支撑体改性对钙铜复合材料热化学储能特性的影响

doi:10.19799/j.cnki.2095-4239.2024.0940

摘要/Abstract

摘要：

钙铜循环热化学储能工艺通过简单的气固反应，提供了一种高效的氢能储存与释放途径，具备较高的工业化应用潜力。尽管该工艺展现出广阔的应用前景，钙铜复合材料的碳酸化性能在长期循环中存在显著衰减问题。为解决这一难题，本工作采用支撑体改性策略，研究了支撑体改性对钙铜复合材料热化学储能特性的影响。实验结果表明，相比溶液燃烧合成法、共沉淀法和湿法混合法，采用Pechini法制备的ZrO₂改性钙铜复合材料具有最佳的碳酸化性能。该材料首次的碳酸化转化率是67.4%，经过10个循环后下降到64.4%，保留了96%的初始性能。将CeO₂、MgO或ZnO作为第二种支撑体添加到ZrO₂改性的钙铜复合材料，都可以显著提升其碳酸化性能。其中，ZrO₂和MgO共同改性钙铜复合材料具有最高的碳酸化性能。当ZrO₂和MgO的添加量均为5%时，ZrO₂/MgO共同改性钙铜复合材料10次循环的平均碳酸化转化率为74.9%，相比于ZrO₂改性钙铜复合材料，提升了15.4%。本工作合成的钙铜复合材料对钙铜循环热化学储能工艺的应用具有重要意义。

关键词: 热化学储能, 支撑体, 化学链, 复合材料

Abstract:

The combined Ca/Cu thermochemical energy storage process provides an efficient method for storing and releasing hydrogen through simple gas-solid reactions, demonstrating strong industrial potential. Despite its broad application prospects, the carbonation performance of Ca/Cu composites tends to decay over extended cycling. To address this issue, we investigated the effect of support modification on the thermochemical energy storage characteristics of Ca/Cu composites. Experimental results indicated that Ca/Cu composites modified with ZrO₂ using the Pechini method outperformed those prepared via solution combustion synthesis, co-precipitation, and wet mixing. These ZrO₂-modified composites achieved a carbonation conversion of 67.4% in the first cycle, which only slightly dropped to 64.4% after 10 cycles, retaining 96% of their original efficiency. Adding CeO₂, MgO, or ZnO as secondary support to ZrO₂-modified Ca/Cu composites significantly enhanced the carbonation performance. Notably, Ca/Cu composites co-modified with ZrO₂ and MgO demonstrated the highest performance. With 5% of ZrO₂ and MgO, these composites maintained an average carbonation conversion rate of 74.9% over 10 cycles, which is 15.4% higher than composites modified with ZrO₂. In conclusion, the Ca/Cu composites synthesized in this study are highly significant for the practical application of the combined Ca/Cu thermochemical energy storage process.

Key words: thermochemical energy storage, support, chemical looping, composite

中图分类号:

TK 91

王梦茹, 孙希瑞, 张浩煜, 陈健, 李友势. 支撑体改性对钙铜复合材料热化学储能特性的影响[J]. 储能科学与技术, 2024, 13(12): 4290-4298.

Mengru WANG, Xirui SUN, Haoyu ZHANG, Jian CHEN, Youshi LI. Investigation on support modification on thermochemical energy storage characteristics of Ca/Cu composites[J]. Energy Storage Science and Technology, 2024, 13(12): 4290-4298.

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