高温相变储热材料制备与应用研究进展

doi:10.19799/j.cnki.2095-4239.2022.0521

储能科学与技术 ›› 2023, Vol. 12 ›› Issue (2): 398-430.doi: 10.19799/j.cnki.2095-4239.2022.0521

高温相变储热材料制备与应用研究进展

刘伟¹(), 李振明¹(), 刘铭扬¹, 杨岑玉¹, 梅超², 李迎²

^1.中国电力科学研究院有限公司储能与电工新技术研究所，北京 100192
^2.国网福建省电力有限公司厦门供电公司，福建厦门 361004

收稿日期:2022-09-13 修回日期:2022-10-21 出版日期:2023-02-05 发布日期:2023-02-24
通讯作者: 李振明 E-mail:liuwei3@epri.sgcc.com.cn;lizhenming@epri.sgcc.com.cn
作者简介:刘伟（1974—），男，高级工程师，研究方向为相变储能技术、储能材料，E-mail：liuwei3@epri.sgcc.com.cn；
基金资助:
国家电网有限公司科技项目“面向工业领域电能替代的蒸汽型高温相变储热关键技术研究与示范”(5419-202021250A-0-0-00)

Review of high-temperature phase change heat storage material preparation and applications

Wei LIU¹(), Zhenming LI¹(), Mingyang LIU¹, Cenyu YANG¹, Chao MEI², Ying LI²

^1.Energy Storage and Novel Technology of Electrical Engineering Department, China Electric Power Research Institute Limited Company, Beijing 100192, China
^2.State Grid Xiamen Electric Power Supply Company, Xiamen 361004, Fujian, China

Received:2022-09-13 Revised:2022-10-21 Online:2023-02-05 Published:2023-02-24
Contact: Zhenming LI E-mail:liuwei3@epri.sgcc.com.cn;lizhenming@epri.sgcc.com.cn

摘要/Abstract

摘要：

面向工业领域蒸汽供热需求，大力发展高温相变储热技术，有效调节电网峰谷负荷，有力促进电能替代，助力实现“碳达峰、碳中和”目标。本文通过对近期相关文献的回顾，首先介绍了相变材料优选原则与方法，其次介绍了高温相变材料的分类，着重阐述了盐基高温复合相变材料的最新研究动态，包括金属泡沫/无机盐、石墨泡沫/无机盐、膨胀石墨/无机盐、多孔陶瓷/无机盐复合相变材料和黏土矿物/无机盐相变复合材料，指出高温复合相变材料可以改善无机盐低热导率和热稳定性、腐蚀密封材料等问题。然后总结了高温相变材料的制备方法，指出浸渗法、溶胶-凝胶法、冷压烧结法在实际应用中各有利弊，相比之下，冷压烧结法是制备盐基复合材料最具成本效益的方法。最后重点介绍了高温复合相变材料在工业过程余热回收、电力调峰、太阳能热发电三个领域的应用现状，为研究不同场景下蒸汽型高温相变储热系统容量配置和经济评估方法提供了理论基础。

关键词: 高温储热, 相变材料, 制备方法, 储热装置

Abstract:

Faced with the demand for steam heating in the industrial field, we will vigorously develop high-temperature phase change heat storage technology, effectively adjust the peak and valley loads of power grids, effectively promote the replacement of electric energy, and help achieve the goal of "carbon peak and carbon neutrality." This article comprises a literature review of the principles and methods of phase change material optimization. High-temperature phase change materials are also classified. The latest research trends of high-temperature composite phase change materials are emphatically described, including metal foam/inorganic salt, graphite foam/inorganic salt, expanded graphite/inorganic salt, porous ceramic/inorganic salt, and porous clay mineral/inorganic salt composite phase change materials. Notably, high-temperature composite phase change materials can improve the low thermal conductivity and stability of inorganic salts and corrosion of sealing materials. Next, the preparation methods of high-temperature phase change materials are summarized; the advantages and disadvantages of the infiltration method, sol-gel method, and cold pressing sintering method in practical application are highlighted. In comparison, the cold pressing sintering method is the most cost-effective for preparing salt matrix composites. Finally, the application statuses of high-temperature composite phase change materials in industrial waste heat recovery, power peak regulation, and solar thermal power generation are discussed, providing a basis for studying the capacity allocation and economic evaluation methods of high-temperature phase change heat storage systems of the steam type under different scenarios. This review has a certain reference value for the development of high-temperature phase change heat storage technology.

Key words: high temperature heat storage, phase change material, preparation method, thermal storage device

中图分类号:

TK 02

刘伟, 李振明, 刘铭扬, 杨岑玉, 梅超, 李迎. 高温相变储热材料制备与应用研究进展[J]. 储能科学与技术, 2023, 12(2): 398-430.

Wei LIU, Zhenming LI, Mingyang LIU, Cenyu YANG, Chao MEI, Ying LI. Review of high-temperature phase change heat storage material preparation and applications[J]. Energy Storage Science and Technology, 2023, 12(2): 398-430.

图/表 22

表1

部分高温相变材料无机盐的热物理性质[6-7, 17-21]"

化合物	熔化温度/℃	熔化热/(kJ/kg)	导热系数/[W/(m·K)]	比热容/[kJ/(kg·K)]
NaNO₃	306	182	0.5/—(液固)	—/1.1(液固)
KNO₃	334	266	—/0.5	—/0.953(液固)
NaOH	323	170	0.92/—(液固)	2.09/2.01(液固)
KOH	380	149.7	—/0.5(液固)	—
Na₂CO₃	854	275.7	—	—/2(液固)
K₂CO₃	897	235.8	—	—/2(液固)
96KNO₃-4KCl	320	150	—/0.5(液固)	—/1.21(液固)
60MgCl₂-20.4KCl-19.6NaCl	380	400	—	—/0.96(液固)
52MgCl₂-48NaCl	450	430	0.95/—(液固)	1/0.92(液固)
64MgCl₂-36KCl	470	388	0.83/—(液固)	0.96/0.84(液固)
48MgCl₂-27CaCl₂-25KCl	487	342	0.88/—(液固)	0.92/0.8(液固)
53BaCl₂-28KCl-19NaCl	542	221	0.86/—(液固)	0.8/0.63(液固)
44Li₂CO₃-56Na₂CO₃	496	370	2.09/—(液固)	2.09/1.8(液固)
39MgCl₂-61NaCl	435	351	0.81/—(液固)	0.96/0.8(液固)
22Li₂CO₃-16Na₂CO₃-62K₂CO₃	580	288	1.95/—(液固)	2.09/1.80(液固)
67CaCl₂-33NaCl	500	281	1.02/—(液固)	1/0.84(液固)
33LiF-67KF	442	618	3.98/—(液固)	1.63/1.34(液固)
12NaF-59KF-29LiF	454	590	4.50/—(液固)	1.55/1.34(液固)
20Li₂CO₃-60Na₂CO₃-20K₂CO₃	550	283	1.83/—(液固)	1.88/1.59(液固)
54KCl-46ZnCl₂	432	218	0.83/—(液固)	0.88/0.67(液固)
28KCl-19NaCl-53BaCl₂	542	221	0.86/—(液固)	0.80/0.63(液固)
48NaCl-52MgCl₂	450	430	0.95/—(液固)	1.00/0.92(液固)
47BaCl₂-24KCl-29CaCl	551	219	0.95/—(液固)	0.84/0.67(液固)
36KCl-64MgCl₂	470	388	0.83/—(液固)	0.96/0.84(液固)
33NaCl-67CaCl₂	500	281	1.02/—(液固)	1.00/0.84(液固)
37MgCl₂-63SrCl₂	535	239	1.05/—(液固)	0.80/0.67(液固)
47Li₂CO₃-53K₂CO₃	488	342	1.99/—(液固)	1.34/1.03(液固)
17NaF-21KF-62K₂CO₃	520	274	1.50/—(液固)	1.38/1.17(液固)
28Li₂CO₃-72K₂CO₃	498	263	1.85/—(液固)	1.80/1.46(液固)
51K₂CO₃-49Na₂CO₃	710	163	1.73/—(液固)	1.56/1.67(液固)
24KCl-47BaCl₂-29CaCl₂	551	219	0.95/—(液固)	0.84/0.67(液固)
32Li₂CO₃-35K₂CO₃-Na₂CO₃	397	276	2.02/—(液固)	1.63/1.67(液固)
61KCl-39MgCl₂	435	351	0.81/—(液固)	0.96/0.8(液固)
40KCl-23KF-37K₂CO₃	528	283	1.19/—(液固)	1.26/1(液固)
35Li₂CO₃-65K₂CO₃	505	344	1.89/—(液固)	1.76/1.34(液固)

表1

表2

表3

图1

图 2

图3

图4

图 5

图6

图7

图8

图9

图 10

图 11

图12

图 13

图14

图15

图16

图17

图18

图19

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材料	过冷度/℃	材料	过冷度/℃	材料	过冷度/℃
NaF-22CaF₂-13MgF₂	15～30	CaF₂-50MgF₂	3～20	KCaF₃	20～30
NaF-40MgF₂-20CaF₂	40～60	KF-69MgF₂	20	KMgF₃	20～30
NaF-20MgF₂-16KF	20～30	NaF-60MgF₂	70～80	MgF₂-40CeF₃	7～20
NaF-23MgF₂	60～80	NaMgF₃	30～120	KF-61CaF₂	30～40

金属及金属合金	熔化温度/℃	熔化热/(kJ/kg)
Zn	419	112
Al	661	388
96Zn-4Al	381	138
86.4Al-9.4Si-4.2Sb	471	471
59Al-33Mg-6Zn	443	310
65.35Al-34.65Mg	497	285
60.8Al-33.2Cu-6Mg	506	365
64.6Al-28Cu-5.2Si-2.2Mg	507	374
68.5Al-26.5Cu-5Si	525	364
Mg	648	365
46.3Mg-53.7Zn	341	185
86Si-12Al	576	560
56Si-44Mg	946	757
49Zn-45Cu-6Mg	703	176
49.1Cu-46.3Al-4.6Si	571	406
83.14Al-11.7Si-5.16Mg	555	485
64.1Al-28Mg-5.2Si-2.2Cu	507	374
66.92Al-33.08Cu	548	372

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高温相变储热材料制备与应用研究进展

Review of high-temperature phase change heat storage material preparation and applications

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