Zhenxin Zhao, Zonglin Yi, Rong Niu, Jiajun Chen, Rajesh Pathak, Yongzhen Wang, Jeffrey W Elam, Xiaomin Wang
{"title":"Deciphering the multi-electron redox chemistry of metal-sulfide electrode toward advanced aqueous Cu ion storage","authors":"Zhenxin Zhao, Zonglin Yi, Rong Niu, Jiajun Chen, Rajesh Pathak, Yongzhen Wang, Jeffrey W Elam, Xiaomin Wang","doi":"10.1016/j.jmst.2024.08.071","DOIUrl":null,"url":null,"abstract":"While neutral aqueous metal batteries, featuring cost-effectiveness and non-flammability, hold significant potential for large-scale energy storage, their practical application is hampered by the limited specific capacity of cathode materials (less than 500 mAh g<sup>−1</sup>). Herein, capacity-oriented CoS<sub>2</sub> and rate-optimized Co<sub>9</sub>S<sub>8</sub> cathodes are developed based on the aqueous copper ion system. The charge-storage mechanism is systematically investigated through a series of ex-situ tests and density functional theory calculations, focusing on the reversible transitions of Co<sub>9</sub>S<sub>8</sub>→Cu<sub>7</sub>S<sub>4</sub>→Cu<sub>9</sub>S<sub>5</sub>/Cu<sub>1.8</sub>S and CoS<sub>2</sub>→Cu<sub>7</sub>S<sub>4</sub>→Cu<sub>2</sub>S, which are associated with the redox reactions of Cu<sup>2+</sup>/Cu<sup>+</sup>‖Co<sup>2+</sup>/Co and Cu<sup>2+</sup>/Cu<sup>+</sup>‖S<sub>2</sub><sup>2−</sup>/S<sup>2−</sup>, respectively. The electrochemical results show that CoS<sub>2</sub> can exhibit a superior capacity of 619 mAh g<sup>−1</sup> at 1 A g<sup>−1</sup> after 400 cycles, while Co<sub>9</sub>S<sub>8</sub> maintains an outstanding rate performance of 497 mAh g<sup>−1</sup> at 10 A g<sup>−1</sup> (the retention rate is 95% compared to 521 mAh g<sup>−1</sup> at 1 A g<sup>−1</sup>). As a proof of concept, an advanced CoS<sub>2</sub>//Zn hybrid aqueous battery demonstrates a working voltage of 1.20 V and a specific energy of 663 Wh kg<sub>cathode</sub><sup>−1</sup>. This work provides an alternative direction for developing sulfide cathodes in energetic aqueous metal batteries.","PeriodicalId":16154,"journal":{"name":"Journal of Materials Science & Technology","volume":null,"pages":null},"PeriodicalIF":11.2000,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Materials Science & Technology","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1016/j.jmst.2024.08.071","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
While neutral aqueous metal batteries, featuring cost-effectiveness and non-flammability, hold significant potential for large-scale energy storage, their practical application is hampered by the limited specific capacity of cathode materials (less than 500 mAh g−1). Herein, capacity-oriented CoS2 and rate-optimized Co9S8 cathodes are developed based on the aqueous copper ion system. The charge-storage mechanism is systematically investigated through a series of ex-situ tests and density functional theory calculations, focusing on the reversible transitions of Co9S8→Cu7S4→Cu9S5/Cu1.8S and CoS2→Cu7S4→Cu2S, which are associated with the redox reactions of Cu2+/Cu+‖Co2+/Co and Cu2+/Cu+‖S22−/S2−, respectively. The electrochemical results show that CoS2 can exhibit a superior capacity of 619 mAh g−1 at 1 A g−1 after 400 cycles, while Co9S8 maintains an outstanding rate performance of 497 mAh g−1 at 10 A g−1 (the retention rate is 95% compared to 521 mAh g−1 at 1 A g−1). As a proof of concept, an advanced CoS2//Zn hybrid aqueous battery demonstrates a working voltage of 1.20 V and a specific energy of 663 Wh kgcathode−1. This work provides an alternative direction for developing sulfide cathodes in energetic aqueous metal batteries.
期刊介绍:
Journal of Materials Science & Technology strives to promote global collaboration in the field of materials science and technology. It primarily publishes original research papers, invited review articles, letters, research notes, and summaries of scientific achievements. The journal covers a wide range of materials science and technology topics, including metallic materials, inorganic nonmetallic materials, and composite materials.