钛合金双极板表面纳米晶Zr涂层在质子交换膜燃料电池环境中的性能

doi:10.3866/PKU.WHXB201411262

摘要/Abstract

摘要：

为改善金属双极板在质子交换膜燃料电池(PEMFC)环境中的耐腐蚀性能及降低其界面接触电阻, 采用双阴极等离子溅射沉积技术, 在Ti-6A1-4V合金表面制备了纳米晶Zr 涂层. 利用扫描电子显微镜(SEM), X射线衍射(XRD)和透射电子显微镜(TEM)等微观分析手段对该涂层的组织结构进行了表征. 结果表明: 所制备的涂层具有沉积层和扩散层的双层结构, 其微观组织连续、致密. 在分别通入氢气/空气、70 ℃ 的0.5 mol·L^-1H₂SO₄+2 mg·L^-1 HF的溶液中, 对比研究了纳米晶Zr 涂层与Ti-6A1-4V合金在模拟电池的阳极/阴极工作环境中的电化学腐蚀性能. 动电位极化测试结果表明: 在模拟电池的阳极/阴极工作环境中, 纳米晶Zr 涂层的腐蚀电位均明显高于Ti-6A1-4V合金; 在阴极工作电极电位为+0.6 V下, 纳米晶Zr 涂层与Ti-6A1-4V合金均位于钝化区内, Zr 涂层的钝化电流密度较Ti-6A1-4V合金降低约4 个数量级; 而在阳极工作电极电位为-0.1 V下, 纳米晶Zr 涂层呈现出阴极保护特征. 电化学阻抗谱测试结果表明, 在0.5 mol·L^-1 H₂SO₄+2 mg·L^-1 HF的溶液中, 纳米晶Zr 涂层的容抗弧半径和相位角的最大值及其频率宽度均明显大于Ti-6A1-4V合金. 此外, 纳米晶Zr 涂层同时改善了Ti-6A1-4V合金的导电性与憎水性能.

关键词: 质子交换膜燃料电池, 双极板, 纳米晶Zr涂层, 耐腐蚀性能, 接触电阻

Abstract:

A zirconium nanocrystalline coating has been fabricated on a Ti-6A1-4V alloy bipolar plates using a double cathode glow discharge technique to improve the corrosion resistance and reduce the interfacial contact resistance in polymer electrolyte membrane fuel cells (PEMFCs). The microstructure of Zr coating was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). The microstructure of the Zr coating was found to be continuous and compact; consisting of deposited and diffusion layers. The deposited layer was 30 μm thick and composed of equiaxed grains with an average grain size of around 15 nm, whereas the diffusion layer was 10 μm thick with a gradient distribution of alloying elements, which offered a smooth transition of mechanical properties that were suitable for improving the adhesion strength of the Zr coating on the Ti-6A1-4V substrate. The electrochemical behavior of the Zr coating was evaluated in 0.5 mol·L^-1 H₂SO₄ solution containing 2 mg·L^-1 of HF solution at 70 ℃ to simulate the environment found in a PEMFC. The solution was purged with H2 (simulated PEMFC anodic environment) or air (simulated PEMFC cathodic environment). The Ecorr of the deposited Zr nanocrystalline coating was much higher than that of the Ti-6A1-4V alloy in the simulated PEMFC environment. At the applied cathode (+0.6 V) potentials for PEMFCs, both the Zr nanocrystalline coating and Ti-6A1-4V alloy were in the passive region, but the passive current density of the as-deposited Zr nanocrystalline coating was four orders of magnitude lower than that of the Ti-6A1-4V alloy. At the applied anode (-0.1 V), the Zr nanocrystalline coating exhibited characteristic cathodic protection behavior. The results of electrochemical impedance spectroscopy (EIS) showed that the values of the capacitance semicircle, phase angle maximum and frequency range were larger than those of the Ti-6A1-4V alloy in the simulated PEMFC environment when the phase angle was near -80°. Moreover, the Zr nanocrystalline coating effectively improved the conductivity and hydrophobicity of the Ti-6A1- 4V alloy bipolar plate.

Key words: Proton exchange membrane fuel cell, Bipolar plate, Zr nanocrystalline coating, Corrosion resistance, Interfacial contact resistance

钱阳, 徐江. 钛合金双极板表面纳米晶Zr涂层在质子交换膜燃料电池环境中的性能[J]. 物理化学学报, 2015, 31(2), 291-301. doi: 10.3866/PKU.WHXB201411262

QIAN Yang, XU Jiang. Properties of Zr Nanocrystalline Coating on Ti Alloy Bipolar Plates in Simulated PEMFC Environments[J]. Acta Phys. -Chim. Sin. 2015, 31(2), 291-301. doi: 10.3866/PKU.WHXB201411262

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201411262

https://www.whxb.pku.edu.cn/CN/Y2015/V31/I2/291

参考文献

(1) Karimi, S.; Fraser, N.; Roberts, B.; Foulkes, F. R. Adv. Mater. Sci. Eng. 2012, 2012, 22.
(2) Feng, K.; Li, Z.; Sun, H.; Yu, L.; Cai, X.;Wu, Y.; Chu, P. K. J. Power Sources 2013, 222, 351. doi: 10.1016/j.jpowsour.2012.08.087
(3) Liang, P.; Xu, H. F.; Liu, M.; Lu, L.; Fu, J. Acta Phys. -Chim. Sin. 2010, 26, 595. [梁鹏, 徐洪峰, 刘明, 卢璐, 傅杰. 物理化学学报, 2010, 26, 595.] doi: 10.3866/PKU.WHXB20100329
(4) Wang, Y.; Northwood, D. O. J. Power Sources 2007, 165, 293. doi: 10.1016/j.jpowsour.2006.12.034
(5) Lai, D.; Xu, J.; Xie, Z. H.; Munroe, P. R. J. Mater. Res. 2011, 26, 3020. doi: 10.1557/jmr.2011.367
(6) Xu, J.; Liu, L.; Lu, X. J. Alloy. Compd. 2011, 509, 2450. doi: 10.1016/j.jallcom.2010.11.051
(7) Xu, J.; Xie, Z. H.; Munroe, P. Intermetallics 2011, 19, 1146. doi: 10.1016/j.intermet.2011.03.019
(8) Liu, L.; Xu, J.; Xie, Z. H.; Munroe, P. J. Mater. Chem. A 2013, 1, 2064. doi: 10.1039/c2ta00510g
(9) Wang, H.; Sweikart, M. A.; Turner, J. A. J. Power Sources 2003, 115, 243. doi: 10.1016/S0378-7753(03)00023-5
(10) Ito, K.; Hayashi, T.; Yokobayashi, M.; Numakura, H. Intermetallics 2004, 12, 407. doi: 10.1016/j.intermet.2003.12.009
(11) Ceschini, L.; Lanzoni, E.; Martini, C.; Prandstraller, D.; Sambogna, G. Wear 2008, 264, 86. doi: 10.1016/j.wear.2007.01.045
(12) Rauschenbach, B.; Gerlach, J.W. Cryst. Res. Technol. 2000, 35, 675.
(13) Du, N.; Shu,W. F.; Zhao, Q.; Chen, Q. L.;Wang, S. X. The Chinese Journal of Nonferrous Metals 2013, 23, 426. [杜楠, 舒伟发, 赵晴, 陈庆龙, 王帅星. 中国有色金属学报, 2013, 23, 426.] doi: 10.1016/S1003-6326(13)62480-2
(14) Tawfik, H.; Hung, Y.; Mahajan, D. J. Power Sources 2007, 163, 755. doi: 10.1016/j.jpowsour.2006.09.088
(15) Wang, Y.; Northwood, D. O. Electrochim. Acta 2007, 52, 6793. doi: 10.1016/j.electacta.2007.05.001
(16) Wang, L.; Sun, J.; Sun, J.; Lv, Y.; Li, S.; Ji, S.;Wen, Z. J. Power Sources 2012, 199, 195. doi: 10.1016/j.jpowsour.2011.10.034
(17) Wang, J. L.; Sun, J. C.; Tian, R. J.; Xu, J. Chinese Journal of Power Sources 2007, 31, 725. [王剑莉, 孙俊才, 田如锦, 徐靖. 电源技术, 2007, 31, 725.]
(18) Fekry, A. M. Electrochim. Acta 2009, 54, 3480. doi: 10.1016/j.electacta.2008.12.060
(19) Macdonald, D. D.; Biaggio, S. R.; Song, H. J. Electrochem. Soc. 1992, 139, 170. doi: 10.1149/1.2069165
(20) Macdonald, D. D. J. Electrochem. Soc. 1992, 139, 3434. doi: 10.1149/1.2069096
(21) Meng, G.; Li, Y.;Wang, F. Electrochim. Acta 2006, 51, 4277. doi: 10.1016/j.electacta.2005.12.015
(22) Yuan, L.;Wang, H. M. Electrochim. Acta 2008, 54, 421. doi: 10.1016/j.electacta.2008.07.056
(23) Bonnel, K.; Le Pen, C.; Pebere, N. Electrochim. Acta 1999, 44, 4259. doi: 10.1016/S0013-4686(99)00141-3
(24) Assis, S. L. D.;Wolynec, S.; Costa, I. Electrochim. Acta 2006, 51, 1815. doi: 10.1016/j.electacta.2005.02.121
(25) Fekry, A. M.; El-Sherif, R. M. Electrochim. Acta 2009, 54, 7280. doi: 10.1016/j.electacta.2009.07.047
(26) Li, J. F.; Zhang, Z.; Cao, F. H.; Cheng, Y. L.; Zhang, J. Q.; Cao, C. N. Acta Metall. Sin. 2003, 39, 426. [李劲风, 张昭,曹发和, 程英亮, 张鉴清, 曹楚南. 金属学报, 2003, 39, 426.]
(27) Cheng, X.; Li, X.; Yang, L.; Du, C. Journal of Wuhan University of Technology-Materials Science Edition 2008, 23, 574. doi: 10.1007/s11595-006-4574-0
(28) Potucek, R. K.; Rateick, R. G.; Birss, V. I. J. Electrochem. Soc. 2006, 153, B304.
(29) Brug, G. J.; Van Den Eeden, A. L. G.; Sluyters-Rehbach, M.; Sluyters, J. H. J. Electroanal. Chem. 1984, 176, 275. doi: 10.1016/S0022-0728(84)80324-1
(30) Igual Muñoz, A.; García Antón, J.; Guiñón, J. L.; Pérez Herranz, V. Corrosion Sci. 2007, 49, 3200. doi: 10.1016/j.corsci.2007.03.002
(31) Arutunow, A.; Darowicki, K. Electrochim. Acta 2008, 53, 4387. doi: 10.1016/j.electacta.2008.01.063
(32) Kaufmann, R.; Klewe, N. H.; Moers, H.; Pfennig, G.; Jenett, H.; Ache, H. J. Surf. Interface Anal. 1988, 11, 502.
(33) Balaceanu, M.; Braic, M.; Braic, V.; Vladescu, A.; Negrila, C. C. J. Optoelectron. Adv. Mater. 2005, 7, 2557.
(34) Wagner, C. D.; Zatko, D. A.; Raymond, R. H. Anal. Chem. 1980, 52, 1445. doi: 10.1021/ac50059a017
(35) Lindberg, B. J.; Hamrin, K.; Johansson, G.; Gelius, U.; Fahlman, A.; Nordling, C.; Siegbahn, K. Phys. Scr. 1970, 1, 286. doi: 10.1088/0031-8949/1/5-6/020
(36) Monticelli, C.; Bellosi, A.; Dal Colle, M. J. Electrochem. Soc. 2004, 151, B331.
(37) Weber, A. Z.; Newman, J. J. Electrochem. Soc. 2006, 153, A2205.
(38) Fu, Y.; Lin, G.; Hou, M.;Wu, B.; Shao, Z.; Yi, B. Int. J. Hydrog. Energy 2009, 34, 405. doi: 10.1016/j.ijhydene.2008.10.068
(39) Kim, J. S.; Peelen,W. H. A.; Hemmes, K.; Makkus, R. C. Corrosion Sci. 2002, 44, 635. doi: 10.1016/S0010-938X(01)00107-X

[1]	兰畅, 楚宇逸, 王烁, 刘长鹏, 葛君杰, 邢巍. 质子交换膜燃料电池阴极非贵金属M-N_x/C型氧还原催化剂研究进展[J]. 物理化学学报, 2023, 39(8): 2210036 -0 .
[2]	韩爱娣, 闫晓晖, 陈俊任, 程晓静, 章俊良. 分散溶剂对PEMFC催化层中超薄Nafion离聚物质子传导的影响[J]. 物理化学学报, 2022, 38(3): 1912052 - .
[3]	罗芳, 潘书媛, 杨泽惠. 中高温质子交换膜燃料电池催化剂研究进展[J]. 物理化学学报, 2021, 37(9): 2009087 - .
[4]	王健, 丁炜, 魏子栋. 超低铂用量质子交换膜燃料电池[J]. 物理化学学报, 2021, 37(9): 2009094 - .
[5]	樊润林, 彭宇航, 田豪, 郑俊生, 明平文, 张存满. 燃料电池复合石墨双极板基材的研究进展：材料、结构与性能[J]. 物理化学学报, 2021, 37(9): 2009095 - .
[6]	丁亮, 唐堂, 胡劲松. 基于金属-氮-碳结构催化剂的质子交换膜燃料电池研究进展[J]. 物理化学学报, 2021, 37(9): 2010048 - .
[7]	梁嘉顺, 刘轩, 李箐. 提升燃料电池铂基催化剂稳定性的原理、策略与方法[J]. 物理化学学报, 2021, 37(9): 2010072 - .
[8]	陈雯慧,陈胜利. 墨水溶剂对低铂含量质子交换膜燃料电池性能的影响[J]. 物理化学学报, 2019, 35(5): 517 -522 .
[9]	吕洋,宋玉江,刘会园,李焕巧. 内核含Pd的Pt基核壳结构电催化剂[J]. 物理化学学报, 2017, 33(2): 283 -294 .
[10]	常乔婉,肖菲,徐源,邵敏华. 核-壳结构氧还原反应电催化剂[J]. 物理化学学报, 2017, 33(1): 9 -17 .
[11]	孟优权,王超,张卿雷,沈水云,朱凤鹃,杨宏,章俊良. 阴极Pt负载量和背压对PEMFC性能的协同影响规律[J]. 物理化学学报, 2016, 32(6): 1460 -1466 .
[12]	杨翼,罗来明,杜娟娟,张荣华,代忠旭,周新文. 电位置换反应在空心结构Pt基燃料电池纳米催化剂中的研究进展[J]. 物理化学学报, 2016, 32(4): 834 -847 .
[13]	夏继业,董国栋,田博元,严秋平,韩杰,邱松,李清文,梁学磊,彭练矛. 碳纳米管薄膜晶体管中的接触电阻效应[J]. 物理化学学报, 2016, 32(4): 1029 -1035 .
[14]	朱红,骆明川,蔡业政,孙照楠. 核壳结构催化剂应用于质子交换膜燃料电池氧还原的研究进展[J]. 物理化学学报, 2016, 32(10): 2462 -2474 .
[15]	尚明丰,段佩权,赵天天,唐文超,林瑞,黄宇营,王建强. 用于质子交换膜燃料电池催化剂结构研究的原位XAFS实验方法[J]. 物理化学学报, 2015, 31(8): 1609 -1614 .