Mn/Al改性的高稳定性钙基储能材料

doi:10.11949/0438-1157.20250262

摘要/Abstract

摘要：

使用安全无污染前驱体，通过改进的溶胶凝胶法合成了Mn、Al共掺杂钙基储能材料，对材料的各项储能性能进行了研究，并考察了初步放大合成对材料性能的影响。结果表明，乙酸钙前驱体合成的共掺杂材料Ca100Mn15Al10-Ac在1000次储能循环中表现出优异的稳定性，性能仅衰减23.2%，且主要集中在前期，其平均光吸收率也达到70%，通过形貌分析发现共掺杂材料在循环过程中演化出的稳定多孔结构有效抑制性能衰减。材料的初步放大合成以及添加微晶纤维素黏结剂不会对Ca100Mn15Al10-Ac的稳定性造成负面影响，有利于后续大规模制备。

关键词: 太阳能, 钙基材料, 储能, 吸附, 稳定性

Abstract:

Mn and Al co-doped calcium-based energy storage materials were synthesized using safe and non-toxic precursors through a modified sol-gel method. The energy storage performance of the materials was carefully studied, and the effects of preliminary scale-up synthesis on material properties were examined. Results demonstrate that the co-doped material Ca100Mn15Al10-Ac synthesized from calcium acetate exhibited excellent stability during 1000 energy storage cycles with only 23.2% performance degradation (mainly occurring in the initial stage), and the average solar absorptance reaches 70%. Morphology analysis revealed that the evolution of stable porous structure during cycling effectively suppressed performance decay. Preliminary scale-up experiments and the addition of microcrystalline cellulose binder showed no negative impacts on the stability of Ca100Mn15Al10-Ac, indicating favorable prospects for industrial production.

Key words: solar energy, calcium-based materials, energy storage, adsorption, stability

刘辉, 魏进家. Mn/Al改性的高稳定性钙基储能材料[J]. 化工学报, DOI: 10.11949/0438-1157.20250262.

Hui LIU, Jinjia WEI. Mn/Al modified calcium-based energy storage materials with high stability[J]. CIESC Journal, DOI: 10.11949/0438-1157.20250262.

图/表 11

图1 石英管固定床反应装置示意图

Fig.1 Quartz tubular fixed-bed reactor

图2 循环中二氧化碳流量曲线（围成的面积为煅烧阶段的二氧化碳释放量）

Fig.2 CO2 flow rate in one energy storage cycle (The yellow area is equal to the volume of carbon dioxide released in calcination process)

图3 乙酸钙合成材料储能性能注:(a)100次循环曲线 (b)各样品衰减速率拟合

Fig.3 Energy storage performance of materials synthesized by calcium acetate

图4 Ca100Mn15Al10-Ac的长周期循环性能

Fig. 4 The long-term energy storage performance of Ca100Mn15Al10-Ac

表1 各种用于储能的改性钙基材料对比

Table 1 Comparison of various modified calcium-based materials for energy storage

掺杂钙基材料	碳酸化温度 [℃]	碳酸化时间 [min]	首次储能密度 [kJ/kg]	循环次数 /衰减率	文献
CaCO₃/Fe,Mn	700	10	1500	60 / 3.3%	[10]
CaO/Al,Mn,Fe,Li	725	20	1746	60 / 4.26%	[29]
CaCO₃/Ti,Al,Mg	750	10	1157	100 / 7%	[31]
CaO/Mn,Mg	800	10	1604	100 / 6.23%	[32]
CaO/Al	850	10	1496	100 / 32%	[33]
CaO/Mn,Al	800	10	1245.7	1000 / 23.2%	This study

图5 各样品的XRD图谱。（a）10°-80°全谱图；（b）和（c）主峰放大图

Fig.5 XRD patterns of various samples. (a) Patterns ranged from 10° to 80°; (b) and (c) the magnified pattern of the CaO peaks ((200) and (220))

图6 样品光吸收能力图

Fig 6 Solar absorption capacity of different samples

图7 各样品扫描电镜图。（a）新鲜Ca100Al10-Ac样品；（b）100次循环后Ca100Al10-Ac样品；（c）新鲜Ca100Al10-Ac样品EDS图谱；（d）新鲜Ca100Mn15-Ac样品；（e）100次循环后Ca100Mn15-Ac样品（f）新鲜Ca100Mn15-Ac样品EDS图谱；（g）（j）新鲜Ca100Mn15Al10-Ac样品；（h）（k）1000次循环后Ca100Mn15Al10-Ac样品；（i）新鲜Ca100Mn15Al10-Ac样品EDS图谱

Fig.7 SEM images and corresponding EDS images of various samples. (a) Fresh Ca100Al10-Ac; (b) 100th cycled Ca100Al10-Ac; (c) EDS images of fresh Ca100Al10-Ac; (d) Fresh Ca100Mn15-Ac; (e) 100th cycled Ca100Mn15-Ac; (f) EDS images of fresh Ca100Mn15-Ac; (g)(h) Fresh Ca100Mn15Al10-Ac; (j)(k) Ca100Mn15Al10-Ac after 1000 cycles; (i) EDS images of fresh Ca100Mn15Al10-Ac

图8 不同材料的反应过程曲线注:(a)碳酸化反应曲线 (b)煅烧反应曲线

Fig.8 Reaction curves of various materials

图9 添加微晶纤维素Ca100Mn15Al10-Ac样品性能曲线

Fig.9 Energy storage performance of Ca100Mn15Al10-Ac sample added with microcrystalline cellulose

图10 Ca100Mn15Al10-Ac放大10倍后循环性能

Fig.10 Cyclic performance of Ca100Mn15Al10-Ac after 10x scaled up

参考文献 35

[1]	Leonard M D, Michaelides E E, Michaelides D N. Energy storage needs for the substitution of fossil fuel power plants with renewables[J]. Renewable Energy, 2020, 145: 951-962.[LinkOut]
[2]	Lv J Q, Xie J F, Mohamed A G A, et al. Solar utilization beyond photosynthesis[J]. Nature Reviews. Chemistry, 2023, 7(2): 91-105.[PubMed]
[3]	Wang G, Zhang Z, Lin J Q. Multi-energy complementary power systems based on solar energy: a review[J]. Renewable and Sustainable Energy Reviews, 2024, 199: 114464.[LinkOut]
[4]	Romero M, Steinfeld A. Concentrating solar thermal power and thermochemical fuels[J]. Energy & Environmental Science, 2012, 5(11): 9234-9245.[LinkOut]
[5]	He Y L, Qiu Y, Wang K, et al. Perspective of concentrating solar power[J]. Energy, 2020, 198: 117373.[LinkOut]
[6]	Raganati F, Chirone R, Ammendola P. Calcium-looping for thermochemical energy storage in concentrating solar power applications: Evaluation of the effect of acoustic perturbation on the fluidized bed carbonation[J]. Chemical Engineering Journal, 2020, 392: 123658.[LinkOut]
[7]	凌祥, 宋丹阳, 陈晓轶, 等. 钙基热化学储能体系装备与系统研究进展[J]. 化工进展, 2021, 40(4): 1777-1796.
	Ling X, Song D Y, Chen X Y, et al. Progress in equipment and systems for calcium-based thermochemical energy storage system[J]. Chemical Industry and Engineering Progress, 2021, 40(4): 1777-1796.[知网中文][知网英文][万方][知网中文带页码]
[8]	Tian X K, Guo S J, Lv X J, et al. Progress in multiscale research on calcium-looping for thermochemical energy storage: From materials to systems[J]. Progress in Energy and Combustion Science, 2025, 106: 101194.[LinkOut]
[9]	Ortiz C, Chacartegui R, Valverde J M, et al. Power cycles integration in concentrated solar power plants with energy storage based on calcium looping[J]. Energy Conversion and Management, 2017, 149: 815-829.[LinkOut]
[10]	Teng L, Xuan Y M, Da Y, et al. Modified Ca-Looping materials for directly capturing solar energy and high-temperature storage[J]. Energy Storage Materials, 2020, 25: 836-845.[LinkOut]
[11]	郑玉圆, 葛志伟, 韩翔宇, 等. 中高温钙基材料热化学储热的研究进展与展望[J]. 化工学报, 2023, 74(8): 3171-3192.
	Zheng Y Y, Ge Z W, Han X Y, et al. Progress and prospect of medium and high temperature thermochemical energy storage of calcium-based materials[J]. CIESC Journal, 2023, 74(8): 3171-3192.[知网中文][知网英文][万方][机构或注册用户_知网中文带页码]
[12]	Tian X K, Lin S C, Yan J, et al. Sintering mechanism of calcium oxide/calcium carbonate during thermochemical heat storage process[J]. Chemical Engineering Journal, 2022, 428: 131229.[LinkOut]
[13]	Wang J F, Xiong W, Ding Z X, et al. Enhancing the stability of CaO-based looping materials in thermochemical energy storage by codoping Y and Mg[J]. ACS Applied Energy Materials, 2024, 7(24): 12165-12173.[LinkOut]
[14]	Wang K, Gu F, Clough P T, et al. Porous MgO-stabilized CaO-based powders/pellets via a citric acid-based carbon template for thermochemical energy storage in concentrated solar power plants[J]. Chemical Engineering Journal, 2020, 390: 124163.[LinkOut]
[15]	Huang X K, Ma X T, Li J, et al. Enhancement effects of hydrolysable/soluble Al-type dopants on the efficiency of CaO/CaCO₃ thermochemical energy storage[J]. Chemical Engineering Journal, 2024, 490: 151555.[LinkOut]
[16]	Han R, Gao J H, Wei S Y, et al. Development of dense Ca-based, Al-stabilized composites with high volumetric energy density for thermochemical energy storage of concentrated solar power[J]. Energy Conversion and Management, 2020, 221: 113201.[LinkOut]
[17]	Hu Y C, He W Z, Cao J X, et al. Decorating CaO with dark Ca₂MnO₄ for direct solar thermal conversion and stable thermochemical energy storage[J]. Solar Energy Materials and Solar Cells, 2022, 248: 111977.[LinkOut]
[18]	Guo H X, Kou X C, Zhao Y J, et al. Effect of synergistic interaction between Ce and Mn on the CO₂ capture of calcium-based sorbent: Textural properties, electron donation, and oxygen vacancy[J]. Chemical Engineering Journal, 2018, 334: 237-246.[LinkOut]
[19]	Chen X B, Tang Y T, Ke C C, et al. CO₂ capture by double metal modified CaO-based sorbents from pyrolysis gases[J]. Chinese Journal of Chemical Engineering, 2022, 43: 40-49.[LinkOut]
[20]	Jiang T, Zhang H, Zhao Y J, et al. Kilogram-scale production and pelletization of Al-promoted CaO-based sorbent for CO₂ capture[J]. Fuel, 2021, 301: 121049.[LinkOut]
[21]	Sun H, Li Y J, Yan X Y, et al. Thermochemical energy storage performance of Al₂O₃/CeO₂ Co-doped CaO-based material under high carbonation pressure[J]. Applied Energy, 2020, 263: 114650.[LinkOut]
[22]	Li C L, Li Y J, Zhang C X, et al. CaO/CaCO₃ thermochemical energy storage performance of high-alumina granule stabilized papermaking soda residue[J]. Fuel Processing Technology, 2022, 237: 107444.[LinkOut]
[23]	Gao C Y, Zhang Y, Liu X L, et al. A dual modification method to prepare carbide slag into highly active CaO-based solar energy storage materials[J]. Industrial & Engineering Chemistry Research, 2024, 63(1): 769-779.[LinkOut]
[24]	Kim S M, Kierzkowska A M, Broda M, et al. Sol-gel synthesis of MgAl₂O₄-stabilized CaO for CO₂ capture[J]. Energy Procedia, 2017, 114: 220-229.[LinkOut]
[25]	Luo T, Luo C, Shi Z W, et al. Optimization of Sol-gel combustion synthesis for calcium looping CO₂ sorbents, part Ⅰ: Effects of Sol-gel preparation and combustion conditions[J]. Separation and Purification Technology, 2022, 292: 121081.[LinkOut]
[26]	Song C, Liu X L, Zheng H B, et al. Decomposition kinetics of Al- and Fe-doped calcium carbonate particles with improved solar absorbance and cycle stability[J]. Chemical Engineering Journal, 2021, 406: 126282.[LinkOut]
[27]	Angeli S D, Martavaltzi C S, Lemonidou A A. Development of a novel-synthesized Ca-based CO₂ sorbent for multicycle operation: Parametric study of sorption[J]. Fuel, 2014, 127: 62-69.[LinkOut]
[28]	Chen H C, Zhang P P, Duan Y F, et al. Reactivity enhancement of calcium based sorbents by doped with metal oxides through the Sol–gel process[J]. Applied Energy, 2016, 162: 390-400.[LinkOut]
[29]	Liu X L, Yuan C J, Zheng H B, et al. Synergy of Li₂CO₃ promoters and Al-Mn-Fe stabilizers in CaCO₃ pellets enables efficient direct solar-driven thermochemical energy storage[J]. Materials Today Energy, 2022, 30: 101174.[LinkOut]
[30]	Carrillo A J, González-Aguilar J, Romero M, et al. Solar energy on demand: a review on high temperature thermochemical heat storage systems and materials[J]. Chemical Reviews, 2019, 119(7): 4777-4816.[PubMed]
[31]	Tian X K, Lin S C, Yan J, et al. Improved durability in thermochemical energy storage using Ti/Al/Mg Co-doped Calcium-based composites with hierarchical Meso/Micro pore structures[J]. Chemical Engineering Journal, 2022, 450: 138142.[LinkOut]
[32]	Liu H, Li Y Z, Wei J J. High performance Mn/Mg co-modified calcium-based material via EDTA chelating agent for effective solar energy storage[J]. Chemical Engineering Journal, 2024, 480: 147892.[LinkOut]
[33]	Koirala R, Reddy G K, Smirniotis P G. Single nozzle flame-made highly durable metal doped Ca-based sorbents for CO₂Capture at high temperature[J]. Energy & Fuels, 2012, 26(5): 3103-3109.[LinkOut]
[34]	Zhou Z M, Qi Y, Xie M M, et al. Synthesis of CaO-based sorbents through incorporation of alumina/aluminate and their CO₂ capture performance[J]. Chemical Engineering Science, 2012, 74: 172-180.[LinkOut]
[35]	Torma A J, Li W B, Zhang H, et al. Interstitial nature of Mn²⁺ doping in 2D perovskites[J]. ACS Nano, 2021, 15(12): 20550-20561.[PubMed]