Ti3AlC2 在含F- 的高温硫酸溶液中的腐蚀行为研究

doi:10.11902/1005.4537.2025.105

中国腐蚀与防护学报

2026, Vol. 46

Issue (2): 533-540 CSTR: 32134.14.1005.4537.2025.105 DOI: 10.11902/1005.4537.2025.105

研究报告

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Ti₃AlC₂ 在含F^- 的高温硫酸溶液中的腐蚀行为研究

迟永晨, 王浩杰, 侯强强, 郑莉莉, 李希超(

)

青岛大学机电工程学院青岛 266071

Corrosion Behavior of Ti₃AlC₂ in High-temperature Sulfuric Acid Solution Containing F^-

CHI Yongchen, WANG Haojie, HOU Qiangqiang, ZHENG Lili, LI Xichao(

)

College of Mechanical and Electronic Engineering, Qingdao University, Qingdao 266071, China

引用本文:

迟永晨, 王浩杰, 侯强强, 郑莉莉, 李希超. Ti₃AlC₂ 在含F^- 的高温硫酸溶液中的腐蚀行为研究[J]. 中国腐蚀与防护学报, 2026, 46(2): 533-540.
Yongchen CHI, Haojie WANG, Qiangqiang HOU, Lili ZHENG, Xichao LI. Corrosion Behavior of Ti₃AlC₂ in High-temperature Sulfuric Acid Solution Containing F^-[J]. Journal of Chinese Society for Corrosion and protection, 2026, 46(2): 533-540.

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摘要:

采用动电位极化、恒电位极化和电化学阻抗谱等方法研究Ti₃AlC₂材料在含有F^-的高温H₂SO₄溶液中的腐蚀行为。利用扫描电子显微镜(SEM)、X射线光电子能谱(XPS)等对腐蚀产物的形貌、微观组织进行分析。结果表明，在模拟质子交换膜燃料电池(PEMFC)环境下(80 ℃，0.5 mol·L^-1 H₂SO₄和2 mg·L^-1 F^-)，Ti₃AlC₂的自腐蚀电位为-128.7 mV，在0~370 mV电压范围内发生钝化，钝化电流密度为75~200 μA·cm^-2，随着电位升高，腐蚀电流密度显著上升并发生了氧化反应；0.6 V恒电位极化后，腐蚀电流密度稳定在1121.66 μA·cm^-2，腐蚀后样品表面表现为明显的晶界腐蚀以及少量的晶粒腐蚀，腐蚀产物主要为TiO₂和Al₂O₃。Ti₃AlC₂的耐蚀性随着酸性下降有大幅的提升，而溶液温度的升高和F^-浓度增加会使Ti₃AlC₂耐蚀性变差。

关键词 ： Ti₃AlC₂, 质子交换膜燃料电池双极板, 电化学腐蚀, 腐蚀机理

Abstract：

In this work, the corrosion behavior of Ti₃AlC₂ in high-temperature sulfuric acid solutions containing F^- was investigated by means of potentiodynamic polarization, potentiostatic polarization, and electrochemical impedance spectroscopy (EIS). Meanwhile, the corrosion products were characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The results show that in a simulated proton exchange membrane fuel cell working environment (80 ℃, 0.5 mol·L^-1 H₂SO₄ and 2 mg·L^-1 F^-), the Ti₃AlC₂ presented free corrosion potential of -128.7 mV. Passivation occurred within the potential range of 0-370 mV, with a passivation current density of 75-200 μA·cm^-2. As the potential increased, the corrosion current density rose significantly, accompanied by oxidation reactions. After potentiostatic polarization at 0.6 V, the corrosion current density stabilized at 1121.66 μA·cm^-2. The corrosion morphology was mainly manifested as obvious grain boundary corrosion and a small amount of grain corrosion, and the corrosion products compose mainly of TiO₂ and Al₂O₃. The corrosion resistance of Ti₃AlC₂ is improved considerably with the decreasing acidity, whereas elevated solution temperature and increased F^- concentration its corrosion resistance is deteriorated.

Key words： Ti₃AlC₂ PEMFC bipolar plate electrochemical corrosion corrosion mechanism

收稿日期: 2025-03-31 32134.14.1005.4537.2025.105

ZTFLH:

TK91

基金资助:国家自然科学青年科学基金(52001179);山东省自然科学基金(ZR2020ME019)

通讯作者: 李希超，E-mail：lixichao@qdu.edu.cn，研究方向为燃料电池双极板表面改性

作者简介: 迟永晨，男，1999年生，硕士生

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https://www.jcscp.org/CN/10.11902/1005.4537.2025.105 或 https://www.jcscp.org/CN/Y2026/V46/I2/533

表1 腐蚀实验条件及对应的样品编号

图1 Ti3AlC2在不同溶液环境中的动电位极化曲线

表2 Ti3AlC2在不同腐蚀环境中极化曲线拟合参数

图2 Ti3AlC2在不同溶液环境中的恒电位极化曲线

图3 Ti3AlC2在不同溶液环境中0.6 V恒电位极化5 h后的表面腐蚀形貌

图4 Ti3AlC2恒电位极化前后的Nyquist图和等效电路图

表3 Ti3AlC2在不同腐蚀环境中的EIS谱拟合结果

图5 Ti3AlC2在80 ℃，pH = 0和2 mg·L-1 F-溶液中恒电位极化后表面XPS分析

图6 Ti3AlC2在PEMFC环境下腐蚀机理

[1]	Sun X W, Li X C, Zhao J X, et al. Research progress on protective coatings for bipolar plates of proton exchange membrane fuel cells [J]. Surf. Technol., 2023, 52(5): 26
[1]	孙贤伟, 李希超, 赵经香等. 质子交换膜燃料电池双极板防护涂层研究进展 [J]. 表面技术, 2023, 52(5): 26
[2]	Cao C H, Liang C H, Huang N B. Electrochemical characteristic of stainless steel bipolar plates deposited with niobium [J]. J. Chin. Soc. Corros. Prot., 2013, 33: 123
[2]	曹彩红, 梁成浩, 黄乃宝. 镀铌不锈钢双极板的电化学性能 [J]. 中国腐蚀与防护学报, 2013, 33: 123
[3]	Dhakate S R, Mathur R B, Kakati B K, et al. Properties of graphite-composite bipolar plate prepared by compression molding technique for PEM fuel cell [J]. Int. J. Hydrogen Energy, 2007, 32: 4537
[4]	Hou Q Q, Li X C, Sun X W, et al. Research progress of nitride coatings on PEMFC metal bipolar plate [J]. Trans. Mater. Heat Treat., 2024, 45(1): 11
[4]	侯强强, 李希超, 孙贤伟等. PEMFC金属双极板氮化物涂层的研究进展 [J]. 材料热处理学报, 2024, 45(1): 11
[5]	Feng K, Li Z G, Cai X, et al. Silver implanted 316L stainless steel as bipolar plates in polymer electrolyte membrane fuel cells [J]. Mater. Chem. Phys., 2011, 126: 6
[6]	Jung H Y, Huang S Y, Ganesan P, et al. Performance of gold-coated titanium bipolar plates in unitized regenerative fuel cell operation [J]. J. Power Sources, 2009, 194: 972
[7]	Li R, Cai Y, Wippermann K, et al. The electrochemical behavior of CrN/Cr coatings with defects on 316L stainless steel in the simulated cathodic environment of an HT-PEFC [J]. J. Electrochem. Soc., 2019, 166: C394
[8]	Wang H C, Hou K H, Lu C E, et al. The study of electroplating trivalent CrC alloy coatings with different current densities on stainless steel 304 as bipolar plate of proton exchange membrane fuel cells [J]. Thin Solid Films, 2014, 570: 209
[9]	Liu Y X, He D Y, Sun Z, et al. Research progress of electrochemical for protective properties of organic coatings [J]. Surf. Technol., 2021, 50(3): 66
[9]	刘玉欣, 何东昱, 孙哲等. 有机涂层防护性能的电化学研究进展 [J]. 表面技术, 2021, 50(3): 66
[10]	Wang P, Mei B C, Lei L. Electrochemical behavior of several compounds of MAX phase in solutions of NaOH, H₂SO₄ and HCl [J]. Corros. Sci. Prot. Technol., 2009, 21: 55
[10]	王苹, 梅炳初, 雷零. 若干MAX相化合物在NaOH、H₂SO₄和HCl中的电化学性质 [J]. 腐蚀科学与防护技术, 2009, 21: 55
[11]	Lu J L, Abbas N, Tang J N, et al. Synthesis and characterization of co-nductive ceramic MAX-phase coatings for metal bipolar plates in simulated PEMFC environments [J]. Corros. Sci., 2019, 158: 108106
[12]	Liu Y, Ren Y J, Chen J, et al. Preparation and corrosion resistance of ternary layered compound Cr₂AlC coating on 304 stainless steel for bipolar plates of PEMFC [J]. J. Chin. Soc. Corros. Prot., 2023, 43: 62
[12]	刘云, 任延杰, 陈荐等. 质子交换膜燃料电池不锈钢双极板表面Cr₂AlC涂层的制备与耐蚀性能 [J]. 中国腐蚀与防护学报, 2023, 43: 62
[13]	Mao S J, Yuan J C, Peng Y Q, et al. Electrophoretic deposition kinetics and corrosion resistance of Ti₃SiC₂ coatings [J]. J. Mater. Sci. Eng., 2023, 41: 545
[13]	茅思佳, 袁经超, 彭雨晴等. Ti₃SiC₂涂层的电泳沉积动力学和耐腐蚀性 [J]. 材料科学与工程学报, 2023, 41: 545
[14]	Li X C, Zheng L L, Qian Y H, et al. Effects of high temperature oxidation on mechanical properties of Ti₃AlC₂ [J]. J. Mater. Sci. Technol., 2017, 33: 596
[15]	Tawfik H, Hung Y, Mahajan D. Metal bipolar plates for PEM fuel cell—A review [J]. J. Power Sources, 2007, 163: 755
[16]	Jiang H F, Zhou Z X, Liu X Q, et al. Study on the performance of F^- doped TiO₂ [J]. Photogr. Sci. Photochem., 2007, 25: 223
[16]	江宏富, 周作兴, 刘杏芹等. F离子掺杂TiO₂的性能研究 [J]. 感光科学与光化学, 2007, 25: 223
[17]	Li Z Y, Wang L B, Sun D D, et al. Synthesis and thermal stability of two-dimensional carbide MXene Ti₃C₂ [J]. Mater. Sci. Eng., 2015, 191B: 33
[18]	Chen Y, Chen X, Liu T, et al. Effect of temperature on electrochemical corrosion behavior of 316L stainless steel in borate buffer solution [J]. Corros. Prot., 2014, 35: 344
[18]	陈宇, 陈旭, 刘彤等. 温度对316L不锈钢在硼酸溶液中腐蚀电化学行为的影响 [J]. 腐蚀与防护, 2014, 35: 344
[19]	Zhu M, Wang R, Chen C, et al. Comparison of corrosion behavior of Ti₃SiC₂ and Ti₃AlC₂ in NaCl solutions with Ti [J]. Ceram. Int., 2017, 43: 5708
[20]	Zhou Y C, Wang X H, Sun Z M, et al. Electronic and structural properties of the layered ternary carbide Ti₃AlC₂ [J]. J. Mater. Chem., 2001, 11: 2335
[21]	Zhang H, Li Y L, Wang J, et al. Effect of pH value on the corrosion behavior of 904L stainless steel under high Cl^- concentration environment [J]. Mater. Prot., 2023, 56(7): 77
[21]	张红, 李元隆, 王杰等. 高含Cl^-环境下pH值对904L不锈钢腐蚀行为的影响 [J]. 材料保护, 2023, 56(7): 77
[22]	Hou Q Q, Li X C, Sun X W, et al. Characterization of the performance of CrN/Nb coated 316L stainless steel bipolar plates for PEMFC [J]. Int. J. Hydrogen Energy, 2025, 100: 882

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