高温淬火对钠离子电池锰基层状正极材料结构和性能的影响

doi:10.19799/j.cnki.2095-4239.2024.0084

摘要/Abstract

摘要：

作为钠离子电池正极材料，锰基层状氧化物具有理论储钠容量高、成本低和热稳定性高等优点，但也存在因结构畸变、Na⁺/空位有序以及过渡金属空位等带来的循环稳定性问题。研究表明，抑制过渡金属空位可有效提升锰基层状氧化物正极的电化学性能。为此，本工作对比研究了溶胶凝胶制备过程中高温淬火对Na_0.67Fe_1/3Co_1/3Mn_1/3O₂ （NFCMO）结构和性能的影响。结果表明，相比于未经高温淬火处理的NFCMO，高温液氮淬火合成的NFCMO-LN具有更高的比容量和倍率性能。NFCMO和NFCMO-LN在0.1 C下的初始放电比容量分别为91.1和129.8 mAh g^-1；1 C倍率下循环100周后的容量保留率分别为100%和90%。即使在10.0 C的高倍率下，NFCMO-LN仍能提供56.2 mAh g^-1的放电比容量。结构分析表明，高温液氮淬火能有效抑制过渡金属空位的产生，提升了材料的结构稳定性。研究结果为钠离子电池正极材料的结构设计和电化学性能优化提供了一种可行的技术途径。

关键词: 钠离子电池, 层状氧化物, 锰酸钠, 掺杂, 淬火

Abstract:

As a typical class of cathode materials for sodium ion batteries, Mn-based layered cathodes have the advantages of high theoretical specific capacity, low cost and high thermal stability. However, these cathode materials have been shown to undergo structure distortion, Na⁺/vacancies ordering, and transition metal vacancy, leading to poor cyclic stability. Previous studies reported that suppressing transition metal vacancy can effectively improve the electrochemical performance of Mn-based layered cathodes. In this work, we investigated the role of high temperature liquid N₂ quenching in the structure and performance of Na_0.67Fe_1/3Co_1/3Mn_1/3O₂ (NFCMO) and Na_0.67Fe_1/3Co_1/3Mn_1/3O₂-Liquid N₂ (NFCMO-LN) cathode materials during sol-gel process. Compared with pristine NFCMO, the NFCMO-LN shows higher specific capacity and rate capability. The NFCMO and NFCMO-LN electrodes deliver 91.1 and 129.8 mAh g^-1 discharge capacity at 0.1 C in the initial cycle. Moreover, the capacity retention of NFCMO and NFCMO-LN are 100% and 90% after 100 cycles at 1C, respectively. In particular, NFCMO-LN can deliver a discharge capacity of 56.2 mAh g^-1 even at 10.0 C. The structural analysis demonstrates that liquid nitrogen quenching at high temperature can effectively suppress transition metal vacancy and increase structural stability. Our findings provide feasible strategies in structure design and electrochemical performance optimization of cathode materials for sodium ion batteries.

Key words: sodium ion battery, layered oxide, sodium manganate, lattice doping, quenching

中图分类号:

TQ 152

谭仕荣, 尹文骥, 曾翠鸿, 黎小琼, 訚硕, 纪方力, 胡思江, 王红强, 李庆余. 高温淬火对钠离子电池锰基层状正极材料结构和性能的影响[J]. 储能科学与技术, doi: 10.19799/j.cnki.2095-4239.2024.0084.

Shirong TAN, Wenji YIN, Cuihong ZENG, Xiaoqiong Li, Shuo YIN, Fangli JI, Sijiang HU, Hongqiang WANG, Qingyu LI. Exploring the role of High Temperature Quenching in Structure and Performance of Mn-based layered cathode materials for sodium ion batteries[J]. Energy Storage Science and Technology, doi: 10.19799/j.cnki.2095-4239.2024.0084.

图/表 6

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样品	Rs (ohm)	Rf (ohm)	Rct (ohm)
NFCMO首次循环之后	5.796	12.5	72.18
NFCMO-LN首次循环之后	6.616	16.15	94.07
NFCMO 100次循环之后	5.643	17.91	106.8
NFCMO-LN 100次循环之后	5.865	10.68	64.18

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