Zhao Yun, Zhang Haoyue, Li Yong, Ma Canliang, Tian Wenjuan, Qi Xingguo, Han Gaoyi, Shao Zongping
Institute of Molecular Science, Key Laboratory of Materials for Energy Conversion and Storage of Shanxi Province, Key Laboratory of Chemical Biology and Molecular Engineering of Education Ministry, Shanxi University, Taiyuan, 030006, P. R. China.
Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering, Taiyuan, 030006, P. R. China.
Adv Sci (Weinh). 2023 Oct;10(28):e2303108. doi: 10.1002/advs.202303108. Epub 2023 Aug 4.
Crystal transformation of metal compound cathodes during charge/discharge processes in alkali metal-ion batteries usually generates profound impact on structural stability and electrochemical performance, while the theme in anode materials, which always occurs and completes during the first redox cycle, is rarely explored probably due to the fast transformation dynamics. Herein, for the first time, a unique crystal transformation behavior with slow dynamics in anode of sodium-ion batteries (SIBs) is reported, which further promotes electrochemical performance. Specifically, irreversible γ → β crystal transformation of In Se is observed, induced by the persistent size degradation of In Se particles during repeated sodiation/desodiation, supported by a series of ex situ characterizations, such as HRTEM, XRD, and XPS of γ-In Se /reduced graphene oxide (γ-In Se @rGO) nanocomposite. The hybrid electrode shows ultrahigh long-term cycling stability (378 mA h g at 1.0 A g after 1000 cycles) and excellent rate capability (272 mA h g at 20.0 A g ). Full battery with Na V (PO ) cathode also manifests superior performance, promising β-In Se dominated electrode materials in high-power and long-life SIBs. The first-principle calculations suggest the crystal transformation enhances electric conductivity of β-In Se and facilitates its accessibility to sodium. In combination with the synergistic effect between rGO matrix, substantially enhanced electrochemical performance is realized.
碱金属离子电池在充电/放电过程中,金属化合物阴极的晶体转变通常会对结构稳定性和电化学性能产生深远影响,而阳极材料中的这一主题(其总是在第一个氧化还原循环中发生并完成)由于转变动力学较快,很少被探究。在此,首次报道了钠离子电池(SIBs)阳极中一种具有缓慢动力学的独特晶体转变行为,这进一步提升了电化学性能。具体而言,通过一系列非原位表征,如γ-InSe/还原氧化石墨烯(γ-InSe@rGO)纳米复合材料的高分辨透射电子显微镜(HRTEM)、X射线衍射(XRD)和X射线光电子能谱(XPS),观察到InSe在反复嵌钠/脱钠过程中因颗粒持续尺寸降解而诱导的不可逆γ→β晶体转变。该混合电极表现出超高的长期循环稳定性(1000次循环后在1.0 A g下为378 mA h g)和优异的倍率性能(在20.0 A g下为272 mA h g)。采用NaV(PO)阴极的全电池也表现出优异性能,这表明β-InSe主导的电极材料在高功率和长寿命SIBs中具有潜力。第一性原理计算表明,晶体转变提高了β-InSe 的电导率并促进了其对钠的可达性。结合rGO基体之间的协同效应,实现了电化学性能的大幅提升。