热化学储能材料的制备及其在跨季节储能中的应用进展研究

doi:10.19799/j.cnki.2095-4239.2025.0381

摘要/Abstract

摘要：

热化学储能技术利用热化学储能材料可逆的化学反应来储放热，材料的性能直接决定了热化学储热系统的效率与应用潜力。目前，热化学储能材料推广应用面临着热传导率低、转化率低、循环稳定性差和成本高昂等问题。本文综述了不同温区分类下热化学储热材料在跨季节储能中的研究进展和优化路径，重点讨论了热化学储热材料的制备方法和改性方式。回顾了低温水合盐、氨络合物、金属氧化物、金属氢化物、氢氧化物、碳酸盐、氨和有机物等材料的热化学储能特性。针对材料的制备方法，阐述了溶胶-凝胶法、封装成型法、微胶囊法、浸渍法的原理和典型应用实例，着重介绍了聚合物、无机氧化物、陶瓷这三种壳封装材料的不同点并对比分析了干法浸渍和湿法浸渍的优缺点及适用场景。针对材料的改性方式，主要介绍了物理改性、化学改性、复合材料掺杂三种方式，对改性前后热化学储能材料的物理和化学特性进行了差异化分析。综合分析表明，通过选择合适材料制备方法以及利用化学元素掺杂、金属表面涂层、物理结构调控和多孔载体复合等改性方式，可以显著提高材料的循环稳定性、使用寿命、反应活性和储热密度，有望促使热化学储能技术商业化应用的早日实现。

关键词: 热化学储能, 储热材料, 吸附材料, 基体改性, 太阳能

Abstract:

Thermochemical energy storage technology utilizes the reversible chemical reactions of thermochemical energy storage materials to store and release heat. The performance of the materials directly determines the efficiency and application potential of the thermochemical heat storage system. At present, the promotion and application of thermochemical energy storage materials are confronted with problems such as low thermal conductivity, low conversion rate, poor cycle stability and high cost. This paper reviews the research progress and optimization paths of thermochemical heat storage materials in cross-seasonal energy storage under different temperature zone classifications, with a focus on discussing the preparation methods and modification approaches of thermochemical heat storage materials. The thermochemical energy storage characteristics of materials such as low-temperature hydrated salts, ammonia complexes, metal oxides, metal hydrides, hydroxides, carbonates, ammonia and organic substances were reviewed. Regarding the preparation methods of materials, the principles and typical application examples of sol-gel method, encapsulation molding method, microcapsule method and impregnation method are expounded. The differences among the three shell encapsulation materials, namely polymers, inorganic oxides and ceramics, are emphatically introduced, and the advantages, disadvantages and applicable scenarios of dry impregnation and wet impregnation are compared and analyzed. For the modification methods of materials, three methods, namely physical modification, chemical modification and doping of composite materials, are mainly introduced. The physical and chemical properties of thermochemical energy storage materials before and after modification are differentiated and analyzed. Comprehensive analysis shows that by choosing appropriate material preparation methods and using modification methods such as chemical element doping, metal surface coating, physical structure regulation and porous carrier composite, the cycling stability, service life, reactivity and heat storage density of materials can be significantly improved, which is expected to promote the early realization of commercial application of thermochemical energy storage technology.

Key words: Thermochemical energy storage, Heat storage materials, Adsorption materials, Matrix modification, Solar energy

杨蕊, 乔洋, 周奕锟, 张雨欣, 王晨, 赵学敏, 折晓会. 热化学储能材料的制备及其在跨季节储能中的应用进展研究[J]. 储能科学与技术, doi: 10.19799/j.cnki.2095-4239.2025.0381.

Rui YANG, Yang QIAO, Yikun ZHOU, Yuxing ZHANG, Chen WANG, Xuemin ZHAO, Xiaohui SHE. Research on the preparation of thermochemical energy storage materials and application in cross-season energy storage[J]. Energy Storage Science and Technology, doi: 10.19799/j.cnki.2095-4239.2025.0381.

图/表 15

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表6

热化学储能材料不同掺杂物改性的优缺点[93]"

材料	实验添加	结果	文献
Co₃O₄基材料	Fe	与纯钴氧化物相比，其还原/再氧化温度更高且两者温差更小(可通过增加Fe含量调节)，再氧化完成度更好，晶粒生长有限且静电充电低、成本低。添加10 mol% Fe：在12次氧化还原循环中具有良好的循环稳定性	[94]
		能量密度和储氧能力降低，且存在烧结和晶粒尺寸增大的问题。Co3O4中添加20摩尔%以上的Fe时，材料不再是单一尖晶石相，而是两种尖晶石的混合物
Co₃O₄基材料	CuO	与纯钴氧化物相比，在40次氧化还原循环中循环稳定性良好，能量密度相当，且还原反应温度降低50K，氧化与还原之间的温差较小，反应效率较高，烧结现象缓解。	[95]
Co₃O₄基材料	CeO₂	改善Co3O4的反应动力学，具有高能量密度496 J/g，但热化学稳定性低	[106]
Co₃O₄基材料	Al₂O₃	体积储能密度由870升至1700 kg/m³、晶粒生长有限、再氧化完成度好、低静电荷、氧化反应起始温度增加约27K，而还原不受影响，且10wt%Al₂O₃在112次循环中显示良好结构稳定性。	[97]
Co₃O₄基材料	Cr₂O₃	良好的再氧化完成、有限的晶粒生长、低静电荷	[108]
Co₃O₄基材料	Y_0.15Zr_0.85O_1.93	还原和再氧化过程温差小、能量密度高	[96]
Co₃O₄基材料	SiC	氧化还原反应弱、能量密度比纯钴氧化物低	[96]
Co₃O₄基材料	NiCo₂O₄(尖晶石)	与纯钴氧化物相比，操作温度大致相同，再氧化反应动力学高且再氧化反应完全但还原反应完成率低	[99]
Co₃O₄基材料	CuCo₂O₄(尖晶石)	工作温度高但操作温度接近CuO的熔点、再氧化反应完成度和动力学性能较差	[99]
Co₃O₄基材料	MgCo₂O₄(尖晶石)	工作温度高但再氧化反应完成度和动力学性能较差	[99]
Mn₂O₃基材料	Cu掺杂	与氧化锰相比反应温度高，还原和再氧化之间的温差减少41K(热滞后)但还原反应动力学缓慢。	[100]
Mn₂O₃基材料	Fe-Cu共掺杂	具有高储能密度、快速再氧化反应动力学和较小的热滞后温差，共掺杂会降低还原动力学，可通过提高加热速率来增强反应速率，20%F-1%Cu和5%Fe-1%Cu掺杂样品在30次氧化还原中具有良好的循环稳定性，但高Fe和Cu掺杂样品易烧结。	[101][102]
Mn₂O₃基材料	LiMnO₂	具有高还原焓(165 ± 1kJ/kg)、还原和氧化之间的温差小(热滞后84 ± 2K)且可逆的氧化还原反应超过45次	[103]
CuO基材料	Co₃O₄	无熔化问题、氧化和还原反应之间的温差提高、能量密度和工作温度低于纯氧化铜	[95]
CuO基材料	Cr₂O₃	反应温度(约为1313K)接近氧化铜的熔点，且反应不可逆	[95][104]
BaO基材料	NiO、TiO₂、Fe₂O₃、SnO、ZnO、BaTiO₃或BaCuOx	纯氧化钡的化学稳定性和氧化还原性能没有改善	[98]
Fe₂O₃基材料	添加Co₃O₄	反应温度降低，反应焓降低，储能密度下降(5%含量的Co添加物使反应焓由599 J/g降至295.9 J/g)	[105]
Al₂O₃基材料	添加Mn₂O₃	不存在氧化还原反应、缓慢的再氧化反应	[95]

表6

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水合盐材料	n的最大值	n的最小值	开放系统能量密度(GJ/m³)	封闭系统能量密度(GJ/m³)	水化温度(K)(1.2kPa)	脱水温度(K)(2kPa)	最低熔点(K)	价格(€/kg)	稳定性
GdCl₃∙nH₂O	6	0	2.7	1.56	363	371	-	稀土金属	-
EuCl₃∙nH₂O	6	0	2.61	1.52	362	370	-	稀土金属	-
CrCl₂∙nH₂O	3	0	2.11	1.31	334	341	372	-	Cr²⁺不稳定
LiCl∙nH₂O	1	0	2.08	1.36	339	345	-	37	-
LiBr∙nH₂O	1	0	2.01	1.37	376	383	393	37	-
FeCl₂∙nH₂O	2	0	1.93	1.26	326	332	-	-	Fe²⁺不稳定
CsF∙nH₂O	1	0	1.79	1.20	357	364	-	>10	-
Ca(ClO₄)₂∙nH₂O	4	0	1.75	1.17	365	373	-	-	爆炸性
CuCl₂∙nH₂O	2	0	1.74	1.13	326	332	>423	3	急性毒性
Na₂S∙nH₂O	5	0.5	2.79	1.58	339	355	355	0.65	产生H₂S
RbF∙nH₂O	1	0	1.57	1.10	357	364	-	>10	-
CrCl₂∙nH₂O	2	0	1.57	1.07	335	342	-	-	Cr²⁺不稳定
CaCl₂∙nH₂O	2	0	1.54	1.06	336	384	449	0.29	-
Mg(NO₃)₂∙nH₂O	6	2	1.53	1.04	334	341	362	-	损失N₂
LiNO₂∙nH₂O	1	0	1.51	1.07	367	375	-	37	损失N₂
Mg(NO₃)₂∙nH₂O	2	0	1.51	1.08	378	386	-	-	损失N₂
LiI∙nH₂O	3	1	1.49	1.02	370	368	-	37	-
LaCl₃∙nH₂O	7	3	1.48	1.03	339	346	364	稀土元素	-
KAl(SO₄)₂∙nH₂O	3	0	1.39	1.01	330	336	365		-
MnI₂∙nH₂O	4	0	1.39	0.90	332	336	353		急性毒性
VOSO₄∙nH₂O	3	1	1.35	0.98	346	353		>10	急性毒性
K₂CO₃∙nH₂O	1.5	0	1.30	0.96	332	338	>423	1	-
MgCl₂∙nH₂O	6	2	1.93	1.24	334	377	390	0.18	产生HCl
Na₂S∙nH₂O	5	2	1.77	1.17	339	346	355	0.65	产生H₂S
Na₂S∙nH₂O	2	0.5	1.60	1.14	348	355	355	0.65	产生H₂S

名称	化学反应	产物	储能密度(kWh/m³)	反应温度(K)	反应压强(MPa)
金属氧化物	2Co₃O₄↔6CoO+O₂	Co₃O₄	295	973–1123	0-1
金属氢化物	MgH₂↔Mg+H₂	MgH₂	580	573–773	5-10
氢氧化物	Ca(OH)₂↔CaO+H₂O	Ca(OH)₂	437	623–1173	0.1-10.0
	Mg(OH)₂↔MgO+H₂O	Mg(OH)₂	388	573–723	0.1-10.0
氨	2NH₃↔N₂+3H₂	NH₃(l)	745	673–973	10-30
碳酸盐	CaCO₃↔CaO+CO₂	CaCO₃	692	973–1273	0-10
	PbCO₃↔PbO+CO₂	PbCO₃	303	573–1723	0-10
甲烷重整	CH₄+H₂O↔CO+3H₂	CH₄(g)	7.8	873–1223	1.0-3.5
	CH₄+CO₂↔2CO+2H₂	CH₄(g)	7.7	973–1173	1.0-3.5

材料	反应温度(K)	优点	缺点	技术现状
氧化物	973以上	高反应焓(205 kJ/mol)	储存O₂	实验室规模
		宽操作温度(973-1300K)	产物有毒(Co₃O₄/CoO)
		低操作压力(0-0.1MPa)	产物成本高
		无催化剂
		无副反应(BaO/BaO₂)
		高可逆性(500次循环)(Co₃O₄/CoO)
金属氢化物	573~973	高能量密度	反应动力学差	中试规模
		高可逆性	氢脆
		大量关于储氢和热泵应用的实验反馈	材料成本较高
氢氧化物	573以上	材料成本低	材料结块	实验室和中试规模
氢氧化物	573以上	无毒	与CO₂的副反应	实验室和中试规模
氨合成/分解	673~973	易于控制	有毒	中试规模
		无副反应	遏制成本高
		丰富的工业经验	体积能量密度低
			工作压力高
碳酸盐	573~1723	廉价、丰富、无毒	可逆性较差	实验室和中试规模
		高能量密度	低循环稳定性
		高工作温度(1700K)	烧结
		适合高温发电	物料结块
			与CO₂的副反应
甲烷重整	873~1223	高操作温度(1223K)	体积能量密度低	中试规模
		高质量能量密度	催化剂成本高
		更便宜的能量输送方法(最远100-300km)	CO毒性
SO₃/O₂/SO₂系统	1073~1473	高工作温度(1473K)	有毒
SO₃/O₂/SO₂系统		硫酸生产中的工业反馈	高度腐蚀
硫基循环	773~1473	价格便宜且市场有售	有毒	实验室规模
		储存稳定	需要高度防护的容器
		能量密度为9 MJ/kg
		硫具有成本效益(<0.2€/kg)

封装壳层材料	聚合物	无机氧化物	陶瓷
优点	1.化学惰性减少副反应	1.化学惰性较强	1.化学惰性强
	2.良好弹性适应体积变化	2.热稳定性高(1273K以上)	2.热稳定性极高(1273K以上)
	3.耐磨性好	3.耐磨性好	3.耐磨性好
	4.不影响导热性	4.机械稳定性好	4.机械稳定性好
	5.加工简单，无需高温烧结	5.成本效益高	5.成本低
缺点	1.受熔融/分解温度限制	1.需高温烧结，不适用低温敏感核材料	1.烧结影响稳定性
	2.热稳定性低	2.脆性高、易断裂	2.脆性大，易断裂
	3.高温环境失效	3.热导性较低	3.需要助熔剂/特殊工艺降低烧结温度
	4.机械强度较弱	4.与材料发生副反应	4.热导性低于金属材料

方法	原理	优点	缺点	适用场景
干法浸渍	气相扩散	无溶剂废液、可浸渍高温热化学材料、高负载性	工艺复杂、成本较高、均匀性较差	高温储热体系、气体吸附剂、难容易升华物质、微孔基质
湿法浸渍	溶液渗透	工艺简单、浸渍均匀、高分散性、成本较低	浸渍率低、需要额外操作去除溶剂	中低温储热体系、可溶性盐类、络合物、亲水多孔材料