Exploration of the oxygen transport behavior in non-precious metal catalyst-based cathode catalyst layer for proton exchange membrane fuel cells

doi:10.1007/s11708-022-0849-1

Front. Energy

2023, Vol. 17

Issue (1) : 123-133 https://doi.org/10.1007/s11708-022-0849-1

RESEARCH ARTICLE

Exploration of the oxygen transport behavior in non-precious metal catalyst-based cathode catalyst layer for proton exchange membrane fuel cells

Shiqu CHEN¹, Silei XIANG², Zehao TAN¹, Huiyuan LI¹, Xiaohui YAN¹, Jiewei YIN¹, Shuiyun SHEN¹(

), Junliang ZHANG¹

¹. Institute of Fuel Cells School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
². School of Vehicle and Mobility, State Key Laboratory of Automotive Safety and Energy, Tsinghua University, Beijing 100084, China

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Abstract

High cost has undoubtedly become the biggest obstacle to the commercialization of proton exchange membrane fuel cells (PEMFCs), in which Pt-based catalysts employed in the cathodic catalyst layer (CCL) account for the major portion of the cost. Although non-precious metal catalysts (NPMCs) show appreciable activity and stability in the oxygen reduction reaction (ORR), the performance of fuel cells based on NPMCs remains unsatisfactory compared to those using Pt-based CCL. Therefore, most studies on NPMC-based fuel cells focus on developing highly active catalysts rather than facilitating oxygen transport. In this work, the oxygen transport behavior in CCLs based on highly active Fe-N-C catalysts is comprehensively explored through the elaborate design of two types of membrane electrode structures, one containing low-Pt-based CCL and NPMC-based dummy catalyst layer (DCL) and the other containing only the NPMC-based CCL. Using Zn-N-C based DCLs of different thickness, the bulk oxygen transport resistance at the unit thickness in NPMC-based CCL was quantified via the limiting current method combined with linear fitting analysis. Then, the local and bulk resistances in NPMC-based CCLs were quantified via the limiting current method and scanning electron microscopy, respectively. Results show that the ratios of local and bulk oxygen transport resistances in NPMC-based CCL are 80% and 20%, respectively, and that an enhancement of local oxygen transport is critical to greatly improve the performance of NPMC-based PEMFCs. Furthermore, the activity of active sites per unit in NPMC-based CCLs was determined to be lower than that in the Pt-based CCL, thus explaining worse cell performance of NPMC-based membrane electrode assemblys (MEAs). It is believed that the development of NPMC-based PEMFCs should proceed not only through the design of catalysts with higher activity but also through the improvement of oxygen transport in the CCL.

Keywords proton exchange membrane fuel cells (PEMFCs) non-precious metal catalyst (NPMC) cathode catalyst layer (CCL) local and bulk oxygen transport resistance

Corresponding Author(s): Shuiyun SHEN

Online First Date: 18 November 2022 Issue Date: 29 March 2023

Cite this article:

Shiqu CHEN,Silei XIANG,Zehao TAN, et al. Exploration of the oxygen transport behavior in non-precious metal catalyst-based cathode catalyst layer for proton exchange membrane fuel cells[J]. Front. Energy, 2023, 17(1): 123-133.

URL:

https://academic.hep.com.cn/fie/EN/10.1007/s11708-022-0849-1
https://academic.hep.com.cn/fie/EN/Y2023/V17/I1/123

Tab.1 Performance of recently reported NPMC-based MEAs

Fig.1 Schematic of MEA.

Fig.2 Introduction to the experimental method used to determine local and bulk oxygen transport resistance.

Fig.3 Limiting current test of MEA with Pt-based CCL and Zn-N-C DCL.

Fig.4 Limiting current test results for MEAs with different DCL thicknesses.

Fig.5 SEM images for accurate thickness measurement.

Sample	DCL thickness/μm	Standard deviation of DCL thickness	$i lim$ / (A·cm^?2)	Standard deviation of i_lim	1/ $i lim$ / (cm²·A^?1)
DCL1	5.39	0.376	0.080	0.00113	12.500
DCL2	8.85	0.257	0.071	0.00185	14.164
DCL3	17.08	0.943	0.055	0.00082	18.293
DCL4	22.53	0.479	0.049	0.00155	20.228

Tab.2 Data summary of electrochemical tests and SEM characterization results

Fig.6 Plot of Eq. (3), which illustrates the relationship between 1/

i lim

and DCL thickness.

Fig.7 Polarization curves and peak power densities of MEA optimization.

Fig.8 MEA with optimal loading tested at 1% and 4% oxygen concentrations.

Fig.9 SEM image of the NPMC-based MEA with optimal loading.

A	Empirical parameter A
a	Half the width of the flow field
B	Empirical parameter B
$c O 2 c h a n n e l$	Concentration of oxygen in flow channel
d	Depth of flow channel
217 $D O 2 C H$	Oxygen diffusion coefficient in flow channel
F	Faraday’s constant
i_lim	Limiting current density
L	Length of flow channel
N	Number of flow channel
P	Gas pressure in flow channel
P₀	Atmospheric pressure
p_channel	Flow channel pressure
P_w	Water vapor partial pressure
Q_dry	Total gas flow
R	gas constant
r_bulk,DCL	Bulk oxygen transport resistance of DCL per unit thickness
R_local,CCL	Local oxygen transport resistance of CCL
R_channel	Oxygen transport resistance of flow channel
R_CCL	Oxygen transport resistance of CCL
R_GDL	Oxygen transport resistance of gas diffusion layer
R_total	Total oxygen transport resistance
Slope	Fitted curve slope
T	Reaction temperature
$x O 2$	Mole fraction of oxygen
δ_CCL	Thickness of CCL
$δ C C L e f f$	Effective thickness of CCL
δ_DCL	Thickness of DCL

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[1]	Yanyan GAO, Ming HOU, Manman QI, Liang HE, Haiping CHEN, Wenzhe LUO, Zhigang SHAO. New insight into effect of potential on degradation of Fe-N-C catalyst for ORR[J]. Front. Energy, 2021, 15(2): 421-430.
[2]	Junliang ZHANG. Recent advances in cathode electrocatalysts for PEM fuel cells[J]. Front Energ, 2011, 5(2): 137-148.

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