杂多酸处理对La-Y-Ni系A2B7型储氢合金电化学性能的影响

兰州理工大学学报 ›› 2025, Vol. 51 ›› Issue (1): 25-33.

杂多酸处理对La-Y-Ni系A₂B₇型储氢合金电化学性能的影响

王成均^1,3, 雷鸣¹, 沈秉金¹, 张乾坤¹, 罗永春^*1,2

1.兰州理工大学材料科学与工程学院, 甘肃兰州 730050;
2.兰州理工大学省部共建有色金属先进加工与再利用国家重点实验室, 甘肃兰州 730050;
3.兰州金川科技园有限公司, 甘肃兰州 730100

收稿日期:2023-12-25 出版日期:2025-02-28 发布日期:2025-03-03
通讯作者: 罗永春(1964-),男,陕西韩城人,教授.Email:luoyc@lut.edu.cn
基金资助:
国家自然科学基金(51761026)

Effect of heteropolyacid treatment on the electrochemical properties of La-Y-Ni system A₂B₇-type hydrogen storage alloy performance

WANG Cheng-jun^1,3, LEI Ming¹, SHEN Bing-jin¹, ZHANG Qian-kun¹, LUO Yong-chun^1,2

1. School of Materials Science and Engineering, Lanzhou University of Technology, Lanzhou 730050, China;
2. State Key Laboratory of Advanced Processing and Recycling of Non-ferrous Metals, Lanzhou University of Technology, Lanzhou 730050, China;
3. Lanzhou Jinchuan Technology Park Co. Ltd., Lanzhou 730100, China

Received:2023-12-25 Online:2025-02-28 Published:2025-03-03

摘要/Abstract

摘要： 制备了退火态A₂B₇型La_0.33Y_0.67Ni_3.23Mn_0.17Al_0.1储氢合金,采用磷钨酸(H₃PW₁₂O₄₀),(phosphotungstic acid,TPA)水溶液对该退火合金进行浸渍处理,研究了TPA处理对合金组织结构、表面形貌、组成以及合金电化学性能的影响.结果表明:经TPA处理后的合金表面形成了腐蚀性凹坑或微孔,同时在合金表面形成了含有高氧化价态钨酸根离子的富Ni层.TPA处理可明显改善合金电极的电化学性能,当TPA质量浓度为0.1 mol/L时,合金电极的交换电流密度I₀最大,此时合金电极具有最大的1 C放电容量(364 mAh/g),其容量保持率S₁₀₀和大电流放电性能HRD₉₀₀分别为93.23%和81.92%,明显优于未处理合金电极的S₁₀₀ (88.12%)和HRD₉₀₀(76.05%).TPA处理前后电极表面与电解质溶液界面处的电子转移阻抗是影响电极高倍率放电动力学性能的控制步骤.

关键词: La-Y-Ni系A₂B₇型储氢合金, 杂多酸, 表面处理

Abstract: The annealed state A₂B₇ type La_0.33Y_0.67Ni_3.23Mn_0.17Al_0.1 hydrogen storage alloy was prepared,and the annealed alloy was impregnated with phosphotungstic acid (H₃PW₁₂O₄₀), (phosphotungstic acid (TPA)) aqueous solution. The effects of TPA treatment on the organization, surface morphology, composition , and the electrochemical properties of the alloy were investigated. The results showed that corrosive pits or micropores are formed on the surface of the TPA-treated alloy, and a Ni-rich layer containing tungstate ions with high oxidation valence is formed on the surface of the alloy. The TPA treatment can significantly improve the electrochemical performance of the alloy electrode. The exchange current density I₀ of the alloy electrode is the largest when the concentration of TPA is 0.1 mol/L. At this time, the alloy electrode has the largest 1C discharge capacity (364 mAh/g), and its capacity retention rate S₁₀₀ and high-current discharge performance HRD₉₀₀ are 93.23% and 81.92%, respectively, which are significantly better than those of the untreated alloy electrode with S₁₀₀(88.12%) and HRD₉₀₀(76.05%). The electron transfer impedance at the interface between the electrode surface and the electrolyte solution before and after the TPA treatment is a controlling step affecting the electrode's high-magnification discharge electrodynamic performance.

Key words: La-Y-Ni system A₂B₇ type hydrogen storage alloy, heteropoly acids, surface treatment

中图分类号:

TG139.7

王成均, 雷鸣, 沈秉金, 张乾坤, 罗永春. 杂多酸处理对La-Y-Ni系A₂B₇型储氢合金电化学性能的影响[J]. 兰州理工大学学报, 2025, 51(1): 25-33.

WANG Cheng-jun, LEI Ming, SHEN Bing-jin, ZHANG Qian-kun, LUO Yong-chun. Effect of heteropolyacid treatment on the electrochemical properties of La-Y-Ni system A₂B₇-type hydrogen storage alloy performance[J]. Journal of Lanzhou University of Technology, 2025, 51(1): 25-33.

导出引用管理器 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

链接本文: https://journal.lut.edu.cn/CN/

https://journal.lut.edu.cn/CN/Y2025/V51/I1/25

参考文献

[1] 王大辉, 张珂, 陈怀敬,等.采用焙烧-水浸法从报废锂离子动力电池中回收金属[J].兰州理工大学学报,2021,47(5):10-18.
[2] 李东琪,张靑松,郑少帅.大倍率充放电循环对锂离子电池特性及热安全性能的影响[J].兰州理工大学学报,2023,49(3):30-35.
[3] 范影强,陈秀娟,王琳琳,等.水热法制备纳米SnO₂电极材料及其储锂性能[J].兰州理工大学学报,2022,48(5):15-20.
[4] KANG Y,ZHANG K,LIN X.Surface modifications of magnesium-based materials for hydrogen storage and nickel-metal hydride batteries:a review[J].Coatings,2023,13(6):1100.
[5] ZHAO X,MA L,GAO Y,et al.Effect of surface treatments on microstructure and electrochemical properties of La-Ni-Al hydrogen storage alloy[J].International Journal of Hydrogen Energy,2009,34(4):1904-1909.
[6] 张庆堂,白永保,马延会,等.金属Ni和NiO纳米颗粒复合结构的制备与储锂性能[J].兰州理工大学学报,2020,46(6):72-76.
[7] WANG Y,TANG W,WANG F,et al.Effects of surface coating with Cu-Pd on electrochemical properties of A₂B₇- type hydrogen storage alloy[J].International Journal of Hydrogen Energy,2018,43(6):3244-3252.
[8] LI Y,TAO Y,KE D,et al.Electrochemical kinetic performances of electroplating Co-Ni on La-Mg-Ni-based hydrogen storage alloys[J].Applied Surface Science,2015,357:1714-1719.
[9] 刘文武,徐志强,雷怡潇,等.磷化铁掺杂硫化聚丙烯腈储锂动力学行为[J].兰州理工大学学报,2023,49(5):10-19.
[10] LI J,ZHOU W,ZHU D,et al.Ni₃S₂-coated metal hydride anode with high-power and long-life performance for low-temperature Ni-MH power batteries[J].Chemical Engineering Journal,2020,379:122204.
[11] LI M M,YANG C C,ZHOU Y T,et al.Clarifying the zeolitic imidazolate framework effect on superior electrochemical properties of hydrogen storage alloys[J].Electrochimica Acta,2022,430:141054.
[12] WANG Z,XIN X,ZHANG M,et al.Recent advances of mixed-transition-metal-substituted polyoxometalates[J].Science China Chemistry,2022,65(8):1515-1525.
[13] YU S P,ZHAO X H,SU G Y.Synthesis and electrocatalytic performance of a P-Mo-V Keggin heteropolyacid modified Ag@Pt/MWCNTs catalyst for oxygen reduction in proton exchange membrane fuel cell[J].Ionics,2019,25:5141-5152.
[14] SAVADOGO O,AMUZGAR K,PIRON D L.Electrode kinetic parameters for the hydrogen evolution reaction on Pd in acid medium:influence of the electrode activation[J].International Journal of Hydrogen Energy,1990,15(11):783-788.
[15] SAVADOGO O,PIRON D L.New hydrogen cathodes in acid medium:case of nickel electrodeposited with heteropolyacids (HPAs)[J].International Journal of Hydrogen Energy,1990,15(10):715-721.
[16] DU Q,SONG D,YOU W,et al.Synthesis,crystal structure and electrochemical properties of a new adduct of benzo-15-crown-5 and H₃PMo₁₂O₄₀[J].Zeitschrift für Naturforschung B,2009,64(3):274-280.
[17] GIZA K,OWCZAREK E,MISZCAYK A.The effect of C45 carbon black-phosphomolybdic acid nanocomposite on hydrogenation and corrosion resistance of La₂Ni₉Co hydrogen storage alloy[J].Energies,2023,16(10):4002.
[18] KARNICKA K,CHOJAK M,MIECZNIKOWSKI K,et al.Polyoxometallates as inorganic templates for electrocatalytic network films of ultra-thin conducting polymers and platinum nanoparticles[J].Bioelectrochemistry,2005,66(1):79-87.
[19] KULESZA P J,SKUNIK M,BARANOWSKA B,et al.Fabrication of network films of conducting polymer-linked polyoxometallate-stabilized carbonnanostructures[J].Electrochimica Acta,2006,51(11):2373-2379.
[20] ERNST A Z,ZOLADEK S,WIADEREK K,et al.Network films of conducting polymer-linked polyoxometalate-modified gold nanoparticles:Preparation and electrochemical characterization[J].Electrochimica Acta,2008,53(11):3924-3931.
[21] GIZA K,ADAMCZYK L.Influence of H₃PW₁₂O₄₀ on electrochemical properties of LaCo_4.8Bi_0.2 alloy[J].Open Chemistry,2013,11(3):330-334.
[22] GIZA K.Communication—a new catalytic application of H₃PMo₁₂O₄₀ in the performance of hydride electrode for Ni-MH battery[J].Journal of The Electrochemical Society,2019,166(14):3332-3334.
[23] TOBY B H,VON DREELE R B.GSAS-II:the genesis of a modern open-source all purpose crystallography software package[J].Journal of AppliedCrystallography,2013,46(2):544-549.
[24] YOUNG R A.The rietveld method[M].New York:Oxford University Press,1993.
[25] LIU J,CHEN P,DENG L,et al.A non-sulfided flower-like Ni-PTA catalyst that enhances the hydrotreatment efficiency of plant oil to produce green diesel[J].Scientific Reports,2015,5(1):15576.
[26] GUAN Q,ZENG Y,SHEN J,et al.Selective hydrogenation of phenol by phosphotungstic acid modified Pd/Ce-AlO x catalyst in high-temperature water system[J].Chemical Engineering Journal,2016,299:63-73.
[27] BAEK Y,YONG K.Controlled growth and characterization of tungsten oxide nanowires using thermal evaporation of WO₃ powder[J].The Journal of Physical Chemistry C,2007,111(3):1213-1218.
[28] YANG J,CAO Y,ZHANG S,et al.Interstitial hydrogen atom to boost Intrinsic catalytic activity of tungsten oxide for hydrogen evolution reaction[J].Small,2023,19(29):2207295.
[29] YUAN H P,JIANG L J.Effect of surface treatment with different alkaline solutions on rare earth-magnesium-nickel based hydrogen storage alloy[J].Chinese Journal of Inorganic Chemistry,2018,34(12):2271-2279.
[30] 熊玮,闫慧忠,吴建民,等.La-Y-Ni储氢材料的表面处理技术[C]//中国稀土学会2017学术年会摘要集.北京:稀土学会,2017.

杂多酸处理对La-Y-Ni系A₂B₇型储氢合金电化学性能的影响

Effect of heteropolyacid treatment on the electrochemical properties of La-Y-Ni system A₂B₇-type hydrogen storage alloy performance

PDF

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 0

编辑推荐

Metrics

本文评价