Ni-Al掺杂的钙基热化学储热循环性能研究  

Enhancement Mechanism of Calcium-based Thermochemical Energy Storage Cyclic Performance Through Ni-Al Doping

作　　者：丁历威 陈冬 吕洪坤 侯成龙 国旭涛 黄泰格 肖刚[2] 祝培旺[2] DING Liwei;CHEN Dong;LYU Hongkun;HOU Chenglong;GUO Xutao;HUANG Taige;XIAO Gang;ZHU Peiwang(State Grid Zhejiang Electric Power Research Institute,Hangzhou 310014,Zhejiang Province,China;State Key Laboratory of Clean Energy Utilization(Zhejiang University),Hangzhou 310027,Zhejiang Province,China)

机构地区：[1]国网浙江省电力有限公司电力科学研究院,浙江省杭州市310014 [2]能源高效清洁利用全国重点实验室(浙江大学),浙江省杭州市310027

出　　处：《中国电机工程学报》2025年第6期2203-2209,I0013,共8页PROCEEDINGS OF THE CHINESE SOCIETY FOR ELECTRICAL ENGINEERING

基　　金：国网浙江省电力有限公司科技项目(B311DS230006)。

摘　　要：以CaCO_(3)/CaO可逆反应为基础的钙基热化学储热具有能量密度高、成本低、储存时间长等特点,是下一代聚光型太阳能热发电(concentrated solar power,CSP)技术的储热方案之一。在储、放热循环过程中,钙基的反应活性会迅速降低,制约其进一步应用。为改善这一问题,该文通过溶胶凝胶法和球磨法制备掺杂NiAl_(2)O_(4)的改性钙基储热材料,系统研究NiAl_(2)O_(4)掺杂对钙基储热循环稳定性和储热/放热过程中反应性能的影响。结果表明:NiAl_(2)O_(4)掺杂对提升CaCO_(3)/CaO循环稳定性起到显著的作用,20次循环时的放热效率可达84%以上,其中,当掺杂摩尔比为100:6:12(Ca:Ni:Al)时,改性材料展现出最佳的稳定性,20次循环时的放热效率为88.7%,是未改性的1.6倍;在反应温度为750℃的煅烧-碳酸化等温循环过程中,NiAl_(2)O_(4)掺杂可以提升反应速率,促使碳酸化反应更早开始,减少反应时间。结合表征结果,该文提出掺杂NiAl_(2)O_(4)改善钙基循环稳定性的反应过程:NiAl_(2)O_(4)均匀分布在钙基材料表面,可以有效抑制钙基的团聚,从而减缓循环性能的衰减,改善CaCO_(3)/CaO在储、放热循环过程中的反应性能。Calcium-based thermochemical storage,utilizing the reversible CaCO_(3)/CaO reaction,offers advantages such as high energy density,affordability,and extended storage periods,making it a potential energy storage solution for emerging concentrated solar power(CSP)technology.Nevertheless,its reactivity diminishes rapidly over successive energy storage and release cycles,limiting its broader utilization.To overcome this limitation,NiAl_(2)O_(4)-doped calcium-based storage materials are synthesized via sol-gel and ball-milling techniques and the impact of NiAl_(2)O_(4)doping on cyclic stability and reactivity during energy storage/release is comprehensively assessed.The results demonstrate that NiAl_(2)O_(4)doping substantially improves the cyclic stability of the CaCO_(3)/CaO reaction,yielding an exothermic efficiency above 84%after 20 cycles.At a molar ratio of 100:6:12(Ca:Ni:Al),the modified material displayed optimal stability with an exothermic efficiency of 88.7%,i.e.a value 1.6 times greater than its undoped counterpart.In isothermal calcinationcarbonation cycles at 750°C,NiAl_(2)O_(4)doping quickens the reaction rate,initiating the carbonation process sooner and consequently shortening the overall reaction duration.Based on characterization outcomes,it is postulated that the improved cyclic stability is attributed to the uniform dispersion of NiAl_(2)O_(4)on the calcium-based material's surface,effectively preventing its agglomeration,slowing cyclic degradation,and optimizing the reactivity of CaCO_(3)/CaO during energy storage/release cycles.

关 键 词：CaCO_(3) CAO 热化学 储热 循环稳定性 

分 类 号：TM91[电气工程—电力电子与电力传动]