高温质子交换膜燃料电池中阴极双催化层孔结构的设计研究★

doi:10.6023/A23040184

摘要/Abstract

优化气体扩散电极(GDE)的结构是提升高温质子交换膜燃料电池(HT-PEMFC)性能、降低成本的重要手段. 本工作通过调控内外催化层中碳酸氢铵造孔剂含量, 构筑了一种梯度孔分布的双催化层阴极, 优化磷酸分布, 降低氧传输阻力, 从而达到电化学性能提升的目的. 结果显示, 当内催化层使用46.7% (w) PtCo/C且不添加造孔剂, 外催化层使用40% (w) Pt/C且铂与造孔剂质量比为0.53时构成的膜电极, 在160 ℃与常压氢空进料下, 其组成的单电池最大功率密度达439 mW•cm^-2, 比未添加造孔剂的单电池最大功率密度高69 mW•cm^-2.

关键词: 高温质子交换膜燃料电池, 双催化层, 造孔剂, 电化学性能

High-temperature proton exchange membrane fuel cell (HT-PEMFCs) has the advantages of simple hydro-thermal management, strong resistance to CO, direct feeding of reforming gas and high efficiency of cogeneration. It is one of the ideal power sources for the development of clean energy. As the core component of HT-PEMFCs, membrane electrode assembly (MEA) is mainly composed of cathode and anode gas diffusion electrode and proton exchange membrane, which determines the performance and cost of HT-PEMFCs. Therefore, optimizing the structure of gas diffusion electrode (GDE) is an important means to improve the performance and reduce the cost of HT-PEMFC. In this work, from the point of view of catalytic layer, pore-forming agent was introduced into catalytic layer to construct double catalytic layer with different pore structure. Among them, MEA 2 uses 46.7% (w) PtCo/C in the inner catalyst layer without adding pore-forming agent, and the outer catalyst layer uses 40% (w) Pt/C and adds 20% (w) pore-forming agent. It has relatively small ohmic polarization, minimum mass transfer polarization and activation polarization, and has the largest electrochemical active area, and the electrochemical performance is the best. At 160 ℃ and atmospheric pressure, hydrogen and air as fuel, the maximum power density of the single cell composed of the membrane electrode is 439 mW•cm^-2, which is 69 mW•cm^-2 higher than that of the single cell without pore-forming agent. Whether the pore-forming agent is added into the inner catalytic layer (CL) or the outer CL, the pore structure is adjusted to optimize the phosphoric acid (PA) distribution and reduce the oxygen mass transfer resistance to improve the electrochemical performance. The former catalyst layer has a greater hydrophobicity change and the electrochemical performance is more affected by the PA content, while the latter catalyst layer hydrophobicity changes less and the electrochemical performance is more affected by the oxygen mass transfer resistance. Excessive addition of pore-forming agent inside or outside CL will produce larger ohmic polarization resistance (R_Ω), and the acid drowning caused by insufficient hydrophobicity of CL will further reduce the electrochemical performance of the battery.

Key words: high-temperature proton exchange-membrane fuel cell, double catalytic layer, pore-forming agent, electrochemical performance

引用此文

刘士琨, 邓程维, 姬峰, 闵宇霖, 李和兴. 高温质子交换膜燃料电池中阴极双催化层孔结构的设计研究^★[J]. 化学学报, 2023, 81(9): 1135-1141.

Shikun Liu, Chengwei Deng, Feng Ji, Yulin Min, Hexing Li. Design and Study on Pore Structure of Cathode Double Catalytic Layer in High-temperature Proton Exchange Membrane Fuel Cell^★[J]. Acta Chimica Sinica, 2023, 81(9): 1135-1141.

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图/表 11

	内CL		外CL
	Pt载量/ (mg•cm^-2)	造孔剂质量∶总固体质量/%	Pt载量/ (mg•cm^-2)	Pt载量/ (mg•cm^-2)
MEA 0	0.250	0	0.253	0.250
MEA 1	0.252	0	0.248	0.252
MEA 2	0.251	0	0.248	0.251
MEA 3	0.250	0	0.251	0.250
MEA 4	0.249	10	0.253	0.249
MEA 5	0.252	10	0.251	0.252
MEA 6	0.250	10	0.252	0.250

表1. 阴极双催化层的基本信息

Table 1. Basic information of cathodic double catalytic layer

图1. SEM形貌图. MEA 0阴极催化层的截面图(a); MEA 0阴极的平面形貌图(b, c); MEA 2阴极催化层的截面图(d); MEA 2阴极的平面形貌图(e, f)

Figure 1. SEM topography. Cross-section view catalytic layer of MEA 0 (a); plane topography of cathodic catalytic layer of MEA 0 (b, c); cross-section view catalytic layer of MEA 2 (d); plane topography of cathodic catalytic layer of MEA 2 (e, f)

图2. Pt/C加入不同比例造孔剂后的孔隙分布

Figure 2. The pore distribution of Pt/C after adding different proportion of pore-forming agent

图3. 亲疏水性测试图. MEA 0内CL (a)、MEA 4内CL (b)、MEA 0外CL (c)、MEA 1外CL (d)、MEA 2外CL (e)和MEA 3外CL (f)的接触角测试结果

Figure 3. Hydrophilic and hydrophobic test pattern. The contact angle test results of CL within MEA 0 (a), CL within MEA 4 (b), CL outside MEA 0 (c), CL outside MEA 1 (d), CL outside MEA 2 (e) and CL outside MEA 3 (f)

图4. 阴极内催化层不含造孔剂、外催化层造孔剂含量不同的MEA极化曲线(a)、功率密度曲线(b). 阴极内催化层含10% (w)造孔剂、外催化层造孔剂含量不同的MEA极化曲线(c)、功率密度曲线(d)

Figure 4. The polarization curve (a) and power density curve (b) of the inner catalytic layer does not contain pore-forming agents and the outer catalytic layer contains cathodic catalytic layers with different proportions of pore-forming agents. The polarization curve (c) and power density curve (d) of the inner catalytic layer contains 10% (w) pore-forming agents and the outer catalytic layer contains cathodic catalytic layers with different proportions of pore-forming agents

	电压/V					最大功率密度/ (mW•cm^-2)
	0.2 A•cm^-2	0.5 A•cm^-2		1.2 A•cm^-2		最大功率密度/ (mW•cm^-2)
MEA 0	0.618		0.507		0.306	370
MEA 1	0.615		0.518		0.352	425
MEA 2	0.632		0.531		0.366	439
MEA 3	0.605		0.500		0.301	363
MEA 4	0.619		0.514		0.316	379
MEA 5	0.606		0.523		0.359	432
MEA 6	0.620		0.521		0.342	410

表2. 各膜电极在0.2 、0.5、1.2 A?cm-2电流密度下的电压以及峰值功率密度

Table 2. Voltage at 0.2, 0.5, 1.2 A?cm-2 current density and peak power density of each membrane electrode

图5. 阴极内催化层不含造孔剂、外催化层造孔剂含量不同的MEA CV曲线(a)以及EIS曲线(b); 阴极内催化层含10% (w)造孔剂、外催化层造孔剂含量不同的MEA CV曲线(c)以及EIS曲线(d)

Figure 5. The CV curve (a) and EIS curve (b) of the inner catalytic layer does not contain pore-forming agents and the outer catalytic layer contains cathodic catalytic layers with different proportions of pore-forming agents. The CV curve (c) and EIS curve (d) of the inner catalytic layer contains 10% (w) pore-forming agents and the outer catalytic layer contains cathodic catalytic layers with different proportions of pore-forming agents

	R_Ω/(m_Ω•cm²)	R_p/(m_Ω•cm²)	(R_ct+R_mt)/(m_Ω•cm²)
MEA 0	0.091	0.038	0.388
MEA 1	0.094	0.018	0.24
MEA 2	0.099	0.021	0.204
MEA 3	0.112	0.043	0.303
MEA 4	0.108	0.049	0.264
MEA 5	0.112	0.025	0.214
MEA 6	0.118	0.046	0.221

表3. 各膜电极的等效电路拟合结果

Table 3. The equivalent circuit fitting results of each membrane electrode

图6. 不同MEA的氧增益曲线

Figure 6. Oxygen gain curves of different MEA

图7. 0.2 A?cm-2下, MEA 2的耐久性测试

Figure 7. Durability test of MEA 2 at 0.2 A?cm-2

图8. 等效电路模型

Figure 8. Equivalent circuit model

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