真空烧结制备高性能正极补锂剂Li2NiO2 的性能研究

doi:10.19799/j.cnki.2095-4239.2024.1093

摘要/Abstract

摘要：

预锂化技术对于提高电池首次库仑效率和循环寿命具有显著作用，其中正极补锂技术是最简单有效的方法之一。Li₂NiO₂(LNO)因其制备工艺简单，成本低且环保而被广泛用作补锂剂，但是存在比容量不高和环境稳定性差等问题。针对此问题，本工作通过真空烧结的方式制备出了环境稳定性高、比容量高的富锂镍酸锂(GP-LNO)，与常压烧结的富锂镍酸锂(NM-LNO)进行了对比分析。通过扫描电子显微技术(SEM)、X射线衍射仪(XRD)分析，发现GP-LNO的颗粒完整性更高，结晶度更高且NiO的杂峰更低。电位滴定的结果显示GP-LNO的环境稳定性更好，在温度为25 ℃，湿度为38%的环境下放置360 min后，GP-LNO的残碱中总Li含量只增加了0.04%，同等条件下NM-LNO增加了0.94%。电化学性能分析结果表明，GP-LNO具有更高的首圈充电比容量，在2.8~4.3 V电压范围内，0.05 C倍率恒流恒压充放电，GP-LNO首圈充电容量达到434.21 mAh/g，超出了NM-LNO约28.2 mAh/g，且随着倍率的增加，GP-LNO首圈充电容量先增加后降低，0.5 C倍率的首圈充电容量达到438.64 mAh/g。本研究通过真空烧结显著提升了LNO材料的首圈充电容量和不可逆容量，避免了Ni的氧化和杂质产生，有效改善了LNO的环境稳定性，对其工业应用具有指导意义。

关键词: Li₂NiO₂, 预锂化技术, 环境稳定性, 首圈性能, 真空烧结

Abstract:

Pre-lithiation technology can significantly enhance the initial coulombic efficiency and cycle life of batteries. Among the various prelithiation approaches, cathode lithium replenishment agent technology is one of the simplest and most effective methods. Li₂NiO₂ (LNO) is a widely used additive owing to its simple preparation process, low cost, and environmental friendliness. However, Li₂NiO₂ currently faces issues such as low specific capacity and poor environmental stability, which limit its wide application. To address these issues, the study prepared a lithium-rich nickelate GP-LNO with high environmental stability and specific capacity through vacuum sintering. For comparison, a lithium-rich nickelate NM-LNO sintered under atmospheric pressure using identical processes. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) analyses revealed that GP-LNO exhibited superior particle integrity, higher crystallinity, and lower NiO impurity peaks. The results of potentiometric titration show that GP-LNO had better environmental stability, After 360 minutes in an environment with a temperature of 25 ℃ and humidity of 38%, the total Li content of GP-LNO increased by only 0.04%, compared to a 0.94% increase for NM-LNO under the same conditions. Electrochemical performance analysis revealed that GP-LNO achieved a higher first-cycle charge capacity. In the voltage range of 2.8—4.3 V, using constant current and constant voltage charging and discharging at a rate of 0.05 C, GP-LNO recorded a first-cycle capacity of 434.21 mAh/g, surpassing NM-LNO's capacity by 28.2 mAh/g. As the rate increased, the first-cycle charging capacity of GP-LNO first increased and then decreased. At a rate of 0.5 C, the first-cycle charge capacity of GP-LNO reached 438.64 mAh/g. This work significantly improved the first-cycle charge capacity and irreversible capacity of LNO material through vacuum sintering, by preventing Ni oxidation and impurity formation, and effectively enhanced the environmental stability of LNO, which provide valuable insights for advancing industrial application.

Key words: Li₂NiO₂, pre-lithiation technology, environmental stability, first cycle capacity, vacuum sinterin

中图分类号:

TK 02

胡志金, 尚雷, 王宗凡, 曾州岚, 刘瑛, 辛小超. 真空烧结制备高性能正极补锂剂Li₂NiO₂ 的性能研究[J]. 储能科学与技术, 2025, 14(5): 1910-1917.

Zhijin HU, Lei SHANG, Zongfan WANG, Zhoulan ZENG, Ying LIU, Xiaochao XIN. Research on the performance of high-performance cathode lithium-compensator Li₂NiO₂ prepared by vacuum sintering[J]. Energy Storage Science and Technology, 2025, 14(5): 1910-1917.

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真空烧结制备高性能正极补锂剂Li₂NiO₂ 的性能研究

Research on the performance of high-performance cathode lithium-compensator Li₂NiO₂ prepared by vacuum sintering

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