非水系纳米流体热再生液流电池串联堆性能特性

doi:10.16085/j.issn.1000-6613.2022-1820

摘要/Abstract

摘要：

热再生电池（thermally regenerative batteries，TRB）在低温热能回收和产电综合利用等方面极具发展与应用前景。非水溶剂的应用提升了TRB的开路电压、能量密度和热效率，然而现有研究电池内阻较大，并且缺乏面向实际应用的拓展性研究。为此，本文采用铜-乙腈非水体系构建了紧凑型TRB反应器和串联电堆，研究了电极间距对单电池性能以及供液方式、子电池数量、电路联接方式和电解液流量对串联堆性能的影响。研究结果表明，构建紧凑型结构获得单电池性能显著提升，并联供液具有更佳的传质效果和子电池性能均一性从而电堆获得更高的输出功率，同时串联堆开路电压和最大输出功率随子电池数量增加而线性增加。需选择合适的子电池数量和电路连接方式以满足实际应用中作为电源的工作电压及电流要求。增加电解质流量有助于强化物质传输，电堆最大输出功率随电解液流量的增加先增加后保持不变。

关键词: 非水系热再生电池, 配合物, 反应器, 串联电堆, 最大功率, 传质

Abstract:

Thermally regenerative batteries (TRBs) have great development and application prospects in low temperature waste heat recovery and comprehensive utilization of electricity. The application of non-aqueous solvents improves the open-circuit voltage, energy density and thermal efficiency of TRBs. However, the internal resistance of TRBs is relatively large, and few research is for practical applications. Therefore, a compact TRB reactor and a series stack reactor were constructed by using copper-acetonitrile non-aqueous system. The effect of electrode spacing on the performance of a single cell and the effects of liquid supply mode, number of sub cells, circuit connection mode and electrolyte flow rate on the performance of the stack were studied. The results showed that single cell performance was significantly improved by constructing the compact structure, and the parallel supply liquid mode enhanced the mass transfer and the uniformity of the sub-cells, so that the reactor gave high output power. Meanwhile, the open-circuit voltage and the maximum output power of the series reactor increased linearly with the increase of the number of sub-cells. Therefore, it is necessary to select appropriate sub-battery number and circuit connection mode to meet the practical power supply requirements of working voltage and current. Increasing the electrolyte flow rate is helpful to strengthen the material transfer and the maximum output power of the series stack increases first and then remains unchanged with the increase of electrolyte flow rate.

Key words: non-aqueous thermally regenerative battery, complexes, reactors, series stack, maximal power generation, mass transfer

中图分类号:

TM911.3

李洞, 王倩倩, 张亮, 李俊, 付乾, 朱恂, 廖强. 非水系纳米流体热再生液流电池串联堆性能特性[J]. 化工进展, 2023, 42(8): 4238-4246.

LI Dong, WANG Qianqian, ZHANG Liang, LI Jun, FU Qian, ZHU Xun, LIAO Qiang. Performance of series stack of non-aqueous nano slurry thermally regenerative flow batteries[J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4238-4246.

图/表 10

图1 紧凑型液流电池结构及串联电堆

图2 紧凑型TRB几何模型及网格划分

表1 几何区域尺寸参数

参数	数值
电极高度H/mm	20
电极宽度W/mm	20
腔室及电极厚度L/mm	3
AEM厚度T/mm	0.1

表2 模型中所使用的参数

参数	数值	来源
Cu²⁺扩散系数D(Cu²⁺)/m²·s^-1	1.5×10^-9	文献[30]
Cu(CH₃CN)₄⁺扩散系数D[Cu(CH₃CN)₄⁺]/m²·s^-1	2.4×10^-10	测量
CH₃CN扩散系数D(CH₃CN)/m²·s^-1	9.3×10^-9	文献[31]
Cu扩散系数D(Cu)/m²·s^-1	1.33×10^-9	测量
BF₄^-扩散系数D(BF₄^-)/m²·s^-1	1.1×10^-9	文献[31]
电极孔隙率ε	0.93	—
电极活性比表面积a_V/m²·m^-3	3504	测量
操作温度T/K	298.15	测量
阳极反应速度常量K₀^a/m·s^-1	2.5×10^-7	文献[31]
阴极反应速度常量K₀^c/m·s^-1	7×10^-7	文献[31]
Cu²⁺初始浓度c(Cu²⁺)/mol·L^-1	0.1	—
CH₃CN初始浓度c(CH₃CN)/mol·L^-1	4	—
Cu初始浓度c(Cu)/mol·L^-1	0.1	—
BF₄^-初始浓度c(BF₄^-)/mol·L^-1	0.15	—
式(5)、式(6)阴极传递系数 $α a c$	0.55	—
式(4)、式(7)阴极传递系数 $α a c$	0.45	—
式(4)、式(6)阳极传递系数 $α a c$	0.55	—
式(5)、式(7)阳极传递系数 $α a c$	0.45	—

表2 模型中所使用的参数

参数	数值	来源
Cu²⁺扩散系数D(Cu²⁺)/m²·s^-1	1.5×10^-9	文献[30]
Cu(CH₃CN)₄⁺扩散系数D[Cu(CH₃CN)₄⁺]/m²·s^-1	2.4×10^-10	测量
CH₃CN扩散系数D(CH₃CN)/m²·s^-1	9.3×10^-9	文献[31]
Cu扩散系数D(Cu)/m²·s^-1	1.33×10^-9	测量
BF₄^-扩散系数D(BF₄^-)/m²·s^-1	1.1×10^-9	文献[31]
电极孔隙率ε	0.93	—
电极活性比表面积a_V/m²·m^-3	3504	测量
操作温度T/K	298.15	测量
阳极反应速度常量K₀^a/m·s^-1	2.5×10^-7	文献[31]
阴极反应速度常量K₀^c/m·s^-1	7×10^-7	文献[31]
Cu²⁺初始浓度c(Cu²⁺)/mol·L^-1	0.1	—
CH₃CN初始浓度c(CH₃CN)/mol·L^-1	4	—
Cu初始浓度c(Cu)/mol·L^-1	0.1	—
BF₄^-初始浓度c(BF₄^-)/mol·L^-1	0.15	—
式(5)、式(6)阴极传递系数 $α a c$	0.55	—
式(4)、式(7)阴极传递系数 $α a c$	0.45	—
式(4)、式(6)阳极传递系数 $α a c$	0.55	—
式(5)、式(7)阳极传递系数 $α a c$	0.45	—

图3 不同电极间距对单电池性能的影响及结构优化后紧凑型电池放电特性

图4 紧凑型电池性能特性数值模拟

图5 供液方式对串联堆性能的影响

图6 不同子电池数量对串联电堆性能的影响

图7 不同连接方式对串联电堆性能的影响

图8 不同电解液流量下电堆性能和最大输出功率

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