碱性电解水析氢电极的研究进展

doi:10.16085/j.issn.1000-6613.2015.10.025

摘要/Abstract

摘要： 电解水制氢将成为未来绿色制氢工业的核心技术。研究新型阴极材料以有效降低阴极过电位,对降低电解水能耗和设备成本、提高生产稳定性和安全性,具有十分重要的现实意义。本文主要对碱性水溶液电解制氢工业的析氢阴极材料进行综述。围绕电极结晶结构设计和尺寸结构设计两个主要的电极发展方向,重点介绍了3类基于电沉积制备技术的Ni基电极材料:合金析氢电极、复合析氢电极、多孔析氢电极。分析了当前析氢电极在实验研发与工业应用中存在的问题。指出采用电沉积法,制备催化活性更高且适用于工业电解环境的多元复合电极材料将是今后析氢电极发展的趋势。

关键词: 电解, 制氢, 催化, 析氢电极, 电沉积

Abstract: Water electrolysis will become the core technology of environmental production for hydrogen industry in the future. It is very important to study new cathode materials for reducing the cathode overpotential. Because it not only can reduce energy consumption and the cost of water electrolysis, but also can enhance the stability and safety of production. This paper mainly discusses the research status of hydrogen electrode materials for alkaline water electrolysis. Based on the major improvement of catalytic activity for hydrogen evolution reaction, this paper mainly focuses on the electrodepositing preparation method for three kinds of nickel-based electrodes, which are alloy hydrogen evolution electrode, composite hydrogen evolution electrode, and porous hydrogen evolution electrode. The existing problems on hydrogen evolution electrode in experimental research and industrial application are analyzed. In the end, it is pointed out that the more catalytic activity and more stable electrochemical performance of multivariate composite electrodes based on electrodepositing preparation will be the future of hydrogen electrode development.

Key words: electrolysis, hydrogen production, catalysis, hydrogen evolution electrode, electrolytic deposition

中图分类号:

O646

张开悦, 刘伟华, 陈晖, 张博, 刘建国, 严川伟. 碱性电解水析氢电极的研究进展[J]. 化工进展, 2015, 34(10): 3680-3687,3778.

ZHANG Kaiyue, LIU Weihua, CHEN Hui, ZHANG Bo, LIU Jianguo, YAN Chuanwei. Research progress in hydrogen electrode materials for alkaline water electrolysis[J]. Chemical Industry and Engineering Progree, 2015, 34(10): 3680-3687,3778.

参考文献

[1] Lubitz W,Tumas W. Hydrogen:An overview[J]. Chemical Reviews,2007,107(10):3900-3903.

[2] 王庆斌,薛贺来,赵宇,等. 工业水电解制氢技术的发展与应用[J]. 气体分离,2011(2):47-50.

[3] Liu B,He J B,Chen Y J,et al. Phytic acid-coated titanium as electrocatalyst of hydrogen evolution reactionin alkaline electrolyte[J]. International Journal of Hydrogen Energy,2013,38(8):3130-3136.

[4] 付银辉,黎学明,李武林,等. Ni-Ru-Ir氧化物阴极涂层的析氢活性[J]. 电化学,2010,16(2):202-205.

[5] 王雯,黎学明,杨文静,等. Ni/PdO/RuO₂复合型电极的制备及表征[J]. 无机化学学报,2010,26(9):1633-1638.

[6] 邢家悟,康建忠,王玉兰,等. 活性阴极及其制备方法:中国,200610008084.9[P]. 2006-02-28.

[7] Derek P,Li X H,Wang S P. A comparision of cathodes for zero gap alkaline water electrolysers for hydrogen production[J]. International Journal of Hydrogen Energy,2012(37):7429-7435.

[8] Kellenberger A,Vaszilcsin N,Brandl W. Roughness factor evaluation of thermal arc sprayed skeleton nickel electrodes[J]. Journal of Solid State Electrochemistry,2007,11(1):84-89.

[9] SeoY-S,JungY-S,YoonW-L,et al. The effect of Ni content on a highly active Ni-Al₂O₃ catalyst prepared by the homogeneous precipitation method[J]. International Journal of Hydrogen Energy,2011,36(1):94-102.

[10] Shumin H,Zhong Z,Yuan L,et al. The effect of vacuum evaporation platingon phase structure and electrochemical properties of AB5-5 mass% LaMg₃ composite alloy[J]. Electrochimica Acta,2005,50(28):5491-5495.

[11] Rosalbino F,Delsante S,Borzone G,et al. Correlation of microstructure and catalytic activity of crystalline Ni-Co-Y alloy electrode for the hydrogen evolution reaction in alkaline solution[J]. Journal of Alloys and Compounds,2007,429(1-2):270-275.

[12] Wu L,He Y,Lei T,et al. Characterization of porous Ni₃Al electrode for hydrogen evolution in strong alkali solution[J]. Materials Chemistry and Physics,2013,141(1):553-561.

[13] Hu C,Wu Y. Bipolar performance of the electroplated iron-nickel deposits for water electrolysis[J]. Materials Chemistry and Physics,2003,82(3):588-596.

[14] Hoor F,Aravinda C L,Ahmed M F,et al. Fe-P and Fe-P-Pt co-deposits as hydrogen electrodes in alkaline solution[J]. Journal of Power Sources,2001,103:147-149.

[15] Sequeira C A C,Santos D M F,Brito P S D. Electrocatalytic activity of simple and modified Fe-P electrodeposits for hydrogen evolution from alkaline media[J]. Energy,2011,36(2):847-853.

[16] Shafia H F,Tharamani C N,Ahmed M F,et al. Electrochemical synthesis of Fe-Mo and Fe-Mo-Pt alloys and their electrocatalytic activity for methanol oxidation[J]. Journal of Power Sources,2007,167:18-24.

[17] 袁铁锤. 电沉积Ni-S合金析氢阴极材料及析氢机理的研究[D]. 长沙:中南大学,2008.

[18] Cao Y,Liu J,Wang F,et al. Electrodeposited Ni-S intermetallic compound film electrodes for hydrogen evolution reaction in alkaline solutions[J]. Materials Letters,2010,64(3):261-263.

[19] Vandenborre H,Vermeiren P,Leysen R. Hydrogen evolution at nickel sulphide cathodes in alkaline medium[J]. Electrochimica Acta,1984,29(84):297-301.

[20] Valanda T,Burchardta T,Grøntoft T. Structure and catalytic behaviour of NiS_x films with respect to the hydrogen evolution[J]. International Journal of Hydrogen Energy,2002,27(1):39-44.

[21] Yuan T C,Li R D,Zhou K C. Electrocatalytic properties of Ni-S-Co coating electrode for hydrogen evolution in alkaline medium[J]. Transactions of Nonferrous Metals Society of China,2007,17(4):762-765.

[22] Han Q,Liu K,Chen J,et al. Study of amorphous Ni-S-Co alloy used as hydrogen evolution reaction cathode in alkaline medium[J]. International Journal of Hydrogen Energy,2004,29(3):243-248.

[23] Shan Z,LiuY,Chen Z,et al. Amorphous Ni-S-Mn alloy as hydrogen evolution reaction cathode in alkaline medium[J]. International Journal of Hydrogen Energy,2008,33(1):28-33.

[24] Ma Q,Ba J Z,Jiang Y X,et al. Study on electrodeposited Ni-S and Ni-P-S alloy cathodes for hydrogen evolution[J]. Chemical Industry and Engineering,2008,25(6):475-479.

[25] Jakši? J M,Vojnovi? M V,Krstaji? N V. Kinetic analysis of hydrogen evolution at Ni-Mo alloy electrodes[J]. Electrochimica Acta,2000,45(25-26):4151-4158.

[26] Han Q,Cui S,Pu N,et al. A study on pulse plating amorphous Ni-Mo alloy coating used as HER cathode in alkaline medium[J]. International Journal of Hydrogen Energy,2010,35(11):5194-5201.

[27] Hu W. Electrocatalytic properties of new electrocatalysts for hydrogen evolution in alkaline water electrolysis[J]. International Journal of Hydrogen Energy,2000,25(2):111-118.

[28] 吴强. 镍钼基合金催化析氢电极的研究[D]. 天津:天津大学,2013.

[29] 魏海兴,周振芳,马强,等. Ni-Mo-Co合金电极的制备和析氢性能研究[J]. 舰船防化,2011,3:24-28.

[30] Huang L,Yang F,Sun S et al. Studies on structure and electrocatalytic hydrogen evolution of nanocrystalline Ni-Mo-Fe alloy electrodeposit electrode[J]. Chinese Journal of Chemistry,2003,21(4):382-386.

[31] Gao C H,Li N. Hydrogen evolution reaction activity of electrodeposited amorphous/nanocrystalline Ni-Mo-La alloy electrode[J]. The Chinese Journal of Nonferrous Metals,2011,21(11):2819-2824.

[32] Yin Z,Chen F. A facile electrochemical fabrication of hierarchically structured nickel-copper composite electrodes on nickel foam for hydrogen evolution reaction[J]. Journal of Power Sources,2014,265(1):273-281.

[33] Zeng K,Zhang D. Evaluating the effect of surface modifications on Ni based electrodes for alkaline water electrolysis[J]. Fuel,2014,116(1):692-698.

[34] Wang M,Wang Z,Guo Z,et al. The enhanced electrocatalytic activity and stability of NiW films electrodeposited under supergravity field for hydrogen evolution reaction[J]. International Journal of Hydrogen Energy,2011,36(5):3305-3312.

[35] Jovi? B M,La?njevac U,Krstaji? N V,et al. Ni-Sn coatings as cathodes for hydrogen evolution in alkaline solutions[J]. Electrochimica Acta,2013,114:813-818.

[36] Jeyasankar V. Electrodeposition of Ni-Co-Sn alloy from choline chloride-based deep eutectic solvent and characterization as cathode for hydrogen evolution in alkaline solution[J]. International Journal of Hydrogen Energy,2013,38(25):10208-10214.

[37] 姚素薇,姚颖悟,张卫国,等. 镍-钨/二氧化锆纳米复合电极析氢性能的研究[J]. 电镀与涂饰,2009,28(2):1-3.

[38] Kasturibai S,Paruthimal Kalaignan G. Physical and electrochemical characterizations of Ni-SiO₂ nanocomposite coatings[J]. Ionics,2013,19(5):763-770.

[39] Lee H K,Lee H Y,Jeon J M. Codeposition of micro- and nano-sized SiC particles in the nickel matrix composite coatings obtained by electroplating[J]. Surface and Coatings Technology,2007,201(8):4711-4717.

[40] Wang S,DuanQ. Electrocatalytic hydrogen evolution characters of electrodeposited Ni-S/LaNi₅ porous composite electrode[J]. The Chinese Journal of Nonferrous Metals,2013,23(8):2221-2228.

[41] 王森林,张艺. Ni-Mo/LaNi₅多孔复合电极的制备及其电催化析氢性能[J]. 物理化学学报,2011,27(6):1417-1423.

[42] TavaresA C,Trasatti S. Ni+RuO₂ co-deposited electrodes for hydrogen evolution[J]. Electrochimica Acta,2000,45(25):4195-4202.

[43] Vázquez-Gómez L,Cattarin S,Guerriero P,et al. Preparation and electrochemical characterization of Ni+RuO₂ composite cathodes of large effective area[J]. Electrochimica Acta,2007,52(28):8055-8063.

[44] Zheng Z,Li N,Wang C Q,et al. Ni-CeO₂ composite cathode material for hydrogen evolution reaction in alkaline electrolyte[J]. International Journal of Hydrogen Energy,2012,37:13921-13932.

[45] Zheng Z,Li N,Wang C Q,Li D Y,Meng F Y,Zhu Y M. Effects of CeO₂ on the microstructure andhydrogen evolution property of Ni-Zn coatings[J]. Journal of Power Sources,2013,222:88-91.

[46] Zheng Z,Li N,Wang C Q,et al. Electrochemical synthesis of Ni-S/CeO₂ composite electrodes for hydrogen evolution reaction[J]. Journal of Power Sources,2013,230:10-14.

[47] Niedba?a J,Budniok A,??giewka E. Hydrogen evolution on the polyethylene-modified Ni-Mo composite layers[J]. Thin Solid Films,2008,516(18):6191-6196.

[48] Niedbala J. Electroevolution of hydrogen on the polytiophene-modified Ni-Mo composite layers[J]. Materials Chemistry and Physics,2009,118(1):46-50.

[49] Corte D A D,Torres C,Correa P D S,et al. The hydrogen evolution reaction on nickel-polyaniline composite electrodes[J]. International Journal of Hydrogen Energy,2012,37(4):3025-3032.

[50] Panek J,Budniok A. Production and electrochemical characterization of Ni-based composite coatings containing titanium,vanadium or molybdenum powders[J]. Surface and Coatings Technology,2007,201(14):6478-6483.

[51] Herraiz-Cardona I,Ortega E,González-Buch C,et al. Co-modification of Ni-based type Raney electrodeposits for hydrogen evolution reaction in alkaline media[J]. Journal of Power Sources,2013,240(31):698-704.

[52] Solmaz R,Döner A,Karda? G. Preparation characterization and application of alkaline leached CuNiZn ternary coatings for long-term electrolysis in alkaline solution[J]. International Journal of Hydrogen Energy,2010,35(19):10045-10049.

[53] Cai J,Xu J,Wang J,et al. Fabrication of three-dimensional nanoporous nickel films with tunable nanoporosity and their excellent electrocatalytic activities for hydrogen evolution reaction[J]. International Journal of Hydrogen Energy,2013,38(2):934-941.

[54] 陈良木,陈范才,李文军,等. 电沉积镍-钼-钴泡沫合金析氢电极的工艺研究[J]. 电镀与涂饰,2010,29(8):1-3.

[55] Huang Y,Lai C,Wu P,et al. Ni inverse opals for water electrolysis in an alkaline electrolyte[J]. Journal of The Electrochemical Society,2009,157(3):18-22.

[56] Herraiz-Cardona I,Ortega E,et al. Double-template fabrication of three-dimensional porous nickel electrodes for hydrogen evolution reaction[J]. International Journal of Hydrogen Energy,2012,37(3):2147-2156.

[57] Xie Z,He P,Du L,et al. Comparison of four nickel-based electrodes for hydrogen evolution reaction[J]. Electrochimica Acta,2013,88(2):390-394.

[58] 张卫国,尚云鹏,刘丽娜,等. 电化学法制备Ni-W-P纳米线阵列电极及其催化析氢性能[J]. 物理化学学报,2011,27(4):900-904.