Study of Polymer-Coating on Various Types of Carbon Supports to Enhance Platinum Utilization Efficiency in Polymer Electrolyte Membrane Fuel Cell Electrocatalysts

Abstract

Polymer electrolyte membrane fuel cells (PEMFCs) have been receiving ample attention as an efficient and clean power source for stationary and automotive applications.1 One of the challenges for commercialization of PEMFCs is to minimize the amount of Platinum (Pt) to lower the cost of PEMFC. Pt is the most stable and active catalyst for oxygen reduction reaction (ORR).2 Incorporation of non-precious metals and decreasing the catalyst particle size are common methods to reduce the amount of Pt used in PEMFC. However, these methods involve dissolution of non-precious metals in acidic condition3 and agglomeration of small sized Pt4, resulting in decreased Pt utilization. Therefore, improvement of Pt utilization efficiency is required. Optimizing catalyst structure by increasing number of reaction sites is a promising strategy to improve the Pt utilization efficiency. One approach is increasing mass diffusion (oxygen, proton) by selecting a non-porous carbon support like acetylene black (AB).5 However, Pt durability and utilization are limited due to lack of anchoring sites for Pt particles in AB.6 Another approach is optimizing ionomer/carbon ratio. However, recent high-resolution transmission electron microscopy studies suggest that the ionomer coverage in the electrode may be rather inhomogeneous.7 In this study, we demonstrate a novel approach to improve Pt utilization efficiency in PEMFC by preventing deposition of Pt particles into interior pores of carbon support and simultaneously providing homogeneous ionomer; Nafion coverage. This approach involves polymer coating onto carbon blacks (CBs). Polybenzimidazole (PBI) is used as the surface coating material of CB where PBI interacts with CB via π-π and acid-base interactions. It is reported that PBI coating works as the micropore capping agent of CB.8 Therefore, PBI coating can reduce number of Pt particles deposited into geometrically restricted areas of CB. Moreover, PBI coating may trigger a homogeneous Nafion coverage due to the acid-base interaction between Nafion and PBI concurrently. Three morphologically different CBs; Vulcan, Ketjen black (KB) and AB were used to investigate the Pt utilization efficiency in polymer coated CBs. The PBI coating onto CB was easily done by addition of CB into PBI dissolved N,N-dimethylacetamide and 1 hr sonication to the mixture to prepare Vulcan/PBI, KB/PBI and AB/PBI. Then Pt nano-particles were deposited via polyol reduction to prepare Vulcan/PBI/Pt, KB/PBI/Pt and AB/PBI/Pt and compared with their non-coated Vulcan/Pt, KB/Pt and AB/Pt. AB/PBI/Pt shows homogeneous Pt dispersion over AB/Pt due to the presence of binding sites through coordination of Pt with imidazole groups in PBI as an additional advantage. The micropore density of CBs is increasing in the order of AB < Vulcan < KB. Power density of CB/Pts was decreased in the following order; AB/Pt < Vulcan/Pt < KB/Pt, consistent with the order of increasing micropore density. The lower performance of KB/Pt is due to the decreased number of accessible Pts for the electrochemical reaction especially for ORR5. Interestingly, power densities of CB/PBI/Pts were higher than that of respective CB/Pts. The higher power density of CB/PBI/Pt can be attributed to the reduced inaccessible amount of Pt deposited into the micropores of CB and the reduced protonic resistance in the catalyst layer due to the homogeneous Nafion layer.9 Furthermore, power densities of CB/PBI/Pts were increasing in the order of KB/PBI/Pt < Vulcan/PBI/Pt < AB/PBI/Pt. The highest performance of AB/PBI/Pt is believed to be due to lower mass transfer limitation in the catalyst layer which is caused by the lower pore density of AB/PBI along with the uniform Nafion coverage. References Kibsgaard, J.; Gorlin, Y.; Chen, Z.; Jaramillo, T. F., J. Am. Chem. Soc. 2012, 134, 7758.Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.; Lindqvist, L.; Kitchin, J. R.; Bligaard, T.; Jónsson, H., J. Phys. Chem. B 2004, 108, 17886.Colón-Mercado, H. R.; Kim, H.; Popov, B. N., Electrochem. Commun. 2004, 6, 795.Tang, L.; Han, B.; Persson, K.; Friesen, C.; He, T.; Sieradzki, K.; Ceder, G., J. Am. Chem. Soc. 2010, 132, 596.Park, Y.-C.; Tokiwa, H.; Kakinuma, K.; Watanabe, M.; Uchida, M., J. Power Sources 2016, 315, 179.Badam, R.; Vedarajan, R.; Matsumi, N., Chem. Commun. 2015, 51, 9841.Lopez-Haro, M.; Guétaz, L.; Printemps, T.; Morin, A.; Escribano, S.; Jouneau, P. H.; Bayle-Guillemaud, P.; Chandezon, F.; Gebel, G., Nat. Commun. 2014, 5, 5229.Fujigaya, T.; Hirata, S.; Berber, M. R.; Nakashima, N., ACS Appl. Mater. Interfaces 2016, 8, 14494.Jayawickrama, S. M; Han, Z. et al., in review.