基于泡沫碳扩散层的直接甲醇燃料电池改性研究

doi:10.11949/0438-1157.20240382

摘要/Abstract

摘要：

扩散层（DL）是直接甲醇燃料电池（DMFC）膜电极组件（MEA）的重要结构，为反应物从流场到催化层的传质提供通道，随着反应的进行，扩散层也为电子从催化层到流场的传输提供通道，因此，扩散层的导电率和表面形貌影响燃料电池的整体性能。泡沫碳（foam carbon，FC）材料具有优异的导电性能和三维网状结构，将其作为阴极扩散层（CDL），能够降低燃料电池膜电极与集流板间的接触电阻、电荷转移电阻和传质电阻。同时，泡沫碳的较高孔隙率和较小的表面接触角，可增加DMFC阴极催化层暴露在空气中的比例，提供更多的气液两相流道，是较好的催化剂载体。研究结果表明，与传统碳纸比较，泡沫碳作为阴极扩散层的燃料电池峰值功率密度从24.47 mW/cm²提升到39.24 mW/cm²，接触电阻由0.588 Ω降低至0.494 Ω，电荷转移电阻由2.784 Ω降低至1.816 Ω，传质阻抗由1.689 Ω降低至1.417 Ω。在100 mA/cm²的电流放电条件下，FC的放电时长为60 min，碳纸作为DL的放电时长为46 min，FC作为扩散层有更长的放电时间。研究结果说明在相同甲醇浓度以及体积下，新型结构有着比常规结构更高的能量效率。

关键词: 燃料电池, 扩散层, 泡沫碳, 两相流, 功率密度

Abstract:

Diffusion layer (DL) is an essential structure of a direct methanol fuel cell (DMFC) membrane electrode assembly (MEA), which provides a channel for the mass transfer of reactants from the flow field to the catalytic layer. As the reaction proceeds, the DL also provides a channel for the transport of electrons from the catalytic layer to the flow field. Therefore, the conductivity and surface morphology of the DL affects the overall performance of the fuel cell. The cathode diffusion layer (CDL) based on the foam carbon (FC) material could reduce the contact, charge transfer, and mass transfer resistance between the fuel cell membrane electrode and the current collector plate thanks to the FC's electrical conductivity and three-dimensional network structure. Moreover, the high porosity and small surface contact angle (CA) of FC could also increase the proportion of DMFC cathode catalytic layer exposed to the air and provide extra gas-liquid two-phase channels, which is the better catalyst support. Experimental results show that compared with the DMFC based on traditional carbon paper (CP-DMFC), the maximum power density of the DMFC with FC as the CDL (FC-DMFC) increases from 24.47 mW/cm² to 39.24 mW/cm², the contact resistance decreases from 0.588 Ω to 0.494 Ω, the charge transfer resistance decreases from 2.784 Ω to 1.816 Ω, and the mass transfer impedance decreased from 1.689 Ω to 1.417 Ω. Under a discharging current of 100 mA/cm², the discharge time of FC-DMFC is 60 min, while the discharge time of CP-DMFC is 46 min, and FC as a diffusion layer has a longer discharge time. It shows that the new structure has higher energy efficiency under the same methanol concentration and volume than the conventional structure.

Key words: fuel cell, diffusion layer, foamy carbon, two-phase flow, power density

中图分类号:

TM 911.4

赵振刚, 周梦瑶, 金典, 张大骋. 基于泡沫碳扩散层的直接甲醇燃料电池改性研究[J]. 化工学报, 2024, 75(S1): 259-266.

Zhengang ZHAO, Mengyao ZHOU, Dian JIN, Dacheng ZHANG. Study on direct methanol fuel cell performance modification based on foam carbon diffusion layer[J]. CIESC Journal, 2024, 75(S1): 259-266.

图/表 11

表1 CP与FC的具体参数

Table 1 Specific parameters of CP and FC

材料

类型

厚度/

μm

电阻率/

(Ω/cm)

孔隙率/

含碳量/

图1 CP和FC的SEM图像

Fig.1 SEM images of CP and FC

图2 湿润接触角

Fig.2 Contact angles

图3 MEA结构示意图(a)；CP-MEA和FC-MEA (b)；DMFC装配图(c)；DMFC实物图(d)

Fig.3 Schematic diagram of MEA (a); CP-MEA, FC-MEA (b); Assembly structural diagram (c); Assembled DMFC (d)

图4 不同甲醇浓度下的极化曲线

Fig.4 Polarization curves of different methanol concentrations

表2 CP-DMFC和FC-DMFC在不同甲醇浓度下的最大功率密度

Table 2 Maximum power density of CP-DMFC and FC-DMFC under different methanol concentrations

甲醇浓度/ (mol/L)	CP-DMFC/(mW/cm²)	FC-DMFC/(mW/cm²)	提升率/%
0.5	18.48	36.00	94.81
1	24.47	39.24	60.36
2	20.65	28.71	39.03
3	15.06	15.58	3.45

图5 电池内部损耗

Fig.5 Internal losses of the cell

图6 DMFC的全电池等效电路模型

Fig.6 Full-cell equivalent circuit model of DMFC

图7 电化学阻抗谱和拟合曲线

Fig.7 Electrochemical impedance spectra and fitting curves

表3 ECM参数识别结果

Table 3 Parameter identification results

项目	CP-DMFC	FC-DMFC	提升率
R_m/Ω	0.588	0.494	-16.0%
R_i/Ω	1.421	1.437	1.1%
R_ct/Ω	2.784	1.816	-34.8%
R_mt/Ω	1.689	1.417	-16.1%

图8 CP-DMFC和FC-DMFC在最佳甲醇浓度下的恒流放电曲线

Fig.8 Constant current discharge curves of CP-DMFC and FC-DMFC under optimal methanol concentration

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