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浙江大学学报(工学版)  2026, Vol. 60 Issue (8): 1611-1626    DOI: 10.3785/j.issn.1008-973X.2026.08.001
能源工程、机械工程     
基于氢氧化物的热化学储能体系研究进展
韩翔宇1,2(),韩伟1,2,*(),王英丞1,2,张可臻1,2,王峰年1,2,姚明宇1,2
1. 西安热工研究院有限公司 清洁低碳热力发电国家工程研究中心,陕西 西安 710054
2. 中国华能集团有限公司 高效灵活煤电及碳捕集利用封存全国重点实验室,陕西 西安 710054
Review on hydroxide-based thermochemical energy storage systems
Xiangyu HAN1,2(),Wei HAN1,2,*(),Yingcheng WANG1,2,Kezhen ZHANG1,2,Fengnian WANG1,2,Mingyu YAO1,2
1. National Engineering Research Center of Clean and Low-carbon Thermal Power Generation, Xi’an Thermal Power Research Institute Co. Ltd, Xi’an 710054, China
2. National Key Laboratory of High-Efficiency Flexible Coal Power Generation and Carbon Capture Utilization and Storage, China Huaneng Group Co. Ltd, Xi’an 710054, China
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摘要:

聚焦于CaO/Ca(OH)2与MgO/Mg(OH)2这2类典型氢氧化物热化学储能体系,系统评述其在材料改性、反应器设计及系统集成3个层面的研究进展;总结了掺杂与纳米结构设计在缓解材料团聚、调控反应温度方面的成效,及固定床模块化与流化床机械辅助流化技术方面的突破;阐述了体系作为“卡诺电池”和“化学热泵”应用的理论验证现状. 当前技术规模化应用仍受限于材料储能密度与循环稳定性的权衡、反应器内材料性能动态演化下的热质传递受阻,以及系统与波动性能源供需侧的动态失配. 建议引入人工智能重构材料定向设计路径,深化跨尺度耦合机制研究以突破反应器传热传质瓶颈,并建立动态响应评价体系与中试示范平台,以验证系统在真实变工况下的负荷调节能力.

关键词: 热化学储能CaO/Ca(OH)2MgO/Mg(OH)2材料改性反应器设计系统集成    
Abstract:

Two typical hydroxide thermochemical energy storage systems of CaO/Ca(OH)2 and MgO/Mg(OH)2 were systematically reviewed from three aspects including material modification, reactor design, and system integration. The effectiveness of doping and nanostructure design in mitigating material agglomeration and regulating reaction temperature was summarized. The breakthroughs in modular fixed-bed and mechanically assisted fluidized-bed designs were highlighted, and the current status of theoretical verification for applications such as “Carnot batteries” and “chemical heat pumps” was elucidated. Large-scale application is currently constrained by the trade-off between energy density and cyclic stability, the hindrance of heat and mass transfer due to the dynamic evolution of material properties within the reactor, and the dynamic mismatches between the system and fluctuating energy supply or demand. The incorporation of artificial intelligence is proposed to reconstruct targeted material design pathways in future. Furthermore, the deepening research on cross-scale coupling mechanism is recommended to overcome reactor transport bottlenecks, alongside the establishment of dynamic response evaluation framework and pilot-scale demonstration platform to validate the load regulation capability under realistic, variable operating conditions.

Key words: thermochemical energy storage    CaO/Ca(OH)2    MgO/Mg(OH)2    material modification    reactor design    system integration
收稿日期: 2025-09-26 出版日期: 2026-07-16
CLC:  TP 393  
基金资助: 国家重点研发计划资助项目(2024YFE0212800).
通讯作者: 韩伟     E-mail: hanxiangyu@tpri.com.cn;hanwei@tpri.com.cn
作者简介: 韩翔宇(1997—),男,博士,工程师,从事热化学储能技术研究. orcid.org/0009-0008-5506-1683. E-mail:hanxiangyu@tpri.com.cn
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引用本文:

韩翔宇,韩伟,王英丞,张可臻,王峰年,姚明宇. 基于氢氧化物的热化学储能体系研究进展[J]. 浙江大学学报(工学版), 2026, 60(8): 1611-1626.

Xiangyu HAN,Wei HAN,Yingcheng WANG,Kezhen ZHANG,Fengnian WANG,Mingyu YAO. Review on hydroxide-based thermochemical energy storage systems. Journal of ZheJiang University (Engineering Science), 2026, 60(8): 1611-1626.

链接本文:

https://www.zjujournals.com/eng/CN/10.3785/j.issn.1008-973X.2026.08.001        https://www.zjujournals.com/eng/CN/Y2026/V60/I8/1611

储热类型材料体系t/℃E/(kJ·kg?1)
SHS系统0~100418
大理石142~522593
LHS系统SAT58.3286
NaNO3306172
MgCl2/KCl/NaCl380400
金属氢化物体系Mg/MgH25002 814
Ti/TiH27003 190
氢氧化物体系CaO/Ca(OH)24601 855
MgO/Mg(OH)23002 010
表 1  氢氧化物、金属氢化物体系与典型SHS和LHS系统储能温度及储能密度对比[13-19]
图 1  中空CaO微球在30次循环后的微观形貌图[61]
储热释热
废热源t/℃应用t/℃
工业窑炉排气250~300纺织品生产70~100
化工蒸馏余热110~300蒸馏90~130
污泥焚烧炉70~350纸浆和纸张干燥90~120
苯、甲苯生产200~300灭菌140~150
表 2  可用废热源与热用户[69]
图 2  花朵状MgO微球SEM图[107]
材料制备工艺E/(kJ·kg?1)L/次原料成本1)规模化生产
难度
参考文献
1)原料价格参考http://www.aladdin-e.com/zh_cn/http://www.1688.com/.
Ca(OH)2+Na2Si3O7手动混合-造粒-煅烧~1 000>200Na2Si3O7溶液:529.20元/L[41]
Ca(OH)2+TEOS-SCA混合-干燥-煅烧>30TEOS:219元/L;SCA:49 999.9元/kg[43]
Ca(OH)2+SiO2高精度混合>10SiO2 A300:411.8元/kg[32]、[44]
混合-干燥-煅烧-筛分691.5 MJ/m3>10高吸水树脂:1 029.9元/kg[46]
Ca(OH)2+铜铬黑混合-干燥-煅烧1 302>100铜铬黑:80元/kg[47]
Ca(OH)2+CMC+蛭石混合-压片机压制-多段煅烧830CMC:187.8元/kg;蛭石:467.9元/kg[53]
Ca(OH)2+SiC滚圆-搅拌包覆-煅烧~600>25CMC:187.8元/kg;活性炭:123.9元/kg;
SiC:97.9元/kg
[58]
Ca(OH)2+SiO2+ Al2O3化学法制备致密硅胶-浸涂-
机械混合-挤出-干燥
836>10TEOS:219元/L;Al2O3:139.8元/kg[60]
Ca(OH)2化学法制备-干燥-煅烧1 755>30D-木糖:223.96元/kg;甘氨酸:130.90元/kg[61]
Ca(OH)2+EG超声分散-干燥719.87>10EG:38.9元/kg[68]
Ca(OH)2+KNO3脱气蒸馏水溶解混合-蒸发
干燥
1 315>5KNO3:509.8元/kg[14]
Mg(OH)2+EG湿混合-干燥-压制成型881鳞片石墨:479.8元/kg[92]
Mg(OH)2+碳纳米管沉积-沉淀法1 30010碳纳米管:28 839元/kg[83]
Mg(OH)2+纳米多孔碳湿混合-干燥-煅烧890>60碳多孔小球:166 780元/kg[96]
Mg(OH)2+CaTiO3混合971CaTiO3:409.8元/kg[97]
Mg(OH)2+Fe-LiNO3-TiN湿混合-干燥-煅烧900>15Fe(NO3)3·9H2O:179.8元/kg;
LiNO3:1 095.8元/kg;1 059.8元/kg
[98]
Mg(OH)2+蛭石浸渍-沉积法540>5蛭石:467.9元/kg[99]
Mg(OH)2+Co共沉淀法1 0596Co(NO3)2·6H2O:353.8元/kg[100]
Mg(OH)2+LiCl浸渍-旋蒸-干燥1 360LiCl·H2O:21 091.8元/kg[101]
Mg(OH)2共沉淀法1 209Mg(CH3COO)2:125.8元/kg;NH4OH:272.9元/L[75]
水热法612>10MgCl2·6H2O:71.8元/kg;Na2CO3:103.8元/kg;
NaOH:117.8元/kg
[107]
表 3  CaO/Ca(OH)2与MgO/Mg(OH)2 TCES体系综合性能对比
图 3  机械流化床反应器中2.5次循环后的粉末图[40]
反应器类型传热/传质性能颗粒循环稳定性系统能耗投资成本适用场景
间接式固定床反应器低:受限于热导率,需大量换热面积中:存在粉化、团聚问题,但无机械磨损低:反应流体仅需克服床层压降中:金属框架占比较高中小型、固定式供热
直接式固定床反应器中:受限于床层渗透率低:结构简单、易于模块化工业蒸汽供应、移动式
供热
气体流化床反应器高:气固接触充分,温度均匀低:颗粒磨损严重,易粉化导致流化失败高:需大量流化气体,热损失大中:需气固分离(旋风分离器)与气体循环系统大规模、非黏性粉体、连续高功率输出
机械流化床反应器极高:机械流化床层,传热系数高中:抑制团聚,但存在机械磨损中:电机能耗高:转动部件导致密封与维护成本高黏性粉体、连续高功率
输出
移动床反
应器
中:逆流换热效率相对较高低:黏性粉末流动性差,堵塞流动通道低:重力驱动粉末
流动
中:需配置固体物料加料、输送系统非黏性粉体、连续高功率输出
表 4  TCES反应器综合性能对比
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