Thermochemical energy storage temperature regulation and kinetics study of Na2CO3-CuO-Co3O4 composites

WANG Wenhao; WU Rongjun; LUO Xianglong; LU Pei

doi:10.19799/j.cnki.2095-4239.2026.0155

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Thermochemical energy storage temperature regulation and kinetics study of Na₂CO₃-CuO-Co₃O₄ composites

Energy Storage Materials and Devices | 更新时间：2026-07-28

- Thermochemical energy storage temperature regulation and kinetics study of Na₂CO₃-CuO-Co₃O₄ composites
- Energy Storage Science and Technology Vol. 15, Issue 7, Pages: 2488-2498(2026)
- 作者机构：
  
  广东工业大学材料与能源学院，广东广州 510006
- 作者简介：
- 基金信息：
- DOI：10.19799/j.cnki.2095-4239.2026.0155
  CLC： TK 01
- Received：12 February 2026，
  
  Revised：2026-03-16，
  
  Online First：28 July 2026，
  
  Published：28 July 2026
- 稿件说明：
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王文浩, 吴榕君, 罗向龙, 等. Na₂CO₃-CuO-Co₃O₄复合材料热化学储热温度调控与动力学研究[J]. 储能科学与技术, 2026, 15(7): 2488-2498. DOI: 10.19799/j.cnki.2095-4239.2026.0155.

WANG Wenhao, WU Rongjun, LUO Xianglong, et al. Thermochemical energy storage temperature regulation and kinetics study of Na₂CO₃-CuO-Co₃O₄ composites[J]. Energy Storage Science and Technology, 2026, 15(7): 2488-2498. DOI: 10.19799/j.cnki.2095-4239.2026.0155.
王文浩, 吴榕君, 罗向龙, 等. Na₂CO₃-CuO-Co₃O₄复合材料热化学储热温度调控与动力学研究[J]. 储能科学与技术, 2026, 15(7): 2488-2498. DOI: 10.19799/j.cnki.2095-4239.2026.0155. DOI：

WANG Wenhao, WU Rongjun, LUO Xianglong, et al. Thermochemical energy storage temperature regulation and kinetics study of Na₂CO₃-CuO-Co₃O₄ composites[J]. Energy Storage Science and Technology, 2026, 15(7): 2488-2498. DOI: 10.19799/j.cnki.2095-4239.2026.0155. DOI：

摘要

/CoO体系凭借其高储能密度与良好的反应可逆性，在高温热化学储热领域展现出重要的应用潜力。为拓宽Co

/CoO体系的储热温区、缩小储/放热反应温差（温度迟滞），本研究提出了一种基于廉价金属（CuO、Na

）的多元掺杂策略。采用研磨混合法制备了系列钴基氧化物复合材料，通过热重法（thermogravimetric analysis，TGA）分析材料的储/放热性能（包括还原-氧化温度、还原-氧化可逆性、温度迟滞等），并结合动力学分析方法探究掺杂对还原反应机理的影响。实验结果表明，CuO-Na

共掺杂样品8/3Co

-1CuO-0.25Na

的还原起始温度由纯Co

的883℃降至818℃，同时将温度迟滞稳定控制在5℃以内，并在50次循环中保持了92%的反应转化率，表现出优异的循环可逆性。动力学分析表明，CuO-Na

共掺杂后反应仍遵循Avrami-Erofeyev（A2）随机成核与生长机理，说明掺杂在调控储热温区、缩小温度迟滞的同时未改变其还原反应机理。本研究为发展高性能、低成本钴基热化学储热材料提供了可行的材料设计思路与理论支撑。

Abstract

Thermochemical energy storage (TCES) is promising for efficient thermal energy management

particularly in concentrated solar power and industrial waste heat recovery. Among various candidate materials

the cobalt oxide system (Co

/CoO) has attracted considerable attention owing to its high energy density and good reversibility during redox cycles. However

practical application is often limited by its relatively high operating temperature and the temperature hysteresis between the reduction

(heat storage) and oxidation (heat release) steps. This hysteresis adversely affects the efficiency and controllability of the system. To address these challenges

this study introduces a novel and economical modification strategy in which low-cost

metal-based additives

specifically copper oxide (CuO) and sodium carbonate (Na

)

are introduced. The objective is to tailor the thermodynamic and kinetic properties of the base material. Composites were synthesized using a straightforward solid-state grinding and mixing technique

ensuring simplicity and scalability. The thermochemical performance of the composites was thoroughly assessed via thermogravimetric analysis

focusing on key parameters

including the onset and peak temperatures for reduction and oxidation

degree of conversion

and magnitude of temperature hysteresis. The results demonstrate a synergistic effect of CuO and Na

co-doping. This combination effectively shifts the reduction reaction to a lower temperature range and dramatically narrows the hysteresis. For the optimally doped formulation (8/3Co

-1CuO-0.25Na

)

the onset temperature was substantially reduced from 883℃ (for pristine Co

) to 818℃. Remarkably

the temperature separation between reduction and oxidation stabilized below 5℃. Moreover

the material exhibited outstanding cycling stability

retaining 92% of its initial conversion after 50 consecutive redox cycles

which underscores its robust reversibility and durability. To gain deeper insight into the role of the dopants

the reduction kinetics were analyzed

confirming that the reaction mechanism remains consistent with the Avrami-Erofeyev model (A2)

governed by random nucleation and subsequent growth. This indicates that the primary role of the CuO-Na

additives is to modify the reaction environment-potentially by enhancing ionic diffusion

forming intermediate compounds

or altering th

e surface properties-without changing the intrinsic nucleation-and-growth controlled pathway for Co

reduction. In summary

a doped cobalt oxide composite with significantly improved properties was successfully developed

affording a lower and wider operational temperature range

minimal hysteresis

and excellent cyclic stability. The findings offer a practical and theoretically grounded material design strategy

paving the way for engineering advanced

cost-effective cobalt-based TCES materials that can be efficiently integrated into graded or cascaded thermal storage systems

thereby enhancing the overall energy utilization.

关键词

Keywords

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