沸石/水合盐吸附储热材料制备及性能研究

doi:10.19799/j.cnki.2095-4239.2025.0237

储能科学与技术 ›› 2025, Vol. 14 ›› Issue (7): 2853-2864.doi: 10.19799/j.cnki.2095-4239.2025.0237

• 第十三届储能国际峰会暨展览会专辑 • 上一篇下一篇

沸石/水合盐吸附储热材料制备及性能研究

陈一鸣¹^,²(), 凌浩恕²^,⁴^,⁵, 刘猛³, 徐玉杰²^,⁴^,⁵(), 沈国清¹(), 贾运²^,⁴^,⁵, 陈海生²^,⁴^,⁵

^1.华北电力大学能源动力与机械工程学院，北京 102206
^2.中国科学院工程热物理研究所，北京 100190
^3.中国标准化研究院，北京 100191
^4.中国科学院大学，北京 101408
^5.长时规模储能重点实验室(中国科学院)，北京 100190

收稿日期:2025-03-24 修回日期:2025-04-02 出版日期:2025-07-28 发布日期:2025-07-11
通讯作者: 徐玉杰,沈国清 E-mail:cym898730398@163.com;xuyujie@iet.cn;shenguoqing@ncepu.edu.cn
作者简介:陈一鸣（2000—），男，硕士研究生，研究方向为沸石/水合盐吸附储热，E-mail：cym898730398@163.com；
基金资助:
国家重点研发计划(2024YFB2408800);中国科学院战略性先导科技专项(XDA0400000);中国科学院青年促进会(2023154);中国科学院国际合作局对外合作重点项目资助(117GJHE2023009MI)

Preparation and performance study of zeolite/hydrated salt adsorption heat storage materials

Yiming CHEN¹^,²(), Haoshu LING²^,⁴^,⁵, Meng LIU³, Yujie XU²^,⁴^,⁵(), Guoqing SHEN¹(), Yun JIA²^,⁴^,⁵, Haisheng CHEN²^,⁴^,⁵

^1.School of Energy Power and Mechanical Engineering, North China Electric Power University, Beijing 102206, China
^2.Institute of Engineering Thermophysics, Chinese Academy of Sciences, Beijing 100190, China
^3.China National Institute of Standardization, Beijing 100191
^4.University of Chinese Academy of Sciences, Beijing 101408, China
^5.Key Laboratory of Long-Duration and Large-Scale Energy Storage (Chinese Academy of Sciences), Beijing 100190, China

Received:2025-03-24 Revised:2025-04-02 Online:2025-07-28 Published:2025-07-11
Contact: Yujie XU, Guoqing SHEN E-mail:cym898730398@163.com;xuyujie@iet.cn;shenguoqing@ncepu.edu.cn

摘要/Abstract

摘要：

在“碳达峰·碳中和”目标引领下，我国正大力发展可再生能源，并针对供需不平衡、时空差异、间歇性和不稳定性等本质问题，积极发展储能技术。热化学吸附储热具有高储热密度、散热损失小等优点，是最具发展前景的储热技术之一。沸石是吸附储热应用最为成熟的材料，但是存在储热密度相对低等缺点。利用水合盐浸渍沸石是改善上述问题的有效方法，但是在沸石/水合盐复合材料中缺少针对水合盐最佳配比的系统研究。利用了常用的MgSO₄·7H₂O，MgCl₂·6H₂O，LaCl₃·7H₂O，CaCl₂·2H₂O等四种水合盐材料浸渍沸石，制备了不同质量分数的沸石/水合盐吸附储热材料，对其吸附性能、储热密度和循环性能进行了深入研究。结果表明，浸渍沸石的MgCl₂最佳质量分数为30%，在80%RH下具有最佳的吸附性能和最高的储热密度，分别为44.99%与638.9 J/g，其次为浸渍沸石的MgSO₄，吸附质量和储热密度在80%RH下为38.0%和568.5 J/g。在后续循环实验的结果表明，浸渍10%MgSO₄的沸石复合材料具有最佳的循环稳定性，但吸附性能和储热密度低于30%质量分数的沸石/MgCl₂储热材料。研究结果有助于完善沸石/水合盐复合材料的研究，为沸石储热材料的性能提升和应用提供参考。

关键词: 吸附储热, 沸石, 水合盐, 吸附性能, 储热密度

Abstract:

Toward the goal of "reaching the peak of carbon and carbon neutrality," China is vigorously developing renewable energy and actively developing energy storage technology to address the critical problems of supply and demand imbalance—space-time difference, intermittence, and instability. Thermochemical adsorption heat storage offers the advantages of high heat storage density and low heat loss, making it one of the most promising heat storage technologies. Zeolite is well-known for its applications in adsorption and heat storage, but it has the disadvantage of relatively low heat storage density. Impregnating zeolite with hydrated salts can effectively address these problems. However, systematic research on the optimal ratio of hydrated salts in zeolite/hydrated salt composites is lacking. In this study, zeolite was impregnated with four commonly used hydrated salt materials, namely, MgSO₄·7H₂O, MgCl₂·6H₂O, LaCl₃·7H₂O, and CaCl₂·2H₂O. Adsorption and heat storage materials composed of zeolite/hydrated salt with different mass fractions were then prepared. The adsorption properties, heat storage density, and cycling properties of these materials were examined comprehensively. The results showed that the optimum mass fraction of MgCl₂ impregnated with zeolite was 30%. This material achieved the best adsorption performance (44.99%) and the highest heat storage density (638.9 J/g) at 80% relative humidity (RH). The second-best performance was achieved by MgSO₄ impregnated with zeolite, which had an adsorption mass of 38.0% and a heat storage density of 568.5 J/g at 80% RH. The results of subsequent cyclic experiments showed that the zeolite composite impregnated with 10% MgSO₄ had the best cyclic stability but lower adsorption property and heat storage density than the zeolite/MgCl₂ heat storage material with a 30% mass fraction. This work will support research on zeolite/hydrated salt composites and provide a reference for the performance improvement and application of zeolite heat storage materials.

Key words: adsorption heat storage, zeolite, hydrous salt, adsorption performance, heat storage density

中图分类号:

TK 02

陈一鸣, 凌浩恕, 刘猛, 徐玉杰, 沈国清, 贾运, 陈海生. 沸石/水合盐吸附储热材料制备及性能研究[J]. 储能科学与技术, 2025, 14(7): 2853-2864.

Yiming CHEN, Haoshu LING, Meng LIU, Yujie XU, Guoqing SHEN, Yun JIA, Haisheng CHEN. Preparation and performance study of zeolite/hydrated salt adsorption heat storage materials[J]. Energy Storage Science and Technology, 2025, 14(7): 2853-2864.

图/表 17

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

参考文献 28

[1]	陈海生, 李泓, 徐玉杰, 等. 2023年中国储能技术研究进展[J]. 储能科学与技术, 2024, 13(5): 1359-1397. DOI: 10.19799/j.cnki.2095-4239.2024.0441.
	CHEN H S, LI H, XU Y J, et al. Research progress on energy storage technologies of China in 2023[J]. Energy Storage Science and Technology, 2024, 13(5): 1359-1397. DOI: 10.19799/j.cnki.2095-4239.2024.0441.
[2]	姜竹, 邹博杨, 丛琳, 等. 储热技术研究进展与展望[J]. 储能科学与技术, 2022,11(9): 2746-2771.
	JIANG Z, ZOU B, CONG L, et al. Recent progress and outlook of thermal energy storage technologies[J]. Energy Storage Science and Technology, 2022, 11(9): 2746-2771.
[3]	YAN T, LI T X, WANG R Z. 18 Thermochemical heat storage for solar heating and cooling systems[J]. Advances in Solar Heating and Cooling, 2016: 491-522. DOI: 10.1016/B978-0-08-100301-5.00018-7.
[4]	闫霆, 王文欢, 王如竹. 化学吸附储热技术的研究现状及进展[J]. 材料导报, 2018, 32(23): 4107-4115, 4124.
	YAN T, WANG W H, WANG R Z. Present status and progress of research on chemical adsorption heat storage[J]. Materials Review, 2018, 32(23): 4107-4115, 4124.
[5]	葛志伟, 叶锋, LASFARGUES Mathieu, 等. 中高温储热材料的研究现状与展望[J]. 储能科学与技术, 2012, 1(2): 89-102.
	GE Z W, YE F, LASFARGUES M, et al. Recent progress and prospective of medium and high temperatures thermal energy storage materials[J]. Energy Storage Science and Technology, 2012, 1(2): 89-102.
[6]	ALVA G, LIN Y X, FANG G Y. An overview of thermal energy storage systems[J]. Energy, 2018, 144: 341-378. DOI: 10.1016/j.energy.2017.12.037.
[7]	LEE D, KANG C. A study on development of the thermal storage type plate heat exchanger including PCM layer[J]. Journal of Mechanical Science and Technology, 2019, 33(12): 6085-6093. DOI: 10.1007/s12206-019-1152-x.
[8]	SUN V, ASANAKHAM A, DEETHAYAT T, et al. Increase of power generation from solar cell module by controlling its module temperature with phase change material[J]. Journal of Mechanical Science and Technology, 2020, 34(6): 2609-2618. DOI: 10.1007/s12206-020-0336-8.
[9]	CAO N V, DUONG X Q, LEE W S, et al. Effect of heat exchanger materials on the performance of adsorption chiller[J]. Journal of Mechanical Science and Technology, 2020, 34(5): 2217-2223. DOI: 10.1007/s12206-020-0443-6.
[10]	YU N, WANG R Z, WANG L W. Sorption thermal storage for solar energy[J]. Progress in Energy and Combustion Science, 2013, 39(5): 489-514. DOI: 10.1016/j.pecs.2013.05.004.
[11]	汪翔, 陈海生, 徐玉杰, 等. 储热技术研究进展与趋势[J]. 科学通报, 2017, 62(15): 1602-1610.
	WANG X, CHEN H S, XU Y J, et al. Advances and prospects in thermal energy storage: A critical review[J]. Chinese Science Bulletin, 2017, 62(15): 1602-1610.
[12]	吴娟, 龙新峰. 太阳能热化学储能研究进展[J]. 化工进展, 2014, 33(12): 3238-3245.
	WU J, LONG X F. Research progress of solar thermochemical energy storage[J]. Chemical Industry and Engineering Progress, 2014, 33(12): 3238-3245.
[13]	LAI Z Y, DING L W, LYU H K, et al. Experimental study on energy storage characteristics of sintered ore particle packed beds[J]. Journal of Thermal Science, 2025, 34(1): 242-253. DOI: 10.1007/s11630-024-2079-9.
[14]	陈佳丽, 赵国祥, 颜亚玉, 等. 机器学习探究电子气体在沸石分子筛上的吸附[J]. 无机化学学报, 2025, 41(1): 155-164.
	CHEN J L, ZHAO G X, YAN Y Y, et al. Machine learning exploring the adsorption of electronic gases on zeolite molecular sieves[J]. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 155-164.
[15]	WU Q M, LUAN H M, XIAO F S. Targeted synthesis of zeolites from calculated interaction between zeolite structure and organic templateOpen Access[J]. National Science Review, 2022, 9(9): nwac023. DOI: 10.1093/nsr/nwac023.
[16]	杨慧, 童莉葛, 尹少武, 等. 水合盐热化学储热材料的研究概述[J]. 材料导报, 2021, 35(17): 17150-17162.
	YANG H, TONG L G, YIN S W, et al. A review on the salt hydrate thermochemical heat storage materials[J]. Materials Reports, 2021, 35(17): 17150-17162.
[17]	张敏, 卢允庄, 王如竹. 沸石分子筛水吸附工质对的吸附性能及导热性能[J]. 太阳能学报, 2003, 24(1): 37-40.
	ZHANG M, LU Y Z, WANG R Z. Experimental study on the adsorption and heat transfer performance of zeolite-water working pair[J]. Acta Energiae Solaris Sinica, 2003, 24(1): 37-40.
[18]	白峰, 马鸿文. 13X沸石分子筛的比表面积和孔分布[J]. 现代地质, 2008, 22(5): 838-844.
	BAI F, MA H W. Specific surface area and pore size distribution of 13X zeolite molecular sieves[J]. Geoscience, 2008, 22(5): 838-844.
[19]	SAYıLGAN Ş Ç, MOBEDI M, ÜLKÜ S. Effect of regeneration temperature on adsorption equilibria and mass diffusivity of zeolite 13x-water pair[J]. Microporous and Mesoporous Materials, 2016, 224: 9-16. DOI: 10.1016/j.micromeso.2015.10.041.
[20]	李威, 王秋旺, 曾敏. 水合盐基中低温热化学储热材料性能测试及数值研究[J]. 化工学报, 2021, 72(5): 2763-2772, 2330.
	LI W, WANG Q W, ZENG M. Performance test and numerical study of salt hydrate-based thermochemical heat storage materials at middle-low temperature[J]. CIESC Journal, 2021, 72(5): 2763-2772, 2330.
[21]	ZONDAG H, KIKKERT B, SMEDING S, et al. Prototype thermochemical heat storage with open reactor system[J]. Applied Energy, 2013, 109: 360-365. DOI: 10.1016/j.apenergy. 2013.01.082.
[22]	WHITING G T, GRONDIN D, STOSIC D, et al. Zeolite-MgCl₂ composites as potential long-term heat storage materials: Influence of zeolite properties on heats of water sorption[J]. Solar Energy Materials and Solar Cells, 2014, 128: 289-295. DOI: 10.1016/j.solmat.2014.05.016.
[23]	WHITING G, GRONDIN D, BENNICI S, et al. Heats of water sorption studies on zeolite-MgSO₄ composites as potential thermochemical heat storage materials[J]. Solar Energy Materials and Solar Cells, 2013, 112: 112-119. DOI: 10.1016/j.solmat. 2013.01.020.
[24]	XU C, YU Z B, XIE Y Y, et al. Study of the hydration behavior of zeolite-MgSO₄ composites for long-term heat storage[J]. Applied Thermal Engineering, 2018, 129: 250-259. DOI: 10.1016/j.applthermaleng.2017.10.031.
[25]	N'TSOUKPOE K E, SCHMIDT T, RAMMELBERG H U, et al. A systematic multi-step screening of numerous salt hydrates for low temperature thermochemical energy storage[J]. Applied Energy, 2014, 124: 1-16. DOI: 10.1016/j.apenergy.2014.02.053.
[26]	张红. 沸石/硫酸镁复合吸附蓄热材料的制备及性能研究[D]. 上海: 上海电力大学, 2023. DOI: 10.27745/d.cnki.gshdl.2023.000013.
	ZHANG H. Study on preparation and performance of zeolite/magnesium sulfate composite sorption heat storage materials[D]. Shanghai: Shanghai University of Electric Power, 2023. DOI: 10.27745/d.cnki.gshdl.2023.000013.
[27]	谢云云. 基于水合盐复合材料的热化学储热性能实验和数值研究[D]. 北京: 华北电力大学, 2018.
	XIE Y Y. Experiment and numerical study on the thermochemical heat storage based on hydrate composite materials[D]. Beijing: North China Electric Power University, 2018.
[28]	XU J X, LI T X, CHAO J W, et al. High energy-density multi-form thermochemical energy storage based on multi-step sorption processes[J]. Energy, 2019, 185: 1131-1142. DOI: 10.1016/j.energy.2019.07.076.

沸石/水合盐吸附储热材料制备及性能研究

Preparation and performance study of zeolite/hydrated salt adsorption heat storage materials

RichHTML

PDF

可视化

摘要/Abstract

引用本文

使用本文

图/表 17

参考文献 28

相关文章 15

编辑推荐

Metrics

本文评价

[1]	刘云汉, 王亮, 张双, 林曦鹏, 葛志伟, 白亚开, 林霖, 王艺斐, 陈海生. 基于圆柱封装单元的水合盐相变储热填充床的储释特性实验研究[J]. 储能科学与技术, 2024, 13(8): 2623-2633.
[2]	王利明, 王梦奇, 罗伊默, 杨格桑, 汪媛媛, 王乐霄. 沸石储热反应器优化设计方法研究[J]. 储能科学与技术, 2024, 13(12): 4272-4281.
[3]	马鸿坤, 纪明希, 丁玉龙. 中低温吸附式热化学储热研究现状与进展[J]. 储能科学与技术, 2024, 13(12): 4436-4451.
[4]	张雪龄, 叶强, 谷军恒, 荀浩云, 张琦, 程传晓, 金听祥, 张业强. MgSO₄-LiCl@MEG复合储热材料的制备与吸附储热性能[J]. 储能科学与技术, 2023, 12(9): 2778-2788.
[5]	张琦, 李银雷, 栗艳芳, 宋俊, 吴学红, 刘重阳, 张雪龄. 膨胀石墨/多壁碳纳米管基共晶盐复合相变材料的制备及热特性[J]. 储能科学与技术, 2023, 12(8): 2435-2443.
[6]	黄渭彬, 张彪, 范金成, 杨伟, 邹汉波, 陈胜洲. ZIF-8复合PEO基固态电解质的制备与改性研究[J]. 储能科学与技术, 2023, 12(4): 1083-1092.
[7]	刘云汉, 王亮, 张双, 林曦鹏, 葛志伟, 白亚开, 林霖, 陈海生. 水合盐/膨胀石墨复合相变材料的热物性及循环稳定性研究[J]. 储能科学与技术, 2023, 12(12): 3627-3634.
[8]	葛继翔, 纪明希, 丁玉龙, 罗伊默, 王利明. 水合盐热化学反应器参数优化与供暖应用案例分析[J]. 储能科学与技术, 2023, 12(12): 3799-3807.
[9]	刘洁, 杨英英, 李爱征, 王文松, 任燕. 用于地板辐射采暖的多元水合盐复合相变砂浆的制备及性能研究[J]. 储能科学与技术, 2023, 12(12): 3655-3662.
[10]	杨娜, 王成成, 杨慧, 胡志昊, 童莉葛, 李仲博, 王立, 丁玉龙, 李娜. 基于热化学反应的硅胶非等温动力学计算及储热性能分析[J]. 储能科学与技术, 2022, 11(5): 1331-1338.
[11]	邓晓华, 江柱, 陈超, 党岱. 沸石咪唑基金属有机框架及其衍生材料用作锌-空气电池高效阴极催化剂的最新进展[J]. 储能科学与技术, 2022, 11(3): 964-981.
[12]	李亚溪, 谭振炜, 李传常. 相变储冷凝胶的制备与应用[J]. 储能科学与技术, 2022, 11(12): 3845-3854.
[13]	徐子杰, 王燕. 多孔基无机复合相变材料的蓄热特性[J]. 储能科学与技术, 2022, 11(10): 3171-3179.
[14]	罗伊默, 芮金金, 徐薇, 彭晋卿, 折晓会, 李念平, 丁玉龙. 热化学储热反应器内水合盐物性调控及传热传质优化研究进展[J]. 储能科学与技术, 2021, 10(4): 1273-1284.
[15]	令狐友强, 徐德厚, 岳秀艳, 周学志, 徐玉杰, 盛勇, 左志涛, 陈海生. 沸石-液态水吸附储热系统的释热特性[J]. 储能科学与技术, 2021, 10(3): 1103-1108.