离子热合成锰基氧化物及其可逆储热性能

doi:10.15541/jim20220658

无机材料学报 ›› 2023, Vol. 38 ›› Issue (7): 793-799.DOI: 10.15541/jim20220658 CSTR: 32189.14.10.15541/jim20220658

离子热合成锰基氧化物及其可逆储热性能

孟波¹(), 肖刚², 王秀丽¹, 涂江平¹, 谷长栋¹()

1.浙江大学材料科学与工程学院, 杭州310058
2.浙江大学能源清洁利用国家重点实验室, 杭州 310027

收稿日期:2022-11-07 修回日期:2022-12-04 出版日期:2022-12-16 网络出版日期:2022-12-27
通讯作者: 谷长栋, 副教授. E-mail: cdgu@zju.edu.cn
作者简介:孟波(1998-), 女, 硕士研究生. E-mail: 22060231@zju.edu.cn
基金资助:
国家自然科学基金(52176207)

Ionic Thermal Synthesis and Reversible Heat Storage Performance of Manganese-based Oxides

MENG Bo¹(), XIAO Gang², WANG Xiuli¹, TU Jiangping¹, GU Changdong¹()

1. College of Materials Science and Engineering, Zhejiang University, Hangzhou 310058, China
2. State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China

Received:2022-11-07 Revised:2022-12-04 Published:2022-12-16 Online:2022-12-27
Contact: GU Changdong, associate professor. E-mail: cdgu@zju.edu.cn
About author:MENG Bo (1998-), female, Master candidate. E-mail: 22060231@zju.edu.cn
Supported by:
National Natural Science Foundation of China(52176207)

摘要/Abstract

摘要：

光热电站需要配备大规模高温储热模块, 金属氧化物可以通过可逆氧化还原反应实现热量的存储与释放。其中锰基氧化物无毒、廉价, 极具潜力, 但可逆性较差。为此, 本研究采用深共溶溶剂离子热合成了锰基氧化物, 探索了合成参数和铁掺杂对其储热性能的影响。离子热合成的MnCO₃前驱体在高温下分解释放CO₂, 使锰基氧化物具有丰富的孔隙结构, 为氧气的传输与扩散提供通道, 有利于氧化还原反应。离子热合成的Mn₂O₃比商业Mn₂O₃反应性能好, 但其氧化反应速度较慢; 合成温度150 ℃、掺杂20% Fe的锰铁氧化物的氧化速率快, 储热密度高达300.66 J/g, 反应可逆性最佳, 可实现长期稳定循环。离子热合成策略可以增加锰氧化物中晶格氧占比, 促进氧空位的迁移, 从而提高可逆性和循环稳定性。

关键词: 光热发电, 储热, 锰基氧化物, 深共溶溶剂

Abstract:

Concentrated solar power plant needs to be equipped with large-scale high-temperature heat storage module. Metal oxides can store and release heat through reversible redox reaction. Manganese oxides is non-toxic and cheap, showing great potential for applying in solar power plant, but it displays poor reversibility. Here, a manganese-based oxides with high reversibility by deep eutectic solvent (DES) ionic thermal synthesis was proposed, and effects of synthesis parameters and iron doping on heat storage performance were studied. MnCO₃, as the raw material, was used to produce manganese oxides by ionic thermal decomposition at high temperature and released CO₂, which could also form abundant pore structure, providing great channels for oxygen transmission and diffusionfor redox. Although this Mn₂O₃ synthesis method showed better reactivity than commercial Mn₂O₃, its oxidation rate was low. It is worth noting that oxidation rate of manganese iron oxide doped with 20% Fe, synthesized at 150 ℃, was fast. Its heat storage density reached 300.66 J/g, and reversibility of the reaction was the best, which could realize long-term stable cycle. Our results demonstrated that ionic thermal synthesis can increase the lattice oxygen ratio in manganese oxides, promoting migration of oxygen vacancies, and further improving reversibility and cyclic stability.

Key words: concentrated solar power, heat storage, manganese-based oxide, deep eutectic solvent

中图分类号:

TK513

孟波, 肖刚, 王秀丽, 涂江平, 谷长栋. 离子热合成锰基氧化物及其可逆储热性能[J]. 无机材料学报, 2023, 38(7): 793-799.

MENG Bo, XIAO Gang, WANG Xiuli, TU Jiangping, GU Changdong. Ionic Thermal Synthesis and Reversible Heat Storage Performance of Manganese-based Oxides[J]. Journal of Inorganic Materials, 2023, 38(7): 793-799.

图/表 13

图1 离子热合成Mn2O3与商业Mn2O3氧化还原反应特性

Fig. 1 Redox reaction characteristics of Mn2O3 by ionic thermal synthesis and commercial Mn2O3 Colorful figure is available on website

图2 (a~d)Mn2O3循环前后的SEM照片和(e)循环前O1s的XPS图谱

Fig. 2 (a-d) SEM images of samples before and after cycling, and (e) O1s XPS spectra of Mn2O3 before cycling (a) Commercial Mn2O3 before cycling; (b) Commercial Mn2O3 after cycling; (c) DES Mn2O3 before cycling; (d) DES Mn2O3 after cycling

图3 不同Fe含量样品的氧化还原反应特性

Fig. 3 Redox reaction of samples with different Fe contents Colorful figure is available on website

图4 不同离子热合成温度制备样品的(a)TG曲线和(b)氧化反应转化率-时间曲线

Fig. 4 (a) TG curves and (b) oxidation reaction conversion rate-time curves of samples prepared at different ionic thermal synthesis temperatures

图5 不同离子热合成温度制备样品循环前的SEM照片

Fig. 5 SEM images of samples prepared by ionic thermal synthesis at different temperatures before cycling (a) 120 ℃-4 h; (b) 150 ℃-4 h; (c) 180 ℃-4 h

图6 150 ℃-4 h的热化学储热密度和热循环曲线

Fig. 6 (a) Thermochemical heat storage density and (b) thermal cycling curves of 150 ℃-4 h

图7 150 ℃-4h的O1s XPS图谱

Fig. 7 O1s XPS spectra of 150 ℃-4h

图8 DES合成锰基氧化物前驱物表征

Fig. 8 Characterization of precursors of manganese-based oxide synthesized by DES (a) XRD pattern; (b) SEM-EDS images; (c) XRD patterns under different heat-treatments; (d) TG curve

图9 DES诱导储热材料形成过程

Fig. 9 Formation process of heat storage materials induced by

图S1 DES照片

Fig. S1 Photos of DES (a) MnCl2/Urea; (b) (MnCl2, FeCl3)/Urea

图S2 离子热合成Mn2O3的DSC曲线

Fig. S2 DSC curve of Mn2O3 by ionic thermal synthesis

图S3 固相法和离子热合成(Mn0.8Fe0.2)2O3的TG曲线

Fig. S3 TG curves of (Mn0.8Fe0.2)2O3 by solid-phase and ionic thermal synthesis

图S4 MnCl2/Urea型DES离子热合成产物在不同温度煅烧后的XRD图谱

Fig. S4 XRD patterns of samples after heat treatment under different temperatures prepared by MnCl2/Urea DES

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离子热合成锰基氧化物及其可逆储热性能

Ionic Thermal Synthesis and Reversible Heat Storage Performance of Manganese-based Oxides

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