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

doi:10.19799/j.cnki.2095-4239.2021.0331

Abstract

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

CLC Number:

TK 513.5

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.

Figures/Tables 13

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

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