石墨毡电极与集流体的简单可靠粘接及其在电解中的应用

摘要石墨毡有比表面积大、导电性强、廉价易得等优点，被认为是极具应用前景的三维电极材料。为使电极与集流体良好接触，采用高导电碳黑做导电填料、聚偏氟乙烯做粘接剂制备了导电胶，实现了对石墨毡电极与柔性石墨纸集流体的简单可靠粘接。探究了导电胶配比、涂胶量和固化压力条件对石墨毡-集流体粘接试样导电性能和粘结强度的影响。粘接试样的接触电阻相较于靠压紧的无胶试样降低了50%，拉伸剪切强度达到与石墨毡自身强度接近的25.3×10^-3 MPa。将胶粘石墨毡电极用于印刷电路板酸性氯化铜蚀刻液的电解再生和铜回收，单槽电压降低了0.08 V。这使得以金属铜计的电解再生和铜回收的比能耗降低了80 kW·h·t^-1。

	Service

	把本文推荐给朋友
	加入我的书架
	加入引用管理器
	Email Alert
	RSS
	作者相关文章
	刘梦真
	常艳
	张文
	王宇新

关键词：三维复合电极；导电胶；接触电阻；槽电压

Abstract： Graphite felt is a good material for making three dimensional electrodes because of its large specific surface area, high conductivity, low cost and easy availability. To make sure good contact between the electrode and the current collector, a facile and reliable adhesion between a graphite felt electrode and a current collector of flexible graphite paper was realized by using an in-house made conductive adhesive made up of highly conductive carbon black as the filler and polyvinylidene fluoride as the binder. The influences of the adhesive composition, the amount of the adhesive used and the curing pressure on the contact resistance and adhesion strength between the graphite felt and the flexible graphite paper were investigated. In contrast to the case without using adhesive, the interface adhered under suitable conditions shows a marked drop of contact resistance by 50% in a wet environment. Meanwhile the tensile shear strength of the adhered samples reaches 25.3×10^-3 MPa, which is at the same magnitude as the strength of the felt. When applied to the electrolytic regeneration of acidic copper chloride etchant in printed circuit board production, the adhering method results in a drop of single cell voltage by 0.08 V. This would translate into a reduction of power consumption by 80 kW·h for 1 ton of metal copper recovered.

Keywords： 3D composite electrode； conductive adhesive； contact resistance； cell voltage

Received 2017-10-13;

Fund:天津市科技支撑计划项目"印刷电路板酸性蚀刻液现场再生和铜回收技术"（15ZCZDSF00040）。

Corresponding Authors: 王宇新,E-mail:yxwang@tju.edu.cn Email: yxwang@tju.edu.cn

About author: 刘梦真(1994-),女,硕士研究生,现从事酸性蚀刻液电化学回收研究。

引用本文:

刘梦真, 常艳, 张文, 王宇新.石墨毡电极与集流体的简单可靠粘接及其在电解中的应用[J]. 化学工业与工程, 2018,35(6): 41-47

Liu Mengzhen, Chang Yan, Zhang Wen, Wang Yuxin.A Facile and Reliable Method of Adhering Graphite Felt Electrode to Current Collector and Its Application in Electrolysis[J]. Chemcial Industry and Engineering, 2018,35(6): 41-47

[1] 吉小庆, 王宇新. 氮掺杂石墨毡用做电化学回收酸性蚀刻液阳极[J]. 化学工业与工程, 2016, 33(5):50-55 Ji Xiaoqing, Wang Yuxin. Nitrogen doped graphic felt as anode for electrochemical regeneration of acidic cupric chloride etchant[J]. Chemical Industry and Engineering, 2016, 33(5):50-55(in Chinese)
[2] Yang Z, Huang C, Wang Y, et al. A new electrolytic method for on-site regeneration of acidic copper(Ⅱ)chloride etchant in printed circuit board prodution[J]. International Journal of Electrochemical Science, 2013, 8(5):6258-6268
[3] 钱鹏, 张华民, 陈剑, 等. 全钒液流电池用电极及双极板研究进展[J]. 能源工程, 2007, (1):7-11 Qian Peng, Zhang Huamin, Chen Jian, et al. Progress on electrode and bipolar plate materials for vanadium redox flow batteries[J]. Energy Engineering, 2007, (1):7-11(in Chinese)
[4] Qian P, Zhang H, Chen J, et al. A novel electrode-bipolar plate assembly for vanadium redox flow battery applications[J]. Power Sources, 2008, 175(1):613-620
[5] 崔旭梅, 王军, 陈孝娥, 等. 全钒氧化还原液流电池一体化复合电极的研究[J]. 电源技术, 2009, 33(11):1019-1021 Cui Xumei, Wang Jun, Chen Xiaoe, et al. Study of integral electrode of vanadium redox flow battery[J]. Chinese Journal of Power Sources, 2009, 33(11):1019-1021(in Chinese)
[6] Wang J, Song X, Wang Y, et al. Effects of electrode material and substrate concentration on the bioenergy output and wastewater treatment in air-cathode microbial fuel cell integrating with constructed wetland[J]. Ecological Engineering, 2017, 99:191-198
[7] 潘贵芳. 石墨毡催化电极制备及其电化学氧化性能研究[D]. 石家庄:河北科技大学, 2016 Pan Guifang. Preparation and electrochemical oxidation performance of catalytic graphite felt electrode[D]. Shijiazhuang:Hebei University of Science and Technology, 2016(in Chinese)
[8] 武彦斌, 王三反, 张学敏, 等. 石墨毡电极预处理模拟邻甲酚废水[J]. 化工环保, 2014, 34(4):311-315 Wu Yanbin, Wang Sanfan, Zhang Xuemin, et al. Pretreatment of simulated o-cresol-containing wastewater with graphite felt electrode[J]. Environmental Protection of Chemical Industry, 2014, 34(4):311-315(in Chinese)
[9] Cui L, Ji M, Mao L, et al. Ni-Seeded growth of carbon nanotubes on graphite felt for high-performance supercapacitors[J]. Journal of the Electrochemical Society, 2016, 163(9):A2017-A2021
[10] Wang G, Zhang L, Zhang J. A review of electrode materials for electrochemical supercapacitors[J]. Chemical Society Reviews, 2012, 43(18):797-807
[11] Zhang L, Zhao X. Carbon-Based materials as supercapacitor electrodes[J]. Chemical Society Reviews,2009, 38(9):2520-2531
[12] Lim B S, Lu H, Choi C, et al. Recovery of silver metal and electric power generation using a microbial fuel cell[J]. Desalination and Water Treatment, 2015, 54(13):3675-3681
[13] Gorgievski M, Bozi? D, Stankovi? V, et al. Copper electrowinning from acid mine drainage:A case study from the closed mine "Cerovo"[J]. Journal of Hazardous Materials, 2009, 170(2/3):716-721
[14] Cheng C, Kelsall G H, Pilone D. Modelling potentials, concentrations and current densities in porous electrodes for metal recovery from dilute aqueous effluents[J]. Journal of Applied Electrochemistry, 2005, 35(12):1191-1202
[15] Lim J W, Dai G. Carbon fiber/polyethylene bipolar plate-carbon felt electrode assembly for vanadium redox flow batteries (VRFB)[J]. Composite Structures, 2015, 134:483-492
[16] Kim K H, Bu G, Dai G. Development of carbon composite bipolar plate (BP) for vanadium redox flow battery (VRFB)[J]. Composite Structures, 2014, 109(1):253-259
[17] 乔永莲. 导电塑料复合电极及其制作方法:CN, 102569825A[P]. 2012-02-18
[18] 任兴华, 张卫中. 一种石墨毡锂溴离子液体电容电池电极:CN, 203367026U[P]. 2013-02-22
[19] 吴涛. 全钒液流电池石墨毡电极改性研究[D]. 长沙:中南大学, 2011 Wu Tao. Modification on graphite felt electrode for vanadium redox battery[D]. Changsha:Central South University, 2011(in Chinese)
[20] 杜琳. 基于纳米碳材料和导电聚合物修饰的高性能微生物燃料电池阳极材料的研究[D]. 郑州:郑州大学, 2016 Du Lin. High performance microbial fuel cell anode materials based on nano-carbon material and conductive polymer[D]. Zhengzhou:Zhengzhou University, 2016(in Chinese)
[21] 陈爱群. 聚偏氟乙烯的特性和用途[J]. 有机氟工业, 1989, (4):1-14 Chen Aiqun. Characteristics and uses of polyvinylidene fluoride[J]. Organo-Fluorine Industry, 1989, (4):1-14(in Chinese)
[22] Chen P, Fang F, Zhang Z, et al. Self-Assembled graphene film to enable highly conductive and corrosion resistant aluminum bipolar plates in fuel cells[J]. International Journal of Hydrogen Energy, 2017, 42(17):12593-12600
[23] 中华人民共和国国家质量监督检验检疫总局. GB/T 7124-2008胶粘剂拉伸剪切强度的测定[S].北京:中国标准出版社, 2008
[24] 王春振, 张文, 王宇新, 等. KOH活化石墨毡阳极用于印刷电路板蚀刻液的电解再生[J]. 化学工业与工程, 2016, 35(5):19-27 Wang Chunzhen, Zhangwen, Wang Yuxin, et al. Preparation and performance of KOH activated graphite felt anode for electrolytic regeneration of PCB etchant[J]. Chemical Industry and Engineering, 2016, 35(5):19-27(in Chinese)
[25] 王红华, 蒋玉思. 酸性氯化铜液蚀刻化学及蚀刻液再生方法评述[J]. 印制电路信息, 2008, (10):57-60 Wang Honghua, Jiang Yusi. The chemistry of acidic cupric chloride etching process and review on regenerating methods for cupric chloride etchant[J]. Printed Circuit Information, 2008, (10):57-60(in Chinese)
[26] 董丽荣, 张伊玮, 王莉, 等. 胶黏剂配方及使用工艺对背板层间粘结力的影响[J]. 信息记录材料, 2016, 17(5):103-105 Dong Lirong, Zhang Yiwei, Wang Li, et al. Adhesive formula and use technology to the influence of the cohesive force between the layers[J]. Information Recording Materials, 2016, 17(5):103-105(in Chinese)