Acta Chimica Sinica ›› 2021, Vol. 79 ›› Issue (12): 1511-1517.DOI: 10.6023/A21080363 Previous Articles     Next Articles

Article

Cu3Si负极脱/嵌锂过程的赝电容行为与二级相变的关联性

史傲迪, 陈思, 郑淞生*(), 王兆林*()   

  1. 厦门大学能源学院 福建厦门 361102
  • 投稿日期:2021-08-04 发布日期:2021-10-08
  • 通讯作者: 郑淞生, 王兆林
  • 基金资助:
    国家自然科学基金面上项目(21875199); 双一流建设重点高校项目(0290-X2100502); 厦门大学能源学院—潍坊赛诺凯特广谱型氢能燃料电池研发中心项目(XDHT2020024C); 厦门大学能源学院—淄博高新技术产业开发区氢能研发中心(XDHT2020023C); 合肥综合性国家科学中心能源研究院委托开发项目(XDHT2020305A)

Correlation between the Pseudo-Capacitance Behavior and the Second-Order Phase Transition in the Li+ Insertion/Desertion in Cu3Si

Aodi Shi, Si Chen, Songsheng Zheng(), Zhaolin Wang()   

  1. College of Energy, Xiamen University, Xiamen, Fujian 361102
  • Received:2021-08-04 Published:2021-10-08
  • Contact: Songsheng Zheng, Zhaolin Wang
  • Supported by:
    National Natural Science Foundation of China(21875199); National “Double First-class” Construction Special Funds Project(0290-X2100502); Xiamen University College of Energy-Weifang Senokate Broad Spectrum Hydrogen Fuel Cell R&D Center Project(XDHT2020024C); Xiamen University College of Energy-Zibo High-tech Industrial Development Zone Hydrogen Energy R&D Center(XDHT2020023C); Commissioned Development Project of Energy Research Institute of Hefei Comprehensive National Science Center(XDHT2020305A)

Lithium-ion batteries with high energy density have urgent demand, especially in the fields of pure electric vehicles, smart phones, laptops, wind power generation and energy storage. Therefore, more and more attention has been paid on materials with high energy density, rapid charge/discharge capability and long cycle life. In this paper, pure Cu3Si phase was prepared by metallurgical process, and the electrochemical characteristics of the as prepared Cu3Si samples were studied by using CR2025 button half-cell structure with metal lithium sheet as reference electrode and Celgard 2500 as diaphragm. The results showed that, at a current density of 0.1C (420 mA•g–1), it possessed a first-cycle discharge specific capacity of 759 mAh•g–1 with a coulomb efficiency of 96.56%. It remained 822 mAh•g–1 after 200 cycles with a capacity retention rate of 98%. It retained 776, 700, 580, 500, 440 and 405 mAh•g–1 at a testing rate of 0.1C, 0.2C, 0.4C, 0.6C, 0.8C and 1C, respectively. The specific capacity was stabilized at around 790 mAh•g–1 when the current density was restored to 0.1C, which did not decrease significantly compared with the initial value. Moreover, the impedance was about 60 Ω, lower than that of the reported Si@C anode. Thus, it suggested that introducing Cu would greatly reduce the charge transfer resistance. It was worth noting that the charge/discharge curve was slope like and had pseudo capacitance characteristics. Furthermore, the cyclic voltammetry (CV) measurement was carried out at scanning rates of 0.1, 0.2, 0.4, 0.6, 0.8 and 1.0 mV/s, respectively. The results discovered for the first time that the as-prepared Cu3Si possessed the characteristic of both battery and capacitance. They together stored the charges, and the capacitance dominated the contribution. Moreover, an clear step could be observed at 550—600 ℃ in the differential scanning calorimetry (DSC) curve of the as-prepared Cu3Si sample after discharged, relating to a change in the specific heat capacity. Moreover, the sample phase did not change before and after the charge/discharge process. Therefore, it was determined that the Li+ insertion/desertion process of Cu3Si was not a first-order phase transition but a second-order phase transition process. To be concluded, for Cu3Si anode materials, the redox process was a second-order phase transition, which exhibited a pseudo capacitive behavior in its electrochemical properties.

Key words: metallurgical method, Cu3Si, electrochemical characteristics, pseudo-capacitance, second order phase transition