Highly Active Transition Metal and Nitrogen Co-Doped Carbon Nanotube Based Cathode Catalysts for Anion Exchange Membrane Fuel Cells
Authors: Kruusenberg Ivar , Ramani Dilip , Ratso Sander , Tammeveski Kaido , Kannan Arunachala Mada 
Published: February 2020

Low cost and high durability are considered as the main challenges in mass scale commercialization of the low temperature fuel cells. Anion exchange membrane fuel cells (AEMFC’s) have attracted tremendous attention because of their promising characteristics to overcome some of the critical problems associated with proton exchange membrane fuel cells. The main advantages of AEMFC´s are possibility of using cheaper non-noble metal catalyst, lower crossover of cationic redox couples, facile reaction kinetics. In recent years, nitrogen-doping of carbon materials has been used to achieve active non-platinum catalyst.1,2 However it has been reported that the presence of transition metals such as Co or Fe can further enhances the electrocatalytic properties of N-doped carbons.3

The main goal of this study was to develop highly active transition metal-nitrogen co-doped catalyst as alternative cathode material to Pt/C in AMFC.
A simple synthesis method was used to receive nitrogen doped multi-walled carbon nanotube supported CoCl2 catalyst material (Co/N-MWCNT). MWCNT treated in a concentrated HNO3-H2SO4 mixture were used as carbon support. MWCNTs were first dispersed in ethanol by sonication, after which dicyandiamide as the nitrogen source and Co salt were added along with a dispersing agent. The mixture was then heat-treated at 800 °C for 2 h in a tube furnace. Polished glassy carbon electrodes were modified with a dispersion containing the resulting materials and Tokuyama OH−ionomer AS-04. The rotating disk electrode (RDE) measurements were performed in 0.1 M KOH. The stability of the catalysts were also tested using RDE method. The structural and compositional properties of the catalyst material were defined by X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The oxygen reduction reaction (ORR) has been studied on Co/N/MWCNT electrocatalyst modified GC electrodes in 0.1 M KOH using the RDE method. The fuel cell performance of Co/N/MWCNT cathode catalyst material was investigated by fabricating membrane-electrode assemblies (MEAs) using Tokuyama membrane (# A201).
The RDE results indicated excellent electrocatalytic properties of Co/N-MWCNT material toward oxygen electroreduction in alkaline media. The comparative study of Co/N-MWCNT with commercial Pt/C catalyst showed fair catalytic activity of our non-platinum catalyst in 0.1M KOH and significant enhancement of the ORR was observed in comparison to unmodified MWCNTs. The number of electrons transferred per oxygen molecule (n) at different potentials for the Co/N-MWCNT modified GC electrode was calculated from the KouteckyLevich equation. The value of n for the Co/N-MWCNT material was 4 over the whole range of potentials studied. The fuel cell performance was investigated with Co/N-MWCNT cathode catalyst and Tokuyama A201 anion exchange membrane. AEMFC performance was evaluated and compared at different temperatures up to 50 ⁰C. Maximum power density with H2/O2 gases at ambient pressure was ~115 mWcm-2. The fuel cell perfomance of the Co/N-MWCNT catalyst was also compared with the perfomance of the commercial Pt/C and cobalt phthalocyanine modified MWCNT catalysts (Fig.1).

References:

S. Ratso, I. Kruusenberg, M. Vikkisk, U. Joost, E. Shulga, I. Kink, T. Kallio, and K. Tammeveski, Carbon, 73, 361 (2014).

M. Vikkisk, I. Kruusenberg, U. Joost, E. Shulga, I. Kink, and K. Tammeveski, Appl. Catal. B, 147, 369 (2014).

A. Sarapuu, L. Samolberg, K. Kreek, M. Koel, L. Matisen, and K. Tammeveski, J. Electroanal. Chem., 746, 9 (2015).

Figure 1