KOH活化石墨毡阳极用于印刷电路板蚀刻液的电解再生
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摘要
石墨毡电极的润湿性和电化学活性对印刷电路板蚀刻液电解再生装置的性能有重要影响。在900℃下,用KOH对石墨毡进行活化处理,并将KOH活化石墨毡作为电解池阳极对酸性蚀刻废液进行电解再生。用SEM、XPS表征和分析了活化前后石墨毡炭纤维的表面形貌和元素组成。通过循环伏安(CV)和电化学阻抗谱(EIS)分析了石墨毡电极的电化学性能。结果表明,KOH活化石墨毡炭纤维表面含氧量由原始石墨毡的2.60%(原子百分数,下同)增加到6.27%,润湿性得到改善。缺陷C数量增多,对Cu(I)电化学氧化活性提高。KOH活化石墨毡比表面积较原始石墨毡增加了约42倍。KOH活化石墨毡用于电解实验,阳极电势和槽电压较原始石墨毡分别降低0.10和0.05~0.06 V。
The wettability and electrochemical activity of the graphite felt(GF) have a significant impact on the performance of the apparatus for electrolytic regeneration of PCB etchant. GF activated with KOH at 900 ℃ is employed as the anode of the cell for electrolytic regeneration of acidic CuCl_2 etchant. The morphology and the element composition of activated GF and untreated GF are characterized by SEM and XPS, respectively. The electrochemical performance of the two GF electrodes is evaluated through cyclic voltammetry(CV) and electrochemical impedance spectroscopy(EIS). The results show that the oxygen content of the activated GF increases to 6.27 at% from 2.60 at% of the untreated GF, and the wettability is improved. The electrochemical activity towards oxidation of Cu(I) is improved, which can be ascribed to the increase of the number of the defective carbon. The BET specific surface of the GF increases by~42 times after KOH activation. The anode potential and the cell voltage of the activated GF decreases by 0.10 V and 0.05~0.06 V,respectively,compared with the untreated GF in the etchant electrolytic regeneration experiment.
The wettability and electrochemical activity of the graphite felt(GF) have a significant impact on the performance of the apparatus for electrolytic regeneration of PCB etchant. GF activated with KOH at 900 ℃ is employed as the anode of the cell for electrolytic regeneration of acidic CuCl_2 etchant. The morphology and the element composition of activated GF and untreated GF are characterized by SEM and XPS, respectively. The electrochemical performance of the two GF electrodes is evaluated through cyclic voltammetry(CV) and electrochemical impedance spectroscopy(EIS). The results show that the oxygen content of the activated GF increases to 6.27 at% from 2.60 at% of the untreated GF, and the wettability is improved. The electrochemical activity towards oxidation of Cu(I) is improved, which can be ascribed to the increase of the number of the defective carbon. The BET specific surface of the GF increases by~42 times after KOH activation. The anode potential and the cell voltage of the activated GF decreases by 0.10 V and 0.05~0.06 V,respectively,compared with the untreated GF in the etchant electrolytic regeneration experiment.
引文
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[15] Kim B J, Lee Y S, Park S J. A study on pore-opening behaviors of graphite nanofibers by a chemical activation process[J]. Journal of Colloid & Interface Science, 2007, 306(2): 454-458
[16] Romanos J, Beckner M, Rash T, et al. Nanospace engineering of KOH activated carbon[J]. Nanotechnology, 2012, 23(1): 1-8
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[19] Wang Y, Liu Y, Wang K, et al. Preparation and characterization of a novel KOH activated graphite felt cathode for the electro-Fenton process[J]. Applied Catalysis B: Environmental, 2015, 165: 360-368
[20] Park M, Jung Y, Kim J, et al. Synergistic effect of carbon nanofiber/nanotube composite catalyst on carbon felt electrode for high-performance all-vanadium redox flow battery [J]. Nano Letters, 2013, 13(10): 4 833-4 839
[21] Chao G, Wang N F, Peng S, et al. Influence of Fenton’s reagent treatment on electrochemical properties of graphite felt for all vanadium redox battery [J]. Electrochimica Acta, 2013, 88: 193-202
[2] 金鸿,陈森. 印制电路技术[M]. 北京: 化学工业出版社, 2003Jin Hong, Chen Sen. Printed circuit technology[M]. Beijing: Chemical Industry Press, 2003 (in Chinese)
[3] 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): 57-60Wang 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)
[4] Oxley J E. Electrolytic regeneration of acid cupric chloride etchant: US, 5421966[P]. 1995-06-06
[5] Garn P D, Sharpe L H. Etching bath for copper and regeneration thereof: US, 2964453[P]. 1960-12-13
[6] Parikh G D, Willard W C. Methods of electrolytic regenerative etching and metal recovery: US, 3784455[P]. 1974-07-08
[7] Rudi O, Heribert R. Method and apparatus for regeneration of a copper-containing etching solution: US, 4508599[P].1985-04-02
[8] Oxley J E, Smialek R J, Putt R A. Apparatus and a process for regenerating a CuCl2 etchant: US, 5705048[P]. 1998-06-06
[9] Hillis M R. Method for the electrolytic regeneration of etchants for metals: US, 4468308[P]. 1984-08-28
[10] 蒋玉思,黄奇书,张建华, 等. 印制电路板酸性蚀刻废液的膜电解再生[J]. 环境污染与防治,2011,33(8): 53-56Jiang Yusi, Huang Qishu, Zhang Jianhua, et al. Membrane electrolytic regeneration of spent acidic etchant for printed circuit board[J]. Environmental Pollution and Control, 2011, 33(8): 53-56 (in Chinese)
[11] Yang Z, Huang C, Ji X, et al. A new electrolytic method for on-site regeneration of acidic copper (II) chloride etchant in printed circuit board production[J]. International Journal of Electrochemical Science, 2013, 8(5): 6 258-6 268
[12] Zhang L, Shao Z, Wang X, et al. The characterization of graphite felt electrode with surface modification for H2/Br2 fuel cell[J]. Journal of Power Sources, 2013, 242(35): 15-22
[13] Zhang W, Xi J, Li Z, et al. Electrochemical activation of graphite felt electrode for VO+2/VO+2 redox couple application [J]. Electrochimica Acta, 2013, 89(1): 429-435
[14] 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): 50-55Ji Xiaoqing, Wang Yuxin. Nitrogen doped graphite felt as anode for electrochemical regeneration of acidic cupric chloride etchant [J]. Chemical Industry and Engineering, 2016, 33(5): 50-55 (in Chinese)
[15] Kim B J, Lee Y S, Park S J. A study on pore-opening behaviors of graphite nanofibers by a chemical activation process[J]. Journal of Colloid & Interface Science, 2007, 306(2): 454-458
[16] Romanos J, Beckner M, Rash T, et al. Nanospace engineering of KOH activated carbon[J]. Nanotechnology, 2012, 23(1): 1-8
[17] Lillo-Ródenas M A, Cazorla-Amorós D, Linares-Solano A. Understanding chemical reactions between carbons and NaOH and KOH-An insight into the chemical activation mechanism [J]. Carbon, 2003, 41: 267-275
[18] Volfkovich Y M, Rychagov A Y, Sosenkin V E. Measuring the specific surface area of carbon nanomaterials by different methods [J]. Russian Journal of Electrochemistry, 2014, 50(11): 1 099-1 101
[19] Wang Y, Liu Y, Wang K, et al. Preparation and characterization of a novel KOH activated graphite felt cathode for the electro-Fenton process[J]. Applied Catalysis B: Environmental, 2015, 165: 360-368
[20] Park M, Jung Y, Kim J, et al. Synergistic effect of carbon nanofiber/nanotube composite catalyst on carbon felt electrode for high-performance all-vanadium redox flow battery [J]. Nano Letters, 2013, 13(10): 4 833-4 839
[21] Chao G, Wang N F, Peng S, et al. Influence of Fenton’s reagent treatment on electrochemical properties of graphite felt for all vanadium redox battery [J]. Electrochimica Acta, 2013, 88: 193-202