基于直流内阻和交流阻抗特性的PEMFC水管理状态分析

doi:10.11949/0438-1157.20191126

摘要/Abstract

摘要：

基于Randles等效电路，研究质子交换膜燃料电池（PEMFC）操作温度和湿度耦合关系，建立电堆直流内阻和交流阻抗特性模型。通过两种方法相结合，研究不同操作条件下的电化学阻抗谱图和U-I输出特性曲线的变化规律，以及不同水管理状态在直流内阻和交流阻抗变化规律中体现出的对应关系，进而分析水管理状态对电堆输出性能的影响作用。仿真和实验结果表明，温湿度耦合关系下的不同水管理状态，在电化学阻抗谱图和U-I特性曲线中具有一致的变化规律和对应的量化关系；电堆输出性能中的膜干、水淹等现象，在直流内阻值和交流阻抗图的变化中具有明显的表现特征；通过研究水管理状态对两者的影响，能够实现操作条件的优化和电堆输出性能的优化控制。

关键词: 电化学阻抗谱, 湿度, 操作条件, 质子交换膜燃料电池, 水管理状态

Abstract:

Based on the Randles equivalent circuit, this paper studies the coupling relationship between operating temperature and humidity of proton exchange membrane fuel cell (PEMFC), establishes the direct current (DC) internal resistance and alternating current (AC) impedance characteristics of the stack, and studies the electrochemical impedance spectrum and U-I output characteristics under different operating conditions. The AC impedance method and the U-I characteristic method are combined to obtain the correspondence between the AC impedance and the DC internal resistance under different water management states, and the influence of the water management state on the output performance of the stack is analyzed. The simulation and experimental results show that the different water management states have consistent variation rules and corresponding quantitative relationships in the AC impedance spectrum and the U-I characteristic curve. The phenomenon of membrane dryness, flooding, etc. in the output performance of the stack is in the DC internal resistance. And the change of the AC impedance map has clear performance characteristics. By studying the impact of water management states on both, it is possible to optimize the operating conditions and optimize the output performance of the stack.

Key words: EIS, humidity, operation conditions, PEMFC, water management

中图分类号:

TM 911.4

王茹, 沈永超, 卫东, 郭倩. 基于直流内阻和交流阻抗特性的PEMFC水管理状态分析[J]. 化工学报, 2020, 71(7): 3247-3257.

Ru WANG, Yongchao SHEN, Dong WEI, Qian GUO. Analysis of PEMFC water management status based on DC internal resistance and AC impedance characteristics[J]. CIESC Journal, 2020, 71(7): 3247-3257.

图/表 13

图1 Randles等效电路

Fig.1 Randles equivalent circuit

图2 电堆温度与湿度的耦合关系

Fig.2 Coupling relationship of TstackandRHstack

表1 模型仿真参数表

Table 1 Model simulation parameter table

参数	数值	参数	数值	参数	数值
V_a	0~30 L/min	δ	80 μm	α	0.05
V_c	0~150 L/min	A	180 cm²	t_m	0.051 mm
$P_{H_{2}, d r y}$	0.1~0.3 MPa	N	16	C_g	4 mol/L
p_air	0.15~0.45 MPa	RH	35%~95%	T	308~368 K
$M_{H_{2}, i n}$	0.1~0.4 g/s	M_air	0.36~0.8 g/s	t^*	5~60 s

表1 模型仿真参数表

Table 1 Model simulation parameter table

参数	数值	参数	数值	参数	数值
V_a	0~30 L/min	δ	80 μm	α	0.05
V_c	0~150 L/min	A	180 cm²	t_m	0.051 mm
$P_{H_{2}, d r y}$	0.1~0.3 MPa	N	16	C_g	4 mol/L
p_air	0.15~0.45 MPa	RH	35%~95%	T	308~368 K
$M_{H_{2}, i n}$	0.1~0.4 g/s	M_air	0.36~0.8 g/s	t^*	5~60 s

图3 活化内阻Rf的变化规律

Fig.3 Variation law of activation internal resistance Rf

图4 欧姆内阻Rm的变化规律

Fig.4 Variation law of ohm internal resistance Rm

图5 浓差内阻Rd的变化规律

Fig.5 Variation law of concentration internal resistance Rd

表2 不同操作条件下Rf、Rm、Rd和Rstack阻值计算结果

Table 2 Calculation results of Rf, Rm, Rd and Rstack resistance under different operating conditions

参数	优化			正常1			正常2			膜干		水淹
i/(A/cm²)	0~0.06	0.06~0.7	0.7~0.9	0~0.09	0.09~0.75	0.75~0.9	0~0.09	0.09~0.75	0.75~0.9	0~0.03	0.03~0.7	0.4~0.8
U/V	13.2~15.4	10.7~13.1	8.65~10.7	12.13~15.4	5.8~15.4	3.25~5.8	11.8~15.4	4.1~11.8	1.44~4.3	12.0~15.5	1.14~12.0	0.5~11.5
T_stack/K	306~309	306~335	335~343	309~312	310~338	338~345	303~306	306~330	330~343	293~303	303~333	320~333
RH_stack	40%~50%	50%~70%	70%~80%	40%~45%	45%~55%	55%~70%	40%~50%	60%~75%	75%~85%	30%~35%	35%~40%	65%~95%
R_f/(Ω·cm²)	33.7~73.7	3.1~33.7	1.66~3.1	22.58~90.1	2.2~22.6	1.38~2.2	23.8~76.5	3.1~23.8	1.68~2.11	88.2~161.4	5.4~100.4	2.05~11.5
R_m/(Ω·cm²)	4.43~5.3	3.28~4.4	1.52~3.3	10.1~11.0	6.82~10.1	7.12~8.8	12.4~13.1	6.02~12.4	5.97~8.0	16.66~18.5	15.65~18.3	2.04~4.40
R_d/(Ω·cm²)	0.02~0.03	0.03~1.12	1.12~4.34	0.02~0.03	0.03~1.17	1.17~5.01	0.02~0.03	0.03~2.45	2.45~7.90	0.02~0.03	0.03~0.54	1.91~27.6
R_stack/(Ω·cm²)	38.2~78.3	6.8~38.3	6.7~8.53	32.7~100.3	9.02~32.7	9.02~13.5	36.3~89.0	9.15~40.1	7.37~15.6	83.4~176.8	20.4~78.3	9.85~30.5

图6 电堆总内阻Rstack变化规律

Fig.6 Variation law of total internal resistance Rstack

图8 不同水管理状态下电化学阻抗图谱实验结果Zre—电化学阻抗实部；Zim—电化学抗虚部

Fig.8 Experimental results of electrochemical impedance map under different water management conditions

图9 不同水管理状态下U-I特性输出曲线实验结果

Fig.9 Experimental results of U-I characteristic curve under different water management conditions

图7 燃料电池堆实验系统

Fig.7 Fuel cell stack experiment system

表3 质子交换膜燃料电池堆性能参数

Table 3 PEMFC stack performance parameters

电堆参数	数值	电堆参数	数值
额定功率	1.5 kW	输出电流范围	0~160 A
额定电压	10.5 V	输出电压范围	7.2~16 V
额定电流	143 A	氢气/空气压力	0.1~0.15 MPa

表4 电化学阻抗图误差分析表

Table 4 Error analysis table of electrochemical impedance map

电流密度/ (A/cm²)	阻抗	不同状态下误差/%
电流密度/ (A/cm²)	阻抗	优化	正常1	正常2	膜干1	膜干2
0.1	R_m	1.13	2.01	2.48	2.45	2.80
	R_stack	-1.93	-3.36	-3.07	-5.13	-5.53
0.4	R_m	1.40	1.02	2.49	-1.78	-2.45
	R_stack	-1.99	-2.59	-2.27	-3.84	-4.02
0.8	R_m	1.89	1.28	1.68	1.49	1.16
	R_stack	-2.27	-3.23	-3.41	-3.49	-3.62

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