阐明O3型NaNi1/3Fe1/3Mn1/3O2的结构演变:一个Na-Ion电池的原型阴极
Kai Fang1, Jianhua Yin1, Guifan Zeng1
1State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, P. R. China.
这项研究揭示了增加离子电池阴极充电深度如何影响相位过渡和局部结构. 更深的充电会激活铁氧化还原,但会导致不可逆转的扭曲,限制长期稳定性.
科学领域:
- 材料科学
- 电化学
- 能量储存
背景情况:
- 多层氧化物正极对于提高离子电池 (Na-ion) 的性能至关重要.
- 了解充电深度 (DoC) 极限对于具有竞争力的离子电池开发至关重要.
- 区分可逆结构变化和高DOC的不可逆性降解仍然具有挑战性.
研究的目的:
- 研究 O3-NaNi1/3Fe1/3Mn1/3O2 中相变,局部共价环境演变和电荷补偿之间的复杂相关性.
- 为了澄清可逆和不可逆的结构扭曲之间的界限,
- 探索高能电池阴极的结构稳定策略.
主要方法:
- 使用O3-NaNi1/3Fe1/3Mn1/3O2作为原型材料.
- 将电荷深度 (DoC) 从Na0.4扩大到Na0.2 (对应于4.0V到4.3V的截止值).
- 分析了相变,电荷补偿机制和局部共价环境的演变.
主要成果:
- 在Na0.4 DoC之前发生O3-P3相过渡,Ni氧化占主导地位.
- 进一步的脱 (Na0.4到Na0.2) 诱导了P到O板的过渡,形成了P3/OP2和OP2/O3相互增长的阶段.
- 在较高的DOC时,Fe3+到Fe4+的氧化被激活,但伴随着加剧的Jahn-Teller扭曲和不可逆转的结构降解.
结论:
- 扩展 DoC 激活新的氧化还原对,但引入不可逆转的结构变化.
- P-to-O 板块转变和 Jahn-Teller 扭曲显著影响高 DOC 的局部结构稳定性.
- 在深度循环过程中提出了依赖于速率的调节和兴奋剂策略来稳定分层氧化物阴极.
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