Co3O4/CoO氧化还原反应储/释热动力学特性

doi:10.19799/j.cnki.2095-4239.2021.0331

储能科学与技术 ›› 2021, Vol. 10 ›› Issue (5): 1701-1708.doi: 10.19799/j.cnki.2095-4239.2021.0331

• 物理储能十年专刊·储热 • 上一篇下一篇

Co₃O₄/CoO氧化还原反应储/释热动力学特性

韩翔宇^1,²(), 王亮^1,², 葛志伟^1,², 凌浩恕^1,², 林曦鹏^1,², 陈海生^1,^2,³(), 彭珑⁴()

^1.中国科学院工程热物理研究所，北京 100191
^2.中国科学院大学，北京 100049
^3.中科南京未来能源系统研究院，江苏南京 211135
^4.毕节高新技术产业开发区国家能源大规模物理储能技术研发中心，贵州毕节 551712

收稿日期:2021-07-12 修回日期:2021-07-14 出版日期:2021-09-05 发布日期:2021-09-08
作者简介:韩翔宇（1997—），男，博士研究生，主要研究方向为热化学储热材料，E-mail：hanxy97@126.com|陈海生，研究员，主要研究方向为新型大规模压缩空气储能、微型燃气轮机、微小尺度流动与传热等，E-mail：chen_hs@iet.cn|彭珑，博士，研究方向为大规模蓄冷蓄热、压缩空气储能和热泵等，E-mail：penglong@iet.com。
基金资助:
国家自然科学基金(52006223);中国科学院国际合作局国际伙伴计划(182211KYSB20170029);贵州省科技计划项目(黔科合基础［2018］1138);内蒙古自治区科技重大专项(2019ZD014)

The thermal storage and release kinetics of Co₃O₄/CoO redox reaction

Xiangyu HAN^1,²(), Liang WANG^1,², Zhiwei GE^1,², Haoshu LING^1,², Xipeng LIN^1,², Haisheng CHEN^1,^2,³(), Long PENG⁴()

^1.Institute of Engineering Thermophysics, Chinese Academy of Sciences, Beijing 100191, China
^2.University of Chinese Academy of Sciences, Beijing 100049, China
^3.Nanjing Institute of Future Energy System, Chinese Academy of Science, Nanjing 211135, Jiangsu, China
^4.National Energy Large Scale Physical Energy Storage Technologies R&D Center of Bijie High-tech Industrial Development Zone, Bijie 551712, Guizhou, China

Received:2021-07-12 Revised:2021-07-14 Online:2021-09-05 Published:2021-09-08

摘要/Abstract

摘要：

Co₃O₄/CoO体系因其较高的储能密度和良好的反应特性，在中高温热化学储热领域具有广阔的应用前景。利用热重分析和差示扫描量热法研究了不同的氧浓度和加热/冷却速率对Co₃O₄/CoO体系氧化还原反应过程的影响，并对还原反应动力学进行了分析。实验结果表明，提高氧浓度和加热/冷却速率均能提高氧化还原速率，但是较高的氧浓度可能会抑制还原反应。而氧浓度和加热速率对还原反应焓的影响不明显。动力学分析结果表明，还原反应符合随机成核模型Avrami-Erofeyev (A2)。经过优化计算，得到了较为精确的还原反应动力学模型，最终为基于金属氧化物氧化还原体系的热化学储热反应器的设计提供理论基础。

关键词: 热化学储热, 金属氧化物体系, 动力学分析

Abstract:

A Co₃O₄/CoO system has broad application prospects in the contexts of medium and high-temperature thermochemical energy storage due to its high-energy storage density and good reaction characteristics. This study used thermogravimetry and differential scanning calorimetry to study the influence of different oxygen concentrations and heating/cooling rates on the redox process of a Co₃O₄/CoO system and analyzed the reduction reaction kinetics. The experimental results showed that increasing the oxygen concentration and heating/cooling rate could increase the redox reaction rate. However, a higher oxygen concentration could inhibit the reduction reaction. The effects of oxygen concentration and heating rate on the enthalpy of the reduction were not obvious. The kinetic analysis results showed that the reduction reaction conformed to the Avrami-Erofeyev random nucleation model (A2). Following optimized calculation, a more accurate kinetic model of reduction reaction was obtained, which provided a theoretical basis for the design of a thermochemical energy storage reactor, based on metal oxide systems.

Key words: thermochemical energy storage, metal oxide systems, kinetics analysis

中图分类号:

TK 513.5

韩翔宇, 王亮, 葛志伟, 凌浩恕, 林曦鹏, 陈海生, 彭珑. Co₃O₄/CoO氧化还原反应储/释热动力学特性[J]. 储能科学与技术, 2021, 10(5): 1701-1708.

Xiangyu HAN, Liang WANG, Zhiwei GE, Haoshu LING, Xipeng LIN, Haisheng CHEN, Long PENG. The thermal storage and release kinetics of Co₃O₄/CoO redox reaction[J]. Energy Storage Science and Technology, 2021, 10(5): 1701-1708.

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参考文献 25

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体系	BaO₂/BaO	Co₃O₄/CoO	Mn₂O₃/Mn₃O₄	CuO/Cu₂O
还原温度/℃	714	914.6	948	1042.5
氧化温度/℃	704	879.7	667	1021.1
理论储能密度/(kJ·kg^-1)	474	844	202	811
优点	中等反应焓 +	高反应焓 ++ 良好的循环稳定性 ++ 快速的反应动力学 ++	材料成本低 ++ 无毒无害 +	高反应焓 ++ 还原反应速度快 ++
缺点	可逆性差 -- 烧结 --	材料成本高 --- 有毒性 -	氧化反应缓慢 -- 低反应焓 - 不完整的反应 --	熔化问题 --- 氧化反应缓慢 --

模型	f(α)
	成核模型
幂律 (P2)	2α^1/2
幂律 (P3)	3α^2/3
幂律 (P3)	4α^3/4
Avrami-Erofeyev (A2)	2(1-α)[-ln(1-α)]^1/2
Avrami-Erofeyev (A3)	3(1-α)[-ln(1-α)]^2/3
Avrami-Erofeyev (A4)	4(1-α)[-ln(1-α)]^3/4
Prout-Tompkins (B1)	α(1-α)
	几何收缩模型
收缩面积 (R2)	2(1-α)^1/2
收缩体积 (R3)	3(1-α)^2/3
	扩散模型
1-D扩散 (D1)	1/(2α)
2-D扩散 (D2)	-[1/ln(1-α)]
3-D扩散 (D3)	[3(1-α)^2/3]/[2(1-(1-α)^1/3)]
Ginstling-Brounshtein (D4)	3/[2(1-α)^-1/3-1]
	反应级数模型
0级 (F0/R1)	1
1级 (F1)	(1-α)
2级 (F2)	(1-α)²
3级 (F3)	(1-α)³

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Co₃O₄/CoO氧化还原反应储/释热动力学特性

The thermal storage and release kinetics of Co₃O₄/CoO redox reaction

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