石油炼制与化工 ›› 2025, Vol. 56 ›› Issue (9): 1-9.

• 基础研究 •    下一篇

基于机械球磨法的钛系储氢合金性能优化

徐睿,程涛,李朝宇,荣峻峰   

  1. 中石化石油化工科学研究院有限公司
  • 收稿日期:2025-03-14 修回日期:2025-05-21 出版日期:2025-09-12 发布日期:2025-08-28
  • 通讯作者: 荣峻峰 E-mail:rongjf.ripp@sinopec.com
  • 作者简介:2025-06-30
  • 基金资助:
    低温型储氢材料高安全储氢工程应用示范

REFINING TITANIUM-BASED HYDROGEN STORAGE ALLOYS WITH MECHANICAL BALL MILLING METHOD


  • Received:2025-03-14 Revised:2025-05-21 Online:2025-09-12 Published:2025-08-28

摘要: 针对传统钛系储氢合金(TM)储氢量低、成分分布不均、易氧化等问题,采用机械球磨法向钛系储氢合金中引入多种单质金属(Co、Ni、V、Cu、Mg)进行改性,并通过扫描电镜-能量色散荧光光谱(SEM-EDX)、X射线衍射光谱(XRD)、电感耦合等离子光谱(ICP)、X射线光电子能谱(XPS)等手段以及储氢动力学性能测试和氧毒化试验,表征了制备改性合金材料的微观形貌、表面元素分布、晶相结构、表层和体相元素含量、材料储氢能力和储氢速率、改性金属赋存化学状态以及改性金属对TM合金储氢性能的影响。结果表明:V改性使合金的最大储氢量(w,下同)明显提高,从1.70%提高至2.15%;Co改性显著提高了合金的储氢速率,使其30 min储氢量从1.67%增加至1.71%;Co的引入同时增强了合金的抗氧中毒能力,使合金氧毒化后的最大储氢量下降率从41.8%降为1.74%。改性合金引入的Co主要分布在材料表面层,不但能替代储氢活性位点优先氧化而减少其氧化比例,而且能形成致密氧化层,抑制氧从表面层向体相扩散,从而保护了体相的储氢活性位点。

关键词: 氢气储存, 钛系储氢合金, 掺杂金属元素, 机械球磨法, 抗氧中毒

Abstract: To address low hydrogen storage capacity, compositional heterogeneity, and oxidation vulnerability in traditional titanium-based hydrogen storage alloys (TM), mechanical ball milling was used to introduce Co, Ni, V, Cu, and Mg for modification. Multimodal characterizations,including SEM-EDX for microstructure, XRD for phase analysis, ICP for quantificationand XPS for chemical state identification,were combined with hydrogen storage kinetics and oxygen poisoning tests. Results showed that V significantly enhanced maximum hydrogen storage capacity (w) from 1.70% to 2.15%, Co modification accelerated hydrogen absorption kinetics, increasing 30-min storage from 1.67% to 1.71%. Critically, Co addition improved oxygen poisoning resistance: the decline rate of post-oxidation storage capacity dropped from 41.8% to 1.74%. Microstructural analysis revealed that Co preferentially localized at the surface layer, where it formed a dense oxide barrier. This dual role—sacrificial oxidation of Co instead of active sites and physical inhibition of oxygen diffusion—protected bulk hydrogen storage functionality. These findings highlight element-specific modifications as an effective strategy to optimize both storage capacity and oxidative stability in TM alloys.

Key words: hydrogen storage, titanium-based alloys, metal elements doping, mechanical ball milling, oxygen poisoning resistance