Preparation and thermal performance of porous composite thermochemical heat storage materials of calcium sulfate dihydrate

YANG Guang; MU Fei; LI Yuanyuan; CHENG Xiaomin

doi:10.19799/j.cnki.2095-4239.2025.1010

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Preparation and thermal performance of porous composite thermochemical heat storage materials of calcium sulfate dihydrate

Special Issue on Multi\-Scenario Applications of Thermal and Cold Energy Storage | 更新时间：2026-07-01

- Preparation and thermal performance of porous composite thermochemical heat storage materials of calcium sulfate dihydrate
- Energy Storage Science and Technology Vol. 15, Issue 3, Pages: 735-746(2026)
- 作者机构：
  
  武汉理工大学材料科学与工程学院，湖北武汉 430070
- 作者简介：
- 基金信息：
- DOI：10.19799/j.cnki.2095-4239.2025.1010
  CLC： TB 34;TB 33;TK 02
- Received：10 November 2025，
  
  Revised：2025-12-07，
  
  Published：28 March 2026
- 稿件说明：
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杨光, 牟飞, 李元元, 等. 二水合硫酸钙多孔复合热化学储热材料的制备及热性能研究[J]. 储能科学与技术, 2026, 15(3): 735-746.

YANG Guang, MU Fei, LI Yuanyuan, et al. Preparation and thermal performance of porous composite thermochemical heat storage materials of calcium sulfate dihydrate[J]. Energy Storage Science and Technology, 2026, 15(3): 735-746.
杨光, 牟飞, 李元元, 等. 二水合硫酸钙多孔复合热化学储热材料的制备及热性能研究[J]. 储能科学与技术, 2026, 15(3): 735-746. DOI： 10.19799/j.cnki.2095-4239.2025.1010.

YANG Guang, MU Fei, LI Yuanyuan, et al. Preparation and thermal performance of porous composite thermochemical heat storage materials of calcium sulfate dihydrate[J]. Energy Storage Science and Technology, 2026, 15(3): 735-746. DOI： 10.19799/j.cnki.2095-4239.2025.1010.

摘要

二水合硫酸钙(CaSO

·2H

O)作为磷石膏的主要成分，具有储热密度高、成本低廉、来源广泛等优势，其脱水/水合可逆反应可实现中温领域热能的高效存储与释放，在太阳能中温集热、工业余热回收等场景中具有巨大应用潜力。但该材料具有固有热导率低、循环过程中易团聚和板结的缺陷，严重制约了其传热传质与长期服役稳定性，成为其工程化应用的核心难题。为解决上述问题，本研究以CaSO

·2H

O为储热基体，通过功能组分协同改性与多孔结构复合策略，开展了热化学储热材料的制备与性能优化研究。具体采用溶液合成法制备高纯度CaSO

·2H

O粉末，添加质量分数为3%的膨胀石墨(EG)作为导热增强相、5%的纳米二氧化硅(SiO

)作为团聚抑制剂，经球磨工艺制备CaSO

·2H

O/3EG/5SiO

储热基质(HSM)，再通过真空浸渍法将储热基质与多孔泡沫铜(CF)复合，构建CF@HSM多孔复合热化学储热材料。借助扫描电子显微镜(SEM)、X射线衍射仪(XRD)、傅里叶变换红外光谱仪(FTIR)、差示扫描量热仪(DSC)、激光导热仪等表征手段，系统分析材料的微观形貌、晶体结构、化学相容性、热性能及循环稳定性。结果表明，膨胀石墨的高导热特性使CaSO

·2H

O热导率从0.577 W/(m·K)提升至0.797 W/(m·K)，提升幅度达38.1%；纳米二氧化硅通过分散颗粒、抑制晶界迁移，显著改善了材料循环后的团聚现象；泡沫铜的多孔结构与高导热性进一步优化了传热传质路径，使复合后材料热导率提升至1.509 W/(m·K)，较纯CaSO

·2H

O提高161.5%。该复合材料焓值达359 J/g、封装率为70.4%、反应温度区间为120~160℃，与太阳能中温集热条件高度适配；经80次水合/脱水循环后，储热密度仍保持在92.3%，晶体结构与化学相容性未发生明显变化，循环稳定性优异。本研究通过多孔结构与功能组分改性的协同设计，有效破解了水合盐热化学储热体系热导率低、易团聚的关键技术难题，为水合盐类储热材料的性能优化提供了兼具科学性与实用性的新策略，同时为磷石膏资源化利用开辟了高附加值应用路径，对推动中温热化学储热技术的工程化应用具有重要参考价值。

Abstract

Calcium sulfate dihydrate (CaSO

·2H

the main component of phosphogypsum

exhibits significant potential for medium-temperature thermal energy stor

age because of its high heat storage density

low cost

and wide availability. Its reversible dehydration-hydration reaction enables efficient thermal energy storage and release

making it suitable for applications such as medium-temperature solar heat collection and industrial waste heat recovery. However

inherent limitations

including low thermal conductivity and severe agglomeration during cycling

restrict heat and mass transfer efficiency and long-term operational stability

thereby hindering engineering applications. To address these challenges

this study focuses on the preparation and performance optimization of thermochemical heat storage materials through synergistic modification using functional additives and a composite porous structure. High-purity CaSO

·2H

O powder was synthesized via a solution method. Subsequently

3% expanded graphite was introduced as a thermal conductivity enhancer and 5% nano-silica (SiO

) as an agglomeration inhibitor

followed by ball milling to obtain a CaSO

·2H

O /3EG/5SiO

heat storage matrix. A porous composite thermochemical heat storage material was then fabricated by vacuum impregnation of the matrix into porous copper foam. The microstructure

crystal structure

chemical compatibility

thermal performance

and cyclic stability were systematically characterized using scanning electron microscopy

X-ray diffraction

Fourier transform infrared spectroscopy

differential scanning calorimetry

and a laser thermal conductivity tester. The results show that the incorporation of expanded graphite increases the thermal conductivity of CaSO

·2H

O from 0.577 W/(m·K) to 0.797 W/(m·K)

corresponding to an improvement of 27.6%. Nano-SiO

effectively suppresses particle agglomeration after cycling by enhancing particle dispersion and inhibiting grain boundary migration. The porous structure and high thermal conductivity of copper foam further improve heat and mass transfer pathways

resulting in a thermal conductivity of 1.509 W/(m·K)

which is 161.5% higher than that of pure CaSO

·2H

O. The composite material exhibits a reaction enthalpy of 359 J/g

a packaging efficiency of 70.4%

and an operating temperature range of 120—160℃

which is well matched with medium-temperature solar thermal systems. After 80 hydration-dehydration cycles

the heat storage density remains at 92.3%

with no significant changes in crystal structure or chemical compatibility

demonstrating excellent cyclic stability. Through the synergistic design of porous support and functional modification

this study effectively addresses the key challenges of low thermal conductivity and agglomeration in hydrated salt thermochemical heat storage systems

providing a practical strategy for performance enhancement and high-value utilization of phosphogypsum resources.

关键词

Keywords

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