A Cation and Anion Dual Doping Strategy for the Elevation of Titanium Redox Potential for High-Power Sodium-Ion Batteries

被引:103
作者
Chen, Mingzhe [1 ,2 ]
Xiao, Jin [3 ]
Hua, Weibo [4 ]
Hu, Zhe [1 ]
Wang, Wanlin [1 ]
Gu, Qinfen [5 ]
Tang, Yuxin [2 ]
Chou, Shu-Lei [1 ]
Liu, Hua-Kun [1 ]
Dou, Shi-Xue [1 ]
机构
[1] Univ Wollongong, Australian Inst Innovat Mat, Inst Superconducting & Elect Mat, Innovat Campus,Squires Way, North Wollongong, NSW 2522, Australia
[2] Univ Macau, Inst Appl Phys & Mat Engn, Macau, Peoples R China
[3] Hunan Univ Technol, Sch Sci, Zhuzhou 412007, Peoples R China
[4] Karlsruhe Inst Technol KIT, Inst Appl Mat Energy Storage Syst IAM ESS, D-76344 Eggenstein Leopoldshafen, Germany
[5] Australian Synchrotron, 800 Blackburn Rd, Clayton, Vic 3168, Australia
基金
澳大利亚研究理事会; 中国国家自然科学基金;
关键词
cation; anion doping; elevation of potential; sodium-ion batteries; Ti-based polyanions; zero strain; PRUSSIAN BLUE ANALOGS; NA-ION; CATHODE MATERIALS; LONG-LIFE; ELECTRODE MATERIAL; RECENT PROGRESS; ENERGY-STORAGE; HIGH-VOLTAGE; CARBON; CRYSTAL;
D O I
10.1002/anie.202003275
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Titanium-based polyanions have been intensively investigated for sodium-ion batteries owing to their superior structural stability and thermal safety. However, their low working potential hindered further applications. Now, a cation and anion dual doping strategy is used to boost the redox potential of Ti-based cathodes of Na3Ti0.5V0.5(PO3)(3)N as a new cathode material for sodium ion batteries. Both the Ti3+/Ti4+ and V3+/V4+ redox couples are reversibly accessed, leading to two distinctive voltage platforms at ca. 3.3 V and ca. 3.8 V, respectively. The remarkably improved cycling stability (86.3 %, 3000 cycles) can be ascribed to the near-zero volume strain in this unusual cubic symmetry, which has been demonstrated by in situ synchrotron-based X-ray diffraction. First-principles calculations reveal its well-interconnected 3D Na diffusion pathways with low energy barriers, and the two-sodium-extracted intermediate NaTi0.5V0.5(PO3)(3)N is also a stable phase according to formation energy calculations.
引用
收藏
页码:12076 / 12083
页数:8
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