Use of Boron Doped Diamond Corrosion Free Supports to Evaluate Fuel Cell Electrocatalyst Stability Under Accelerated Stress Testing

Abstract

Proton exchange membrane fuel cell (PEMFC) electrocatalysts are typically Pt or Pt alloy nanoparticles (NPs) supported on high surface area carbon black powders, the latter which contain a significant sp 2 carbon component. One of the barriers to PEMFC commercialisation is the lifetime of the catalyst-support system, which should be at least 5,000 hours for automotive applications. [1] During the start-up and shut-down of the PEMFC, the cathode is subjected to significant oxidative potentials (greater than 1 V vs RHE) which can lead to corrosion of the predominantly sp2 bonded carbon support, a key factor which can limit the lifetime of PEMFCs. [2] High quality boron doped diamond (BDD) is an sp 3 bonded network with above 1:1000 B:C ratio, which is required for metal-like electronic conductivity. BDD has many favourable properties for electrochemical experiments, most notably: higher electrochemical corrosion resistance with respect to sp 2 carbons, low background currents, and a wide aqueous solvent window. [3] In this work we first explore the electrochemical corrosion stability of BDD when undergoing electrochemical cycling in acid solutions. To achieve this BDD substrates (BDD TEM grid) suitable for both electrochemical experiments and high magnification (single atom resolution) transmission electron microscopy (TEM) experiments were produced using precision ion polishing (Gatan PIPS-II). The surface was characterised using X-ray photoelectron spectroscopy to ensure the polishing process did not significantly alter the diamond substrate. Under aggressive electrochemical potential cycling in perchloric acid and sulfuric acid solutions, both TEM morphological analysis and Electron Energy Loss Spectroscopy (EELS) thickness measurements showed no evidence of BDD corrosion. [4] The BDD-TEM substrate was then used as a platform for investigating the degradation of a PEMFC electrocatalyst (Pt NPs) under accelerated stress testing (AST) [1] conditions on an atomic level, using the corrosion free carbon support. This enables the influence of other degradation pathways [2] (such as aggregation, Ostwald Ripening & direct dissolution) to be explored in more detail, free from issues associated with corrosion of the support. Pt NPs, in the size range 1 – 4 nm, were sputter coated onto the BDD TEM grid. Identical location ex-situ TEM (IL-TEM) [5] in combination with image analysis was used to probe NP changes e.g. size, shape, position, on an individual basis before, and after, AST (Fig. 1, which contains c.a. 200 NPs for analysis). Such measurements were complemented by Inductively Coupled Plasma – Optical Emission Spectroscopy analysis for any dissolved Pt, and electrochemical cyclic voltammetry measurements of the Pt to highlight changes in electrocatalytic behaviour (hydrogen evolution reaction and oxygen reduction reaction) due to AST cycling. Figure 1 – High magnification annular dark field (ADF) identical location images of Pt NPs, a) Pt/BDD before AST, b) Pt NPs after AST, c) Cyclic voltammogram of the 1000 cycle AST from 0.8 to 1.4 V vs Ag|AgCl (1.6 to 1.6 V vs RHE). References: U.S. D.O.E.; Multi-Year Research, Development, and Demonstration Plan; 2016; 3.4 Fuel Cells. Mayrhofer, K.J.J.; et al.; Beilstein J. Nanotechnol.; 2014; 5; 44–67. Macpherson, J.V.; Phys. Chem. Chem. Phys.; 2015;17; 2935-2949 Hussein, H.E.M.; Wood. G.; Houghton. D.; Walker, M.; Han, Y.; Zhao, P.; Beanland, R.; Macpherson, J.V.; ACS Meas. Sci. Au; 2022; 2; 5; 439–448 Feliu, J.M.; Abruña, H.D.; J. Am. Chem. Soc. ; 2015; 137; 47; 14992–14998 Figure 1