质子交换膜燃料电池内含水气体扩散层的冻结特性研究

doi:10.11949/0438-1157.20201184

摘要/Abstract

摘要：

为了研究含水气体扩散层（GDL）的冻结特性及水分迁移规律，设计并搭建了含水GDL冻结过程的可视化观测系统。制备了不同润湿性的含水GDL，并对含水GDL的冻结过程进行了可视化实验研究，分析了含水GDL冻结过程中的温度变化，以及润湿性和过冷度对于结冰概率的影响。实验结果表明：含水GDL中的某点突然结冰引发整个GDL内水的过冷状态释放，随后在液固相变的体积膨胀作用下，尚未冻结的过冷水被挤压到GDL孔隙外；疏水性GDL会在更高过冷度下产生冻结现象；随着含水GDL温度的降低，内部过冷水的冻结概率不断增加。本研究探索了含水GDL的冻结特性，可为今后解决质子交换膜燃料电池（PEMFC）冷启动过程中GDL低温冻结问题奠定基础。

关键词: 燃料电池, 成核, 气体扩散层, 冻结特性, 润湿性, 多孔介质

Abstract:

To study the freezing characteristics of the water-containing gas diffusion layer (GDL) and the law of water migration, a visual observation system of the freezing process of the water-containing GDL was designed and built. The freezing process of the water-containing GDL was studied by visual experiment research. The temperature change during the freezing process of the water-containing GDL was analyzed. The influence of wettability and supercooling degree on freezing probability were analyzed. Experimental results show that the sudden freezing at a nucleation point of the GDL causes the release of the supercooled state of the water inside the entire GDL, and then the supercooled water is squeezed out of the GDL pores under the volume expansion force of liquid-solid phase change. Water inside the hydrophobic GDL freezes at higher supercooling degree. With the decrease of GDL temperature, the freezing probability of supercooled water inside GDL increases continuously. This study explores the freezing characteristics of the water-containing GDL, which can lay a foundation for solving the problem of the water-containing GDL freezing during the cold start-up of the proton exchange membrane fuel cell (PEMFC) in the future.

Key words: fuel cell, nucleation, gas diffusion layer, freezing characteristic, wettability, porous media

中图分类号:

TK 124

宇高义郎, 许竞莹, 王国卓, 陈志豪. 质子交换膜燃料电池内含水气体扩散层的冻结特性研究[J]. 化工学报, 2021, 72(4): 2276-2282.

UTAKA Yoshio, XU Jingying, WANG Guozhuo, CHEN Zhihao. Study on freezing characteristics of water in gas diffusion layer of proton exchange membrane fuel cells[J]. CIESC Journal, 2021, 72(4): 2276-2282.

图/表 12

图1 实验系统示意图1—低温水浴；2—泵；3—高速红外相机；4—GDL低温冷却容器；5—CCD相机；6—计算机

Fig.1 Schematic diagram of experimental system

图2 GDL低温冷却容器1—容器壁；2—含水的气体扩散层；3—玻璃（表面疏水处理）；4—石英玻璃片；5—真空隔热玻璃

Fig.2 Cooling vessel for GDL

表1 不同GDL的参数

Table 1 Parameters of different GDLs

GDL	PTFE/%(质量)	孔隙率ε/%	密度/(g/cm³)	饱和度S
GDL-0	0	78	0.39	60%~70%
GDL-10	10	76	0.42	60%~70%
GDL-20	20	73	0.45	60%~70%
GDL-40	40	66	0.53	60%~70%

图3 GDL冷却过程中的表面平均温度变化

Fig.3 The average temperature variation of GDL surface during its cooling process

图4 GDL的过冷态释放过程

Fig.4 Release of supercooled state of water in GDL

图5 GDL冻结后继续降温过程

Fig.5 Decrease of GDL surface temperature after freezing

图6 成核点

Fig.6 Nucleation points

图7 成核点的切除过程

Fig.7 Removal process of nucleation points

表2 不同成核点的平均冻结温度

Table 2 Average freezing temperatures at different nucleation points

位置	平均冻结温度/℃	标准差
A	-8.7	0.3
B	-8.4	0.2
C	-8.7	0.3

图8 GDL过冷度的频数分布

Fig.8 Frequency distribution of GDL subcooling degree

图9 频数分布模型[30]

Fig.9 Frequency distribution model[30]

图10 结冰概率W与过冷度T的关系

Fig.10 Relationship between freezing probability W and subcooling degree T

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