溶胶-凝胶法制备TiO2增强LiAlH4放氢性能

doi:10.15541/jim20250492

摘要/Abstract

摘要：

氢化铝锂(LiAlH₄)因其高理论储氢容量(质量分数约10.5%)被视为极具潜力的固态储氢材料, 但其较高的热分解温度与缓慢的动力学严重制约了实际应用。过渡金属氧化物TiO₂作为有效的催化剂, 在改善储氢材料性能方面展现出潜力, 然而商业TiO₂形貌与结构不可控, 难以进一步提升其催化性能。本研究采用溶胶-凝胶法制备具有大比表面积和丰富缺陷的纳米TiO₂催化剂, 将不同质量分数(1%、3%、5%、7%)的自制TiO₂与LiAlH₄通过球磨复合, 系统研究了其放氢性能。结果表明, 5%(质量分数)TiO₂的掺杂效果最优, 使LiAlH₄的起始放氢温度降至112 ℃, 较纯LiAlH₄ (165 ℃)降低了53 ℃。在200 ℃恒温条件下, 该复合体系可在更短时间内完成放氢, 总放氢量达7.84%(质量分数), 且放氢总时间较纯LiAlH₄缩短约30 min。即使在150 ℃较低温度下, 掺杂样品仍能释放4.64%(质量分数)的氢气, 远超纯LiAlH₄在此温度下的放氢量(质量分数<1%)。动力学分析表明, TiO₂掺杂使LiAlH₄第一步放氢反应的活化能从116.2 kJ/mol显著降低至55.6 kJ/mol, 降幅高达52%。LiAlH₄放氢性能显著提升源于放氢过程中原位生成的AlTi和LiAl活性中间相, 它们作为高效的催化活性中心, 为氢气分子的重组与脱附提供了新路径。本研究不仅证实了通过溶胶-凝胶法合成TiO₂可有效突破商业催化剂性能瓶颈, 还为设计下一代高性能储氢材料催化剂提供了新的思路与实验依据。

关键词: LiAlH₄, TiO₂, 掺杂, 放氢性能, 反应活化能

Abstract:

Lithium alanate (LiAlH₄) is considered a promising solid-state hydrogen storage material due to its high theoretical hydrogen capacity (mass fraction about 10.5%). However, its practical application is hampered by high decomposition temperatures and sluggish kinetics. Titanium dioxide (TiO₂) has shown potential as an effective catalyst for improving the dehydrogenation properties of hydrides. Nevertheless, the catalytic performance of commercial TiO₂ is often limited by its uncontrollable morphology and structure. To overcome this limitation, this study used the Sol-Gel method to synthesize nanostructured TiO₂ catalysts with high specific surface area and abundant defects. The as-prepared TiO₂ was ball-milled with LiAlH₄ at different mass ratios (1%, 3%, 5%, and 7%) to form composites, whose dehydrogenation properties were systematically investigated. Results demonstrated that the 5% (in mass) TiO₂-doped sample exhibited optimal performance, lowering the onset dehydrogenation temperature of LiAlH₄ to 112 ℃, which is 53 ℃ lower than that of pristine LiAlH₄ (165 ℃). Under isothermal conditions at 200 ℃, the composite released a total hydrogen capacity of 7.84% (in mass) within a significantly shorter time, and completed dehydrogenation approximately 30 min faster than the undoped sample. Even at a lower temperature of 150 ℃, the doped sample released 4.64% (in mass) hydrogen, far exceeding the capacity of pure LiAlH₄ (<1% (in mass)) at the same temperature. Kinetic analysis revealed that TiO₂ doping reduced the activation energy for the first dehydrogenation step from 116.2 kJ/mol to 55.6 kJ/mol, a remarkable decrease of 52%. In-situ formation of active AlTi and LiAl intermediate phases during dehydrogenation played a critical role, which served as efficient catalytic centers, providing new pathways for hydrogen recombination and desorption. This work not only verifies that TiO₂ synthesized via the Sol-Gel method can effectively break through the performance ceiling of commercial catalysts, but also offers new insights and experimental basis for designing next-generation high-performance catalysts for hydrogen storage materials.

Key words: LiAlH₄, TiO₂, doping, hydrogen release property, reaction activation energy

中图分类号:

TQ174

郑雪萍, 胡春旭, 李雪, 马秋花, 梁琳坤, 刘文帅, 刘胜林. 溶胶-凝胶法制备TiO₂增强LiAlH₄放氢性能[J]. 无机材料学报, 2026, 41(9): 1265-1272.

ZHENG Xueping, HU Chunxu, LI Xue, MA Qiuhua, LIANG Linkun, LIU Wenshuai, LIU Shenglin. Enhancing Hydrogen Release Performance of LiAlH₄ by TiO₂ Prepared via Sol-Gel Method[J]. Journal of Inorganic Materials, 2026, 41(9): 1265-1272.

图/表 11

图1 溶胶-凝胶法制备的TiO2的SEM照片

Fig. 1 SEM image of TiO2 prepared by the Sol-Gel method

图2 TiO2及球磨后LiAlH4+5% TiO2的SEM照片和EDS元素分布图

Fig. 2 SEM images and EDS mappings of TiO2 and ball- milled LiAlH4+5% TiO2 (a-c) SEM images of (a, b) TiO2 and (c) ball-milled LiAlH4+5% TiO2; (d-f) EDS mappings of ball-milled LiAlH4+5% TiO2

图3 纯LiAlH4和球磨后LiAlH4+5% TiO2的XRD图谱

Fig. 3 XRD patterns of pure LiAlH4 and ball-milled LiAlH4+ 5% TiO2

图4 商业TiO2掺杂LiAlH4的催化性能对比

Fig. 4 Comparison of the catalytic performance of commercial TiO2-doped LiAlH4 Colorful figure is available on website

图5 TiO2掺杂LiAlH4的放氢性能

Fig. 5 Hydrogen release performance of TiO2-doped LiAlH4 (a) Time dependent hydrogen release curves; (b) Maximum hydrogen release amount. Colorful figures are available on website

图6 掺杂不同质量分数TiO2的LiAlH4的放氢量与温度的关系曲线

Fig. 6 Temperature dependent of hydrogen evolution of LiAlH4 doped with different mass fractions of TiO2 Colorful figure is available on website

表1 不同试样在200 ℃下的放氢性能参数

Table 1 Hydrogen release performance parameters of different samples at 200 ℃

Sample	Initial hydrogen release temperature/℃		Hydrogen release amount/% (in mass)		Total hydrogen release amount/% (in mass)
Sample	Stage Ⅰ	Stage Ⅱ	Stage Ⅰ	Stage Ⅱ	Total hydrogen release amount/% (in mass)
LiAlH₄	165	185	4.37	2.78	7.15±0.15
LiAlH₄+1% TiO₂	136	182	4.63	2.28	6.91±0.15
LiAlH₄+3% TiO₂	121	173	5.31	2.37	7.68±0.15
LiAlH₄+5% TiO₂	112	164	5.02	2.82	7.84±0.15
LiAlH₄+7% TiO₂	121	167	4.64	2.59	7.23±0.15

图7 不同温度下TiO2掺杂LiAlH4的放氢性能

Fig. 7 Hydrogen release performance of TiO2-doped LiAlH4 at different temperatures (a) Time dependent hydrogen release curves of pure LiAlH4 and LiAlH4+5% TiO2 at different temperatures; (b) Arrhenius curves of LiAlH4+5% TiO2 at stage I

表2 不同催化剂对LiAlH4第一阶段放氢反应活化能及最大放氢量的影响[25-27]

Table 2 Effects of different catalysts on the activation energy and maximum hydrogen release amount of LiAlH4 at stage I[25-27]

Catalyst	Synthesis method	Reduced activation energy of hydrogen release at stage I/(kJ·mol^-1)	Maximum hydrogen release amount/% (in mass)	Reference
K₂TiF₆	Business purchase	37.8	7.2	[25]
TiSiO₄	Business purchase	35.0	6.0	[26]
Al₂TiO₅	Business purchase	12.0	6.2	[27]
TiO₂	Sol-Gel method	60.4	7.84	This work

图8 LiAlH4+5% TiO2在不同温度反应后的SEM照片

Fig. 8 SEM images of LiAlH4+5% TiO2 after reaction at different temperatures (a) 130 ℃; (b) 140 ℃; (c) 150 ℃; (d) 200 ℃

图9 LiAlH4+5% TiO2在不同温度反应后的XRD图谱

Fig. 9 XRD patterns of LiAlH4+5% TiO2 after reaction at different temperatures

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溶胶-凝胶法制备TiO₂增强LiAlH₄放氢性能

Enhancing Hydrogen Release Performance of LiAlH₄ by TiO₂ Prepared via Sol-Gel Method

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