锂电负极废涂布浆料破胶减容与资源化利用

doi:10.16085/j.issn.1000-6613.2023-1019

化工进展 ›› 2024, Vol. 43 ›› Issue (8): 4664-4673.DOI: 10.16085/j.issn.1000-6613.2023-1019

• 资源与环境化工 • 上一篇

锂电负极废涂布浆料破胶减容与资源化利用

曾祥菲¹(), 韩昀晖¹, 林凡¹, 黄荣¹, 余茜¹, 黄瑶¹, 王蓉², 舒建成¹, 陈梦君¹()

^1.西南科技大学固体废物处理与资源化教育部重点实验室，四川绵阳 621010
^2.西南科技大学国防与科技学院，四川绵阳 621010

收稿日期:2023-06-20 修回日期:2023-10-02 出版日期:2024-08-15 发布日期:2024-09-02
通讯作者: 陈梦君
作者简介:曾祥菲（1995—），男，博士研究生，研究方向为废弃锂离子电池污染控制与循环利用。E-mail：1084121519@qq.com。
基金资助:
四川省自然科学基金（青年科学基金）(2022NSFSC1026);西南科技大学研究生创新基金(24ycx3006)

Gel breaking-capacity reduction and reutilization of waste lithium anode coating slurry

ZENG Xiangfei¹(), HAN Yunhui¹, LIN Fan¹, HUANG Rong¹, YU Xi¹, HUANG Yao¹, WANG Rong², SHU Jiancheng¹, CHEN Mengjun¹()

^1.Key Laboratory of Solid Waste Treatment and Resource Recycle (SWUST), Ministry of Education, Southwest University of Science and Technology, Mianyang 621010, Sichuan, China
^2.College of National Defense Technology, Southwest University of Science and Technology, Mianyang 621010, Sichuan, China

Received:2023-06-20 Revised:2023-10-02 Online:2024-08-15 Published:2024-09-02
Contact: CHEN Mengjun

摘要/Abstract

摘要：

锂电负极废涂布浆料含水率高、胶态分散稳定性强，难以过滤。本文研究了废涂布浆料的胶态特性，分析了废浆料的高效破胶分离机理，并对其资源化进行了初步探索。羧甲基纤维素钠（CMC-Na）解离产生的羧基负离子（R-COO^-）提供的静电斥力及苯乙烯-丁二烯橡胶（SBR）在颗粒间形成的空间位阻力是废浆料胶态稳定性的根本原因。酸度的降低能够抑制浆料中CMC-Na的解离，减少吸附于石墨颗粒表面的带电基团R-COO^-，削弱静电斥力，造成颗粒团聚，并破坏SBR的架桥作用。pH=2.0时，废浆料破胶过滤效率较佳，过滤常数为0.0741m²/s，含水率降低48个百分点；X射线三维显微成像分析（X-CT）表明细微颗粒团聚破胶的同时，保留的静电斥力能够降低过滤阻力，促进滤饼孔道结构的发育，生成大孔隙半径，长喉道的渗流网络减少滤饼孔道吸附水的量；分离所得固相碳材对亚甲基蓝、铬（Cr⁶⁺）、COD的吸附量分别为435mg/g、0.645mg/g、87mg/g，满足《工业水处理用活性炭技术指标及试验方法》（LY/T 3279—2021）优级品标准。

关键词: 锂电, 胶体, 团聚, 涂布浆料, 过滤, 资源化

Abstract:

Waste lithium anode coating slurry is hard to filtrate and also hard to be reutilized since it contains high water content, which is strongly stable with a wonderful colloid dispersion. The colloidal properties of this waste coating slurry were characterized, its high-efficiency rubber breaking separation mechanisms were discussed, and its reutilization as active carbon was also investigated. The electrostatic repulsion provided by the carboxyl anion (R-COO^-) produced by the dissociation of sodium carboxymethylcellulose (CMC-Na) and the spatial resistance formed between particles by styrene-butadiene rubber (SBR) were the fundamental reasons for the colloidal stability of waste slurry. The decrease in acidity effectively suppressed the dissociation of carboxymethyl cellulose sodium (CMC-Na) in the slurry, resulting in reduced adsorption of charged groups (R-COO^-) onto the surface of graphite particles. Consequently, the electrostatic repulsion between particles weakened, facilitating particle agglomeration and undermining the cross-linking effect of styrene-butadiene rubber (SBR). When pH was 2.0, the filtration constant of the waste slurry escalated to 0.0741m²/s, resulting in a remarkable 48 percentage point reduction in moisture content. X-ray three-dimensional microscopy analysis (X-CT) showed that while fine particles agglomerated and broken, the retained electrostatic repulsion could reduce the filtration resistance, promote the development of the filter cake pore structure, generate a large pore radius, and the seepage network of the long throat channel reduced the amount of water adsorbed by the filter cake pores. Moreover, the separated solid carbon material demonstrated impressive adsorption capacities of 435mg/g, 0.645mg/g and 87mg/g for methylene blue, chromium (Cr⁶⁺) and COD, respectively. These values adhered to the first-rate standards set forth in the “LY/T 3279—2021”.

Key words: lithium battery, colloid, agglomeration, coating slurry, filtration, reutilization

中图分类号:

X789

曾祥菲, 韩昀晖, 林凡, 黄荣, 余茜, 黄瑶, 王蓉, 舒建成, 陈梦君. 锂电负极废涂布浆料破胶减容与资源化利用[J]. 化工进展, 2024, 43(8): 4664-4673.

ZENG Xiangfei, HAN Yunhui, LIN Fan, HUANG Rong, YU Xi, HUANG Yao, WANG Rong, SHU Jiancheng, CHEN Mengjun. Gel breaking-capacity reduction and reutilization of waste lithium anode coating slurry[J]. Chemical Industry and Engineering Progress, 2024, 43(8): 4664-4673.

图/表 14

图1 废涂布浆料稳定分散原理

图2 锂电负极废涂布浆料

图3 正压桶式过滤器

图4 废涂布浆料胶态特性（a）烘干样XRD; （b） CMC-Na与乙炔黑XRD; （c）、（d） SEM-Mapping；（e）粒径分布; （f）极片微结构; （g）、（h） FTIR与添加剂结构

图5 不同pH条件废涂布浆料zeta电位与粒径分布

表1 不同pH条件下废涂布浆料的过滤参数

pH	过滤时间 /min	滤液体积 /mL	透过率 /mL·min^-1	滤饼含水率 /%
1.0	8.40	143	17.02	48.47
1.5	12.06	144	11.94	52.14
2.0	13.01	142	10.91	46.97
2.5	15.06	141	9.36	51.69
3.0	18.31	142	7.76	51.32
6.0（原浆料）	—	0	0	95.00

图6 不同pH条件下废涂布浆料过滤性能

表2 不同pH条件下滤饼孔隙尺寸参数

样品	孔隙率/%	孔隙数	喉道数	平均孔隙半径/μm	平均喉道长度/μm
pH=1.0滤饼	7.95	6209	5476	52.20	105.36
pH=2.0滤饼	0.34	56	21	104.23	212.64

图7 pH=1.0废涂布浆料滤饼X-CT分析

图8 pH=2.0废涂布浆料滤饼X-CT分析

图9 不同pH条件下废涂布浆料FTIR分析及CMC-Na、SBR结构演变

图10 较佳pH条件破胶废涂布浆料与原浆料SEM-Mapping分析原废浆料：（a）、（b） pH=2.0；（c）、（d）pH=6.0

图11 不同pH条件下分离所得碳材料XRD谱图

表3 废涂布浆料再生活性炭吸附性能

污染物种类	吸附值/mg·g^-1	标准参考值/mg·g^-1
污染物种类	吸附值/mg·g^-1	优级品	合格品
碘	66	700	500
亚甲基蓝	435	120	90
铬（Cr⁶⁺）	0.645	0.5
COD	87	40	35

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锂电负极废涂布浆料破胶减容与资源化利用

Gel breaking-capacity reduction and reutilization of waste lithium anode coating slurry

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