology, 758-65 Bibi, Chitose 066-8655, JapanChitose Institute of Science and Technology, 758-65 Bibi, Chitose 066-8655, JapanDepartment of Material Science, School of Engineering, Kwansei Gakuin University, Gakuen 2-1, Sanda 669-1337, JapanChemistry and Biochemistry Division, Department of Integrated Engineering, National Institute of Technology, Yonago College, 4448 Hikona-cho, Yonago 683-8502, JapanChemistry and Biochemistry Division, Department of Integrated Engineering, National Institute of Technology, Yonago College, 4448 Hikona-cho, Yonago 683-8502, JapanUnsymmetrical disulfides, in which different organic groups are bonded to disulfide bonds, have been synthesized by cross-coupling reactions using thiols as substrates. However, due to the low-binding energy of unsymmetrical disulfides, its disproportionation occurs based on the side reactions with nucleophilic thiols, resulting in the impurity of symmetric disulfides. In this study, we developed a solvent-free synthesis method for unsymmetrical disulfides using thiosulfonates, thiols, and a base. This synthetic method enabled us to obtain highly pure diaryl-substituted unsymmetrical disulfides with particularly low-binding energy without control over the nucleophilicity and elimination properties of the substrate. Furthermore, it was observed that the disproportionation of unsymmetrical disulfides occurred in the solvent. This means that solvent-free condition is one of the factors to obtain unsymmetrical disulfides. As a new application of unsymmetrical disulfides, we applied unsymmetrical disulfides to cathode active materials of lithium batteries based on the reversible multi-electron redox activity of S–S bonds. The batteries using unsymmetrical disulfide cathode-active materials with a carbon nanotube exhibited initial capacities of 127 and 158 Ah/kg, equal to 42 and 53% of their theoretical ones. We demonstrated that unsymmetrical disulfides could be used as cathode-active materials for rechargeable batteries.https://www.mdpi.com/1996-1944/17/3/699disulfide bondunsymmetrical disulfidedisproportionationsolvent-free reactionrechargeable battery |
| spellingShingle | Yuta Tsukaguchi Kazuki Shinoda Yusei Noda Yui Hatta Kentaro Tsubouchi Naoko Shokura Fumiya Nakamura Hiromi Kimura-Suda Hirofumi Yoshikawa Takeshi Shimizu Naoki Tanifuji Solvent-Free Reaction for Unsymmetrical Organodisulfides with High Purity and Application as Cathode-Active Materials Materials disulfide bond unsymmetrical disulfide disproportionation solvent-free reaction rechargeable battery |
| title | Solvent-Free Reaction for Unsymmetrical Organodisulfides with High Purity and Application as Cathode-Active Materials |
| title_full | Solvent-Free Reaction for Unsymmetrical Organodisulfides with High Purity and Application as Cathode-Active Materials |
| title_fullStr | Solvent-Free Reaction for Unsymmetrical Organodisulfides with High Purity and Application as Cathode-Active Materials |
| title_full_unstemmed | Solvent-Free Reaction for Unsymmetrical Organodisulfides with High Purity and Application as Cathode-Active Materials |
| title_short | Solvent-Free Reaction for Unsymmetrical Organodisulfides with High Purity and Application as Cathode-Active Materials |
| title_sort | solvent free reaction for unsymmetrical organodisulfides with high purity and application as cathode active materials |
| topic | disulfide bond unsymmetrical disulfide disproportionation solvent-free reaction rechargeable battery |
| url | https://www.mdpi.com/1996-1944/17/3/699 |
| work_keys_str_mv | AT yutatsukaguchi solventfreereactionforunsymmetricalorganodisulfideswithhighpurityandapplicationascathodeactivematerials AT kazukishinoda solventfreereactionforunsymmetricalorganodisulfideswithhighpurityandapplicationascathodeactivematerials AT yuseinoda solventfreereactionforunsymmetricalorganodisulfideswithhighpurityandapplicationascathodeactivematerials AT yuihatta solventfreereactionforunsymmetricalorganodisulfideswithhighpurityandapplicationascathodeactivematerials AT kentarotsubouchi solventfreereactionforunsymmetricalorganodisulfideswithhighpurityandapplicationascathodeactivematerials AT naokoshokura solventfreereactionforunsymmetricalorganodisulfideswithhighpurityandapplicationascathodeactivematerials AT fumiyanakamura solventfreereactionforunsymmetricalorganodisulfideswithhighpurityandapplicationascathodeactivematerials AT hiromikimurasuda solventfreereactionforunsymmetricalorganodisulfideswithhighpurityandapplicationascathodeactivematerials AT hirofumiyoshikawa solventfreereactionforunsymmetricalorganodisulfideswithhighpurityandapplicationascathodeactivematerials AT takeshishimizu solventfreereactionforunsymmetricalorganodisulfideswithhighpurityandapplicationascathodeactivematerials AT naokitanifuji solventfreereactionforunsymmetricalorganodisulfideswithhighpurityandapplicationascathodeactivematerials |