Mn/Al改性的高稳定性钙基储能材料

doi:10.11949/0438-1157.20250262

摘要/Abstract

摘要：

使用安全无污染前体，通过改进的溶胶-凝胶法合成了Mn、Al共掺杂钙基储能材料，对材料的各项储能性能进行了研究，并考察了初步放大合成对材料性能的影响。结果表明，乙酸钙前体合成的共掺杂材料Ca100Mn15Al10-Ac在1000次储能循环中表现出优异的稳定性，性能仅衰减23.2%，且主要集中在前期，其平均光吸收率也达到70.1%，通过形貌分析发现，共掺杂材料在循环过程中演化出的稳定多孔结构有效抑制性能衰减。材料的初步放大合成以及添加微晶纤维素黏结剂不会对Ca100Mn15Al10-Ac的稳定性造成负面影响，有利于后续大规模制备。

关键词: 太阳能, 钙基材料, 储能, 吸附, 稳定性

Abstract:

Mn and Al co-doped calcium-based energy storage materials were synthesized using safe and non-toxic precursors through a modified sol-gel method. The energy storage performance of the materials was carefully studied, and the effects of preliminary scale-up synthesis on material properties were examined. The results demonstrate that the co-doped material Ca100Mn15Al10-Ac synthesized from calcium acetate exhibited excellent stability during 1000 energy storage cycles with only 23.2% performance degradation (mainly occurring in the initial stage), and the average solar absorptance reaches 70.1%. Morphology analysis revealed that the evolution of stable porous structure during cycling effectively suppressed performance decay. The initial scale-up synthesis of the material and the addition of microcrystalline cellulose binder will not have a negative impact on the stability of Ca100Mn15Al10-Ac, which is conducive to subsequent large-scale preparation.

Key words: solar energy, calcium-based materials, energy storage, adsorption, stability

中图分类号:

TB 34

刘辉, 魏进家. Mn/Al改性的高稳定性钙基储能材料[J]. 化工学报, 2025, 76(11): 6018-6026.

Hui LIU, Jinjia WEI. Mn/Al modified calcium-based energy storage materials with high stability[J]. CIESC Journal, 2025, 76(11): 6018-6026.

图/表 11

图1 石英管固定床反应装置示意图

Fig.1 Quartz tubular fixed-bed reactor

图2 循环中二氧化碳流量曲线（围成的面积为煅烧阶段的二氧化碳释放量）

Fig.2 CO2 flow rate in one energy storage cycle (the enclosed area is equal to the volume of carbon dioxide released in calcination process)

图3 乙酸钙合成材料储能性能

Fig.3 Energy storage performance of materials synthesized by calcium acetate

图4 Ca100Mn15Al10-Ac的长周期循环性能

Fig.4 The long-term energy storage performance of Ca100Mn15Al10-Ac

表1 各种用于储能的改性钙基材料对比

Table 1 Comparison of various modified calcium-based materials for energy storage

掺杂钙基材料	碳酸化温度/℃	碳酸化时间/min	首次储能密度/（kJ/kg）	循环次数/衰减率	文献
CaCO₃/Fe,Mn	700	10	1500	60/3.3%	[10]
CaO/Al,Mn,Fe,Li	725	20	1746	60/4.26%	[29]
CaCO₃/Ti,Al,Mg	750	10	1157	100/7%	[31]
CaO/Mn,Mg	800	10	1604	100/6.23%	[32]
CaO/Al	850	10	1496	100/32%	[33]
CaO/Mn,Al	800	10	1245.7	1000/23.2%	this study

图5 各样品的XRD谱图：（a）10°~80°全谱图；（b）和（c）主峰放大图

Fig.5 XRD patterns of various samples： (a) patterns ranged from 10° to 80°; (b) and (c) the magnified pattern of the CaO peaks [(200) and (220)]

图6 样品光吸收能力

Fig. 6 Solar absorption capacity of different samples

图7 各样品扫描电镜图：（a）新鲜Ca100Al10-Ac样品；（b）100次循环后Ca100Al10-Ac样品；（c）新鲜Ca100Al10-Ac样品EDS谱图；（d）新鲜Ca100Mn15-Ac样品；（e）100次循环后Ca100Mn15-Ac样品；（f）新鲜Ca100Mn15-Ac样品EDS谱图；（g）、（j）新鲜Ca100Mn15Al10-Ac样品；（h）、（k）1000次循环后Ca100Mn15Al10-Ac样品；（i）新鲜Ca100Mn15Al10-Ac样品EDS谱图

Fig.7 SEM images and corresponding EDS images of various samples： (a) fresh Ca100Al10-Ac; (b) 100th cycled Ca100Al10-Ac; (c) EDS images of fresh Ca100Al10-Ac; (d) fresh Ca100Mn15-Ac; (e) 100th cycled Ca100Mn15-Ac; (f) EDS images of fresh Ca100Mn15-Ac; (g),(j) fresh Ca100Mn15Al10-Ac; (h),(k) Ca100Mn15Al10-Ac after 1000 cycles; (i) EDS images of fresh Ca100Mn15Al10-Ac

图8 不同材料的反应过程曲线

Fig.8 Reaction curves of various materials

图9 添加微晶纤维素Ca100Mn15Al10-Ac样品性能曲线

Fig.9 Energy storage performance of Ca100Mn15Al10-Ac sample added with microcrystalline cellulose

图10 Ca100Mn15Al10-Ac放大10倍后循环性能

Fig.10 Cyclic performance of Ca100Mn15Al10-Ac after 10 times scaled up

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