磷酸铁锂高温循环性能的改善

doi:10.19964/j.issn.1006-4990.2021-0678

Abstract

Abstract:

LiFePO₄ has stable structure and excellent cycle performance，but with the continuous improvement of the quality assurance requirements of the host manufacturer，LiFePO₄ still faces the situation that the high?temperature cycle performance can not meet the requirements of customers.Taking LiFePO₄ cathode lithium?ion battery as the research object，the effect of the basic electrolyte system and the improved electrolyte[adding lithium difluorodioxalate borate（LiODFB） to the basic electrolyte] system on the high-temperature cycle performance of the battery were compared.The non?destructive analysis methods such as DC internal resistance（DCIR），electrochemical AC impedance spectroscopy（EIS），dQ/dU（change of battery capacity in constant voltage interval） curve were used to compare the data of the recycled battery.The results showed that the charge transfer impedance of the battery with improved electrolyte system was further reduced.Through the dissection of the battery，the thickness analysis，X-ray diffraction（XRD） analysis，scanning electron microscope（SEM） analysis and inductively coupled plasma emission spectroscopy（ICP） element analysis of the battery electrode sheets of the two electrolyte systems were carried out.The results showed that the battery with improved electrolyte system had obvious effects in inhibiting the side reactions on the surface of the negative electrode and reducing the dissolution of positive iron，so the high temperature cycle performance of the battery was better.

Key words: LiFePO₄, high temperature cycle, electrolyte, anode film

CLC Number:

TM912.9

XU Ruilin,ZHAO Lipeng,LIU Xingwei,LIU Huan,WANG Hao,XU Xiaoming,ZENG Tao. Improvement of high temperature cycling performance of LiFePO₄[J]. Inorganic Chemicals Industry, 2022, 54(9): 108-112.

Figures/Tables 9

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Table1

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Table 3

References 16

[1]	YAMADA Y， USUI K， SODEYAMA K， et al.Hydrate⁃melt electrolytes for high⁃energy⁃density aqueous batteries[J].Nature Energy，2016，1.Doi:10.1038/nenergy.2016.129. doi: 10.1038/nenergy.2016.129.
[2]	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.
[3]	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.
[4]	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.
[5]	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.
[6]	HUANG W， ATTIA P M， WANG Hansen， et al.Evolution of the solid⁃electrolyte interphase on carbonaceous anodes visualized by atomic⁃resolution cryogenic electron microscopy[J].Nano Letters，2019，19（8）:5140-5148.
[7]	HOU Zhiguo， DONG Mengfei， XIONG Yali， et al.Formation of so⁃lid⁃electrolyte interfaces in aqueous electrolytes by altering cation⁃solvation shell structure[J].Advanced Energy Materials，2020，10（15）.Doi:10.1002/aenm.201903665. doi: 10.1002/aenm.201903665.
[8]	HOU Chen， HAN Jiuhui， LIU Pan， et al.Operando observations of SEI film evolution by mass⁃sensitive scanning transmission electron microscopy[J].Advanced Energy Materials，2019，9（45）.Doi:10.1002/aenm.201902675. doi: 10.1002/aenm.201902675.
[9]	LOULI A J， ELLIS L D， DAHN J R.Operando pressure measurements reveal solid electrolyte interphase growth to rank Li⁃ion cell performance[J].Joule，2019，3（3）:745-761.
[10]	Duan BIN， WANG Fei， TAMIRAT A G， et al.Progress in aqueous rechargeable sodium⁃ion batteries[J].Advanced Energy Materials，2018，8（17）.Doi:10.1002/aenm.201703008. doi: 10.1002/aenm.201703008.
[11]	张婷，林森，于建国.磷酸铁锂正极材料的制备及性能强化研究进展[J].无机盐工业，2021，53（6）:31-40.
	ZHANG Ting， LIN Sen， YU Jianguo.Research progress in synthesis and performance enhancement of LiFePO₄ cathode materi⁃als[J].Inorganic Chemicals Industry，2021，53（6）:31-40.
[12]	周丹，梁风，姚耀春.锂离子电池电解液负极成膜添加剂的研究进展[J].化工进展，2016，35（5）:1477-1483.
	ZHOU Dan， LIANG Feng， YAO Yaochun.Research progress of ne⁃gative film⁃forming additives in electrolyte for Li⁃ion batteries[J].Chemical Industry and Engineering Progress，2016，35（5）:1477-1483.
[13]	付茂华，黄可龙，刘素琴，等.二氟二草酸硼酸锂对LiFePO₄/石墨电池高温性能的影响[J].物理化学学报，2009，25（10）:1985-1990.
	FU Maohua， HUANG Kelong， LIU Suqin， et al.Effect of lithium difluoro（oxalato）borate on the high⁃temperature performance of LiFePO₄/graphite batteries[J].Acta Physico-Chimica Sinica，2009，25（10）:1985-1990.
[14]	AGUBRA V A， FERGUS J W， FU Rujian， et al.Analysis of effects of the state of charge on the formation and growth of the deposit layer on graphite electrode of pouch type lithium ion polymer batteries[J].Journal of Power Sources，2014，270:213-220.
[15]	贺雨雨，陈炜，冯德圣，等.黏结剂对锂离子电池负极膨胀的影响[J].电池，2017，47（3）:169-172.
	HE Yuyu， CHEN Wei， FENG Desheng， et al.Effects of binders on swelling of anode for Li⁃ion battery[J].Battery Bimonthly，2017，47（3）:169-172.
[16]	郑勇，李建玲，王新东.磷酸铁锂/石墨动力电池的高温衰减机制研究[J].材料导报，2016，30（10）:15-18，32.
	ZHENG Yong， LI Jianling， WANG Xindong.Capacity fading mechanism of LiFePO₄/graphite power battery at high temperature[J].Materials Review，2016，30（10）:15-18，32.

SOC/%	DCIR/mΩ		SOC/%	DCIR/mΩ
SOC/%	基础电解液体系	改善电解液体系	SOC/%	基础电解液体系	改善电解液体系
95	15.7	15.1	45	17.9	18.1
90	16.4	15.8	40	18.2	18.0
85	16.7	16.4	35	18.6	18.2
80	17.6	17.4	30	18.9	18.3
75	18.5	18.3	25	19.0	18.3
70	18.3	17.1	20	19.7	19.1
65	17.4	17.3	15	21.4	19.8
60	17.4	17.5	10	22.0	19.6
55	17.6	17.7	5	26.1	23.0
50	17.8	18.0	0	38.8	31.7

项目		初始极片厚度/μm	EOL极片厚度/μm	极片厚度变化率/%
正极片	改善电解液体系	155	160	3.2
正极片	基础电解液体系	155	169	9.0
负极片	改善电解液体系	114	128	12.3
负极片	基础电解液体系	114	147	28.9

电解液体系	电池负极表面w（Fe）/10^-6
基础电解液	146.7
改善电解液	73.5

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Improvement of high temperature cycling performance of LiFePO₄

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Improvement of high temperature cycling performance of LiFePO4