高性能磷酸铁锂电池补锂技术及机制

doi:10.19799/j.cnki.2095-4239.2023.0924

储能科学与技术 ›› 2024, Vol. 13 ›› Issue (5): 1435-1442.doi: 10.19799/j.cnki.2095-4239.2023.0924

高性能磷酸铁锂电池补锂技术及机制

姜媛媛¹^,²(), 屠芳芳¹(), 张芳平¹, 王盈来¹, 蔡佳文¹, 杨东辉¹, 李艳红¹, 相佳媛¹, 夏新辉², 傅继澎¹^,³

^1.浙江南都电源动力股份有限公司，浙江杭州 311300
^2.浙江工业大学材料科学与工程学院，浙江杭州 310014
^3.中国计量大学光学与电子科技学院，浙江杭州 310018

收稿日期:2023-12-19 修回日期:2024-01-03 出版日期:2024-05-28 发布日期:2024-05-28
通讯作者: 屠芳芳 E-mail:862454486@qq.com;tuff@naradapower.com
作者简介:姜媛媛（1995—），女，博士，研究方向为新能源材料、锂离子电池前瞻技术，E-mail：862454486@qq.com；
基金资助:
浙江省科技计划项目(2022C01160)

Study on technology and mechanism of prelithiation for high-performance lithium iron phosphate battery

Yuanyuan JIANG¹^,²(), Fangfang TU¹(), Fangping ZHANG¹, Yinglai WANG¹, Jiawen CAI¹, Donghui YANG¹, Yanhong LI¹, Jiayuan XIANG¹, Xinhui XIA², Jipeng FU¹^,³

^1.Zhejiang Narada Power Source Co. , Ltd. , Hangzhou 311300, Zhejiang, China
^2.School of Materials Science and Engineering, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China
^3.School of Optical and Electronic Technology, China Jiliang University, Hangzhou 310018, Zhejiang, China

Received:2023-12-19 Revised:2024-01-03 Online:2024-05-28 Published:2024-05-28
Contact: Fangfang TU E-mail:862454486@qq.com;tuff@naradapower.com

摘要/Abstract

摘要：

本工作采用正极磷酸铁锂（LiFePO₄，LFP）搭配高容量石墨掺硅负极体系，以商业化富锂镍酸锂（Li₂NiO₂，LNO）作为正极补锂添加剂，探究补锂技术对磷酸铁锂电池性能的影响及作用机制。通过对LNO的电化学性能、脱锂前后的结构组成与微观形貌变化进行测试与分析，发现LNO的不可逆容量可达212.1 mAh/g，而且脱锂后的LNO主要以仍具活性的Li_0.63Ni_1.02O₂形式存在。然后，将一定量的LNO添加至LFP正极浆料中制作成32 Ah软包电池，并进行容量、倍率、电化学阻抗和循环寿命等性能的测试与研究。结果表明：与基准组相比，添加质量分数3%的LNO补锂剂可以显著提升磷酸铁锂电池的性能，补锂组的能量密度和循环寿命分别提高4.9%和50%。此外，结合三电极测试方法，阐明了补锂技术对循环性能提升的作用机制。添加过量的正极补锂剂可促使部分活性锂预存于负极侧，在循环过程中进行缓慢释放，确保长期稳定的锂损失补偿，从而改善锂离子电池的循环寿命。该研究有助于推动正极补锂技术在储能电池中的应用，不仅为高性能磷酸铁锂电池的设计与开发提供理论和实验依据，也为硅基负极材料的商业化应用奠定基础。

关键词: 磷酸铁锂电池, 正极补锂添加剂, 硅基负极, 能量密度, 循环寿命

Abstract:

In this work, Li₂NiO₂ (LNO) is employed as a cathode prelithiation additive for lithium iron phosphate (LFP) cathodes, paired with a high-capacity graphite-doped silicon oxide anode, to investigate the effects and mechanisms of prelithiation technology on LFP batteries. The electrochemical performance, structural composition, and surface morphology of LNO were meticulously evaluated, revealing that LNO possesses an irreversible capacity of 212.1 mAh/g, primarily comprising active Li_0.63Ni_1.02O₂ postdelithiation. Subsequently, a 32 Ah pouch cell was fabricated by integrating 3% LNO into the cathode slurry, leading to a notable enhancement in the performance of the LFP batteries. Compared to the control group, the energy density and cycle life of the LFP batteries with LNO were increased by 4.9% and 50%, respectively. Moreover, the contribution of prelithiation technology to cycle stability was elucidated using a three-electrode method, revealing that an excessive quantity of cathode prelithiation additive could lead to the retention of active lithium ions on the anode. These ions are gradually released during cycling, ensuring a sustained replenishment of active lithium ions, thereby augmenting the cycle life of lithium-ion batteries. This study advances the application of cathode prelithiation technology in energy storage systems, providing both theoretical and experimental insights for the design and development of high-performance LFP batteries and facilitating the large-scale adoption of silicon-based anode materials.

Key words: lithium iron phosphate battery, cathode prelithiation additive, silicon-based anode, energy density, cycle life

中图分类号:

O 646

姜媛媛, 屠芳芳, 张芳平, 王盈来, 蔡佳文, 杨东辉, 李艳红, 相佳媛, 夏新辉, 傅继澎. 高性能磷酸铁锂电池补锂技术及机制[J]. 储能科学与技术, 2024, 13(5): 1435-1442.

Yuanyuan JIANG, Fangfang TU, Fangping ZHANG, Yinglai WANG, Jiawen CAI, Donghui YANG, Yanhong LI, Jiayuan XIANG, Xinhui XIA, Jipeng FU. Study on technology and mechanism of prelithiation for high-performance lithium iron phosphate battery[J]. Energy Storage Science and Technology, 2024, 13(5): 1435-1442.

图/表 8

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高性能磷酸铁锂电池补锂技术及机制

Study on technology and mechanism of prelithiation for high-performance lithium iron phosphate battery

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