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2222材料工程  2021, Vol. 49 Issue (2): 21-31    DOI: 10.11868/j.issn.1001-4381.2020.000532
  综述 本期目录 | 过刊浏览 | 高级检索 |
PAA类黏结剂在锂电池中电化学性能研究进展
刘梦如1,2, 叶诚曦1,2, 彭黎波1,2, 翁景峥1,2,*()
1 福建师范大学 化学与材料学院, 福州 350007
2 福建师范大学 福建高分子重点实验室, 福州 350007
Research progress in electrochemical properties of lithium batteries with PAA binders
Meng-ru LIU1,2, Cheng-xi YE1,2, Li-bo PENG1,2, Jing-zheng WENG1,2,*()
1 College of Chemistry and Materials Science, Fujian Normal University, Fuzhou 350007, China
2 Fujian Key Laboratory of Polymer Science, Fujian Normal University, Fuzhou 350007, China
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摘要 

黏结剂是维持极片完整性必不可少的部分，对电池比容量、循环稳定等性能的提高非常重要。聚丙烯酸（PAA）因含有较多极性官能团，可溶于水，而被用作锂电池正负极黏结剂。PAA黏附性好，但极性基团使得分子链间形成的氢键导致PAA链刚性较大，不利于维持充放电过程中极片的完整性，因此，控制PAA官能团数量、改变官能团种类及PAA分子链结构，对锂电池电性能的提高势在必行。本文综述了近几年锂电池用PAA黏结剂的研究进展，重点介绍了PAA黏结剂的结构特性、改性及应用方式及其对不同种锂电池首次库伦效率、循环稳定性和阻抗性能的影响，并对PAA黏结剂的未来改性研究热点做了展望，探索PAA引入不同结构的弹性或导电聚合物后，对于黏结剂本身性能的影响，改善界面性能，以适用于不同活性材料正负极，提高锂离子传输速率，更好地提高锂电池的使用性能。
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刘梦如
叶诚曦
彭黎波
翁景峥
关键词 ： 锂电池,  黏结剂,  PAA,  循环性能,  阻抗性能    
Abstract：

Electrode binder is an essential part to maintain the integrity of electrode, and it is very important to improve the specific capacity and cycle stability of the battery. Polyacrylic acid (PAA) is widely used as the binder of anode or cathode in the lithium batteries because it contains more polar functional groups and can be dissolved in water. Due to possessing a lot of polar groups, PAA binder has better adhesion. But the hydrogen bond formed between the molecular chains by polar groups makes the PAA molecular chain more rigid, which is not conducive to maintaining the integrity of the electrodes during charging and discharging. It indicates that controlling the number of PAA functional groups and changing the type of functional groups/molecular chain structure of PAA binder have a great influence on the improvement of battery performance. The effect of PAA binder on electrochemical performance of lithium battery in recent years was reviewed in this paper, focusing on the structural characteristics, modification and application methods and their effects on the initial coulombic efficiency, cycling stability and impedance of different lithium batteries. Perspectives on the future of modified PAA binder were reviewed. The effects on the performance of the binder were explored after introducing different structures such as elastic or conductive groups. Improving the interface performance is to be suitable for cathode and anode with different active materials, and to improve the lithium ion diffusion coefficient. Then the performance of lithium battery is also enhanced.
Key words： lithium battery    binder    PAA    cycling performance    impedance performance
收稿日期: 2020-06-12      出版日期: 2021-02-27
中图分类号:  TM912.9  
基金资助:福建省引导性（重点）项目(2018H0009);福建省科技厅高校产学合作项目(2016H6006);福州市科技局资助项目(2017-G-68)
通讯作者: 翁景峥     E-mail: jackyweng@vip.163.com
作者简介: 翁景峥(1972-), 男, 副研究员, 博士, 研究方向为锂电池用黏结剂, 联系地址: 福州市仓山区对湖街道上三路32号福建师范大学化学与材料学院(350007), E-mail: jackyweng@vip.163.com
引用本文:   
刘梦如, 叶诚曦, 彭黎波, 翁景峥. PAA类黏结剂在锂电池中电化学性能研究进展[J]. 材料工程, 2021, 49(2): 21-31.
Meng-ru LIU, Cheng-xi YE, Li-bo PENG, Jing-zheng WENG. Research progress in electrochemical properties of lithium batteries with PAA binders. Journal of Materials Engineering, 2021, 49(2): 21-31.
链接本文:  
http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2020.000532      或      http://jme.biam.ac.cn/CN/Y2021/V49/I2/21
Fig.1  PAA的结构式
Fig.2  PAA黏结剂与活性材料间的作用机理图
Fig.3  PAA黏结剂解决活性材料体积变化的模型图
Fig.4  PAA-BP黏结剂的合成方法及其适应硅颗粒体积膨胀示意图[71]
(a)功能化PAA-BP黏结剂的合成方法；(b)PAA-BP黏结剂适应充放电循环期间硅阳极的体积膨胀示意图
Binder ICE/% Growth rate/%
Target group Control group
PAANa[65] ≈100 78.5 21.5
PDA-PAA-PEO[29] 74 68 8.1
c-LiPAACA-20% laponite[72] 99.89 99.18 0.71
Table 1  不同PAA黏结剂较PVDF对不同电极首次库仑效率的影响
Binder ICE/% Growth rate/%
Target group Control group
PAA-GA[27] 86.5 85.8 0.81
PVA-g-10PAA[28] 82.4 74.1 10.07
PAA-GL[61] 88.87 87.35 1.71
PAA-Rosin (1∶1)[66] 86.6 85.7 1.04
PAA-PVA (2∶1)[33] 98.5 95.6 2.94
c-PAA-DS[73] 61.3 57.6 6.04
Table 2  不同改性PAA黏结剂较纯PAA对不同电极首次库仑效率的影响
Fig.5  采用PAA-PVA(2∶1)黏结剂的LiFePO4/C正极的倍率性能图[33]
BinderCapacity retention/%Growth rate/%N/cycle
Target group Control group
PAALi[74] 90.8 100 at 0.2 C
ACC-PAA[57] 75 50 33.33 100 at 600 mA·g-1
PAA-PR[70] 97.6 100 at 0.5 C
PVA-g-10PAA[28] 61.4 31.9 48.05 150 at 400 mA·g-1
Table 3  不同改性PAA黏结剂较纯PAA在不同电极中多次循环后的容量保持率
BinderCapacity retention/%Growth rate/%N/cycle
Target group Control group
PAA-GA[27] 81 69.6 14.07 285 at 0.2 C
PAA-10% PANI[67] 56.5 11.3 80 300 at 1 C
PAA-PVA (2∶1)[33] 100.0 88.8 11.2 300 at 5 C
c-PAA-DS [73] Increased 71 >29 500 at 500 mA·g-1
1000 at 5 A·g-1
PVA-g-10PAA[28] 40.3 1000 at 400 mA·g-1
Table 4  不同改性PAA黏结剂纯PAA在不同电极中长期循环后的容量保持率
BinderRSEI/ΩReduction rate/%RCT/ΩReduction rate/%
Target group Control group Target group Control group
PAA-EDTA (9∶1)[41] 16.1 37.9 57.52
CS-PAANa[76] 4.00 4.75 15.79 33.51 76.30 56.08
PAA-PAA/PMA (1∶1)[62] 2.5 7.3 65.75 52.8 156.8 66.33
PAA-PVA (2∶1)[33] 18.0 28.8 37.5
Table 5  不同改性PAA黏结剂较纯PAA在不同电极中的阻抗数据表
BinderDLi/(cm2·s-1)Growth rate/%
Target group Control group
PAA-EDTA (9∶1)[41] 3.92×10-14 3.19×10-15 1128.84
CS-PAANa[76] 5.41×10-15 2.78×10-15 94.6
PAA-PVA (2∶1)[33] 6.8×10-12 1.5×10-13 4433.33
Table 6  不同改性PAA黏结剂较纯PAA在不同电极中的锂离子扩散系数
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