{"title":"锂硫电池隔膜催化剂的制备及其电池性能","authors":"Jiayi Ren and Qihao Zhao","doi":"10.1039/D4RA06366J","DOIUrl":null,"url":null,"abstract":"<p >Lithium–sulfur batteries (LSBs) with metal lithium as the anode and elemental sulfur as the cathode active materials have attracted extensive attention due to their high theoretical specific capacity (1675 mA h g<small><sup>−1</sup></small>), high theoretical energy density (2600 W h kg<small><sup>−1</sup></small>), low cost, and environmental friendliness. However, the discharge intermediate lithium polysulfide undergoes a shuttle side reaction between the two electrodes, resulting in low utilization of the active substances. This limits the capacity and cycle life of LSBs and further delays their commercial development. However, the number of active sites and electron transport capacity of such catalysts still do not meet the practical development needs of lithium–sulfur batteries. In view of these issues, this paper focuses on a zinc–cobalt compound catalyst, modifying it through heteroatom doping, bimetallic synergistic effect and heterogeneous structure design to enhance the performance of LSBs as a separator modification material. A carbon shell-supported boron-doped ZnS/CoS<small><sub>2</sub></small> heterojunction catalytic material (B–ZnS/CoS<small><sub>2</sub></small>@CS) was prepared, and its performance in lithium–sulfur batteries was evaluated. A carbon substrate (CS) was prepared by pyrolysis of sodium citrate, and the boron-doped ZnS/CoS<small><sub>2</sub></small> heterojunction catalyst was formed on the CS using a one-step solvothermal method. The unique heterogeneous interface provides numerous active sites for the adsorption and catalysis of polysulfides. The uniformly doped, electron-deficient boron further enhances the Lewis acidity of the ZnS/CoS<small><sub>2</sub></small> heterojunction, while also regulating electron transport. The B–ZnS/CoS<small><sub>2</sub></small>@CS catalyst effectively inhibits the diffusion of LiPS anions by utilizing additional lone-pair electrons. The lithium–sulfur battery using the catalyst-modified separator achieves a high specific capacity of 1241 mA h g<small><sup>−1</sup></small> at a current density of 0.2C and retains a specific capacity of 384.2 mA h g<small><sup>−1</sup></small> at 6.0C. In summary, B–ZnS/CoS<small><sub>2</sub></small>@CS heterojunction catalysts were prepared through boron doping modification. They can promote the conversion of polysulfides and effectively inhibit the shuttle effect. The findings provide valuable insights for the future modification and preparation of lithium–sulfur battery catalysts.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":" 49","pages":" 36471-36487"},"PeriodicalIF":3.9000,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ra/d4ra06366j?page=search","citationCount":"0","resultStr":"{\"title\":\"Preparation of a lithium–sulfur battery diaphragm catalyst and its battery performance\",\"authors\":\"Jiayi Ren and Qihao Zhao\",\"doi\":\"10.1039/D4RA06366J\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Lithium–sulfur batteries (LSBs) with metal lithium as the anode and elemental sulfur as the cathode active materials have attracted extensive attention due to their high theoretical specific capacity (1675 mA h g<small><sup>−1</sup></small>), high theoretical energy density (2600 W h kg<small><sup>−1</sup></small>), low cost, and environmental friendliness. However, the discharge intermediate lithium polysulfide undergoes a shuttle side reaction between the two electrodes, resulting in low utilization of the active substances. This limits the capacity and cycle life of LSBs and further delays their commercial development. However, the number of active sites and electron transport capacity of such catalysts still do not meet the practical development needs of lithium–sulfur batteries. In view of these issues, this paper focuses on a zinc–cobalt compound catalyst, modifying it through heteroatom doping, bimetallic synergistic effect and heterogeneous structure design to enhance the performance of LSBs as a separator modification material. A carbon shell-supported boron-doped ZnS/CoS<small><sub>2</sub></small> heterojunction catalytic material (B–ZnS/CoS<small><sub>2</sub></small>@CS) was prepared, and its performance in lithium–sulfur batteries was evaluated. A carbon substrate (CS) was prepared by pyrolysis of sodium citrate, and the boron-doped ZnS/CoS<small><sub>2</sub></small> heterojunction catalyst was formed on the CS using a one-step solvothermal method. The unique heterogeneous interface provides numerous active sites for the adsorption and catalysis of polysulfides. The uniformly doped, electron-deficient boron further enhances the Lewis acidity of the ZnS/CoS<small><sub>2</sub></small> heterojunction, while also regulating electron transport. The B–ZnS/CoS<small><sub>2</sub></small>@CS catalyst effectively inhibits the diffusion of LiPS anions by utilizing additional lone-pair electrons. The lithium–sulfur battery using the catalyst-modified separator achieves a high specific capacity of 1241 mA h g<small><sup>−1</sup></small> at a current density of 0.2C and retains a specific capacity of 384.2 mA h g<small><sup>−1</sup></small> at 6.0C. In summary, B–ZnS/CoS<small><sub>2</sub></small>@CS heterojunction catalysts were prepared through boron doping modification. They can promote the conversion of polysulfides and effectively inhibit the shuttle effect. 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引用次数: 0
摘要
以金属锂为正极、元素硫为负极活性材料的锂硫电池(LSBs)因其理论比容量高(1675 mA h g-1)、理论能量密度高(2600 W h kg-1)、成本低和环境友好而受到广泛关注。然而,放电中间体多硫化锂会在两个电极之间发生穿梭副反应,导致活性物质利用率低。这限制了 LSB 的容量和循环寿命,进一步推迟了其商业开发。然而,此类催化剂的活性位点数量和电子传输能力仍无法满足锂硫电池的实际开发需求。针对这些问题,本文以锌钴化合物催化剂为研究对象,通过杂原子掺杂、双金属协同效应和异质结构设计等方法对其进行改性,以提高锂硫电池作为隔膜改性材料的性能。制备了一种碳壳支撑的掺硼 ZnS/CoS2 异质结催化材料(B-ZnS/CoS2@CS),并对其在锂硫电池中的性能进行了评估。通过热解柠檬酸钠制备了碳基底(CS),并采用一步溶热法在 CS 上形成了掺硼的 ZnS/CoS2 异质结催化剂。独特的异质界面为多硫化物的吸附和催化提供了大量活性位点。均匀掺杂的缺电子硼进一步增强了 ZnS/CoS2 异质结的路易斯酸性,同时也调节了电子传输。B-ZnS/CoS2@CS 催化剂通过利用额外的孤对电子,有效抑制了锂硫电池阴离子的扩散。使用催化剂改性隔膜的锂硫电池在 0.2C 电流密度下实现了 1241 mA h g-1 的高比容量,并在 6.0C 时保持了 384.2 mA h g-1 的比容量。总之,通过硼掺杂改性制备了 B-ZnS/CoS2@CS 异质结催化剂。它们能促进多硫化物的转化并有效抑制穿梭效应。这些发现为今后锂硫电池催化剂的改性和制备提供了宝贵的启示。
Preparation of a lithium–sulfur battery diaphragm catalyst and its battery performance
Lithium–sulfur batteries (LSBs) with metal lithium as the anode and elemental sulfur as the cathode active materials have attracted extensive attention due to their high theoretical specific capacity (1675 mA h g−1), high theoretical energy density (2600 W h kg−1), low cost, and environmental friendliness. However, the discharge intermediate lithium polysulfide undergoes a shuttle side reaction between the two electrodes, resulting in low utilization of the active substances. This limits the capacity and cycle life of LSBs and further delays their commercial development. However, the number of active sites and electron transport capacity of such catalysts still do not meet the practical development needs of lithium–sulfur batteries. In view of these issues, this paper focuses on a zinc–cobalt compound catalyst, modifying it through heteroatom doping, bimetallic synergistic effect and heterogeneous structure design to enhance the performance of LSBs as a separator modification material. A carbon shell-supported boron-doped ZnS/CoS2 heterojunction catalytic material (B–ZnS/CoS2@CS) was prepared, and its performance in lithium–sulfur batteries was evaluated. A carbon substrate (CS) was prepared by pyrolysis of sodium citrate, and the boron-doped ZnS/CoS2 heterojunction catalyst was formed on the CS using a one-step solvothermal method. The unique heterogeneous interface provides numerous active sites for the adsorption and catalysis of polysulfides. The uniformly doped, electron-deficient boron further enhances the Lewis acidity of the ZnS/CoS2 heterojunction, while also regulating electron transport. The B–ZnS/CoS2@CS catalyst effectively inhibits the diffusion of LiPS anions by utilizing additional lone-pair electrons. The lithium–sulfur battery using the catalyst-modified separator achieves a high specific capacity of 1241 mA h g−1 at a current density of 0.2C and retains a specific capacity of 384.2 mA h g−1 at 6.0C. In summary, B–ZnS/CoS2@CS heterojunction catalysts were prepared through boron doping modification. They can promote the conversion of polysulfides and effectively inhibit the shuttle effect. The findings provide valuable insights for the future modification and preparation of lithium–sulfur battery catalysts.
期刊介绍:
An international, peer-reviewed journal covering all of the chemical sciences, including multidisciplinary and emerging areas. RSC Advances is a gold open access journal allowing researchers free access to research articles, and offering an affordable open access publishing option for authors around the world.