磷酸铁锂电池循环初期衰减快原因分析及性能改善
收稿日期: 2022-06-20
网络出版日期: 2023-03-17
基金资助
国家重点研发计划项目(2019YFC1907800)
Cause analysis of early cycling attenuation of LiFePO4 battery and its performance improvement
Received date: 2022-06-20
Online published: 2023-03-17
磷酸铁锂电池由于循环性能优异、价格相对低廉、安全性能有保障等诸多优势而备受青睐。磷酸铁锂电池循环曲线的特点是前面衰减很快,到中后期变得平缓。为了挖掘磷酸铁锂电池更长寿命的潜在能力,以磷酸铁锂/石墨电池为研究对象,对衰减较快的前期循环进行了研究,并依据研究结果提出了改善建议。与三元类(NCM)电芯比较,正极材料的首效差异造成磷酸铁锂材料循环衰减快于三元材料,并通过电感耦合等离子体发射光谱(ICP)、X射线衍射(XRD)等手段证实了这一理论。采用电感耦合等离子体发射光谱(ICP)、能谱(EDS)和差式扫描量热分析(DSC)等多种手段对固体电解质界面(SEI)膜进行了表征,证明磷酸铁锂前期衰减快的原因主要是活性锂的消耗,而损失的活性锂主要用于修复破坏的SEI膜。最后提出一系列改善措施,即通过改善负极颗粒的OI值(活性材料取向指数)、负极涂覆量、负极胶的溶胀、正极比表面积等,可以减缓磷酸铁锂电池前期的衰减速率。
徐瑞琳 , 曾涛 , 刘欢 , 刘兴伟 , 王浩 , 徐晓明 , 赵李鹏 . 磷酸铁锂电池循环初期衰减快原因分析及性能改善[J]. 无机盐工业, 2023 , 55(3) : 92 -97 . DOI: 10.19964/j.issn.1006-4990.2022-0275
LiFePO4 battery is highly favored for its′excellent cycling performance,relatively low price and high stability.The cyclic curve faded rapidly in the early stage,and flattened out in the middle and late stages.In order to explore the potential capacity of LiFePO4 battery for longer service life,LiFePO4/graphite battery was taken as the research object to study the early cycle with fast decay,and suggestions for improvement were put forward based on the research results.Compared with the ternary(NCM) cell,the differences of initial efficiency of the anode material caused the cycle attenuation of LiFePO4 material to be faster than that of the ternary material.This theory had been confirmed by means of inductively coupled plasma emission spectroscopy(ICP),X-ray diffraction(XRD),etc.The SEI films were characterized by inductively coupled plasma emission spectroscopy(ICP),energy dispersive spectroscopy(EDS) and differential scanning calorimetry(DSC).It was proved that the main reason for the fast decay of LiFePO4 in the early stage was the consumption of active lithium,and the loss of active lithium was mainly used to repair the damaged SEI film.Finally,the decay rate of the LiFePO4 battery in the early stage could be slowed down by improving the OI value of the negative particles,the coating amount of the cathodes,the swelling of the negative gel,and the specific surface area of the anodes.
| 1 | 张克杰,陈鹏,谢旺旺,等.磷酸铁锂优缺点及改性研究进展[J].无机盐工业,2018,50(6):13-17. |
| ZHANG Kejie, CHEN Peng, XIE Wangwang,et al.Progress in modification of lithium iron phosphate and its advantages and disadvantages[J].Inorganic Chemicals Industry,2018,50(6):13-17. | |
| 2 | 曹利娜,王晨旭,刘成士,等.磷酸铁锂正极材料与电解液的相容性研究[J].无机盐工业,2014,46(10):75-78. |
| CAO Lina, WANG Chenxu, LIU Chengshi,et al.Study on compatibility of LiFePO4 cathode material with electrolyte for lithium ion battery[J].Inorganic Chemicals Industry,2014,46(10):75-78. | |
| 3 | HUANG Xiankun, HE Xiangming, JIANG Changyin,et al.Reaction mechanisms on solvothermal synthesis of nano LiFePO4 crystals and defect analysis[J].Industrial & Engineering Chemistry Research,2017,56(38):10648-10657. |
| 4 | 黄可龙,吕正中,刘素琴.锂离子电池容量损失原因分析[J].电池,2001,31(3):142-145. |
| HUANG Kelong, LU Zhengzhong, LIU Suqin.On capacity fading and its mechanisms for lithium-ion batteries[J].Battery Bimonthly,2001,31(3):142-145. | |
| 5 | 王其钰,王朔,张杰男,等.锂离子电池失效分析概述[J].储能科学与技术,2017,6(5):1008-1025. |
| WANG Qiyu, WANG Shuo, ZHANG Jienan,et al.Overview of the failure analysis of lithium ion batteries[J].Energy Storage Science and Technology,2017,6(5):1008-1025. | |
| 6 | 李昭宇,李红朝,陶亮,等.LiFePO4/石墨电池高温循环失效分析[J].电池,2022,52(4):396-400. |
| LI Zhaoyu, LI Hongchao, TAO Liang,et al.Cycle failure analysis of LiFePO4/graphite battery at high temperature[J].Battery Bimonthly,2022,52(4):396-400. | |
| 7 | 刘晓梅,姚斌,谢乐琼,等.磷酸铁锂动力电池常温循环衰减机理分析[J].储能科学与技术,2021,10(4):1338-1343. |
| LIU Xiaomei, YAO Bin, XIE Leqiong,et al.Analysis of the capacity fading mechanism in lithium iron phosphate power batteries cycled at ambient temperatures[J].Energy Storage Science and Technology,2021,10(4):1338-1343. | |
| 8 | 吴小兰,王光俊,陈炜,等.复合三元电池高温循环劣化分析[J].电池,2017,47(6):347-350. |
| WU Xiaolan, WANG Guangjun, CHEN Wei,et al.Degradation analysis of composite ternary battery after high temperature cycle[J].Battery Bimonthly,2017,47(6):347-350. | |
| 9 | 阮一钊,田艳红,李守涛,等.LiNi0.5Co0.2Mn0.3O2/石墨电池高温失效的机理[J].电池,2020,50(3):220-223. |
| RUAN Yizhao, TIAN Yanhong, LI Shoutao,et al.High temperature failure mechanism of LiNi0.5Co0.2Mn0.3O2/graphite battery[J].Battery Bimonthly,2020,50(3):220-223. | |
| 10 | YANG Yue.Capacity fade characteristics of lithium iron phosphate cell during dynamic cycle[J].Energy,2020,206.Doi:10.1016/j.energy.2020.118155. |
| 11 | 倪江锋,周恒辉,陈继涛,等.锂离子电池中固体电解质界面膜(SEI)研究进展[J].化学进展,2004,16(3):335-342. |
| NI Jiangfeng, ZHOU Henghui, CHEN Jitao,et al.Progress in solid electrolyte interface in lithium ion batteries[J].Progress in Chemistry,2004,16(3):335-342. | |
| 12 | 王利.磷酸铁锂电极界面反应机制研究[D].徐州:中国矿业大学,2016. |
| WANG Li.Electrode/electrolyte interfaces reaction mechanisms studies of LiFePO4[D].Xuzhou:China University of Mining and Technology,2016. | |
| 13 | 王振,李建玲,王康康,等.磷酸铁锂/石墨动力电池衰退机理分析[J].稀有金属与硬质合金,2020,48(3):60-66. |
| WANG Zhen, LI Jianling, WANG Kangkang,et al.Analysis of capacity fading mechanisms of LiFePO4/graphite power battery[J].Rare Metals and Cemented Carbides,2020,48(3):60-66. | |
| 14 | MING Jun, CAO Zhen, WU Yingqiang,et al.New insight on the role of electrolyte additives in rechargeable lithium ion batteries[J].ACS Energy Letters,2019,4(11):2613-2622. |
| 15 | ZHANG Ningxin, TANG Huaqiong.Dissecting anode swelling in commercial lithium-ion batteries[J].Journal of Power Sources,2012,218:52-55. |
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