Three-dimensional porous electrodes for direct formate fuel cells

The dual-layer electrode for fuel cells is typically prepared by binding discrete catalyst nanoparticles onto a diffusion layer.Such a random packing forms a dense catalyst layer and thus creates a barrier for mass/ion transport,particularly for direct liquid fuel cells.Three-dimensional porous electrodes,a thin nano-porous catalyst layer uniformly distributed on the matrix surface of a foam-like structure,are typically employed to improve the mass/ion transport.Such a three-dimensional porous structure brings two critical advantages:(i)reduced mass/ion transport resistance for the delivery of the reactants via shortening the transport distance and(ii)enlarged electrochemical surface area,via reducing the dead pores,isolated particles and severe aggregations,for interfacial reactions.Moreover,the three-dimensional design is capable of fabricating binder-free electrodes,thereby eliminating the use of ionomers/binders and simplifying the fabrication process.In this work,three types of three-dimensional porous electrode are fabricated,via different preparation methods,for direct formate fuel cells:(i)Pd/C nanoparticles coating on the nickel foam matrix surface(Pd-C/NF)via a dip-coating method,(ii)Pd nanoparticles depositing on the nickel foam matrix surface(Pd/NF)via reduction reaction deposition,and(iii)Pd nanoparticles embedding in the nickel foam matrix(Pd/(in)NF)via replacement reaction deposition.The latter two are binder-free three-dimensional porous electrodes.As a comparison,a conventional dual-layer design,Pd/C nanoparticles painting on the nickel foam layer(Pd-C//NF),is also prepared via direct painting method.It is shown that the use of the three-dimensional Pd-C/NF electrode as the anode in a direct formate fuel cell results in a peak power density of 45.0 mW cm^(-2)at 60℃,which is two times of that achieved by using a conventional dual-layer design(19.5 mW cm^(-2)).This performance improvement is mainly attributed to the unique three-dimensional structure design,which effectively enhances the mass/ion transport through the porous electrode and enlarges the electrochemical surface area(accessible active area)for interfacial reactions.In addition,the delivery of the fuel solution is still sufficient even when the flow rate is as low as 2.0 mL min^(-1).It is also demonstrated that direct formate fuel cells using two binder-free electrodes yield the peak power densities of 13.5 mW cm^(-2)(Pd/(in)NF)and 14.0 mW cm^(-2)(Pd/NF)at 60℃,respectively,both of which are much lower than the power density achieved by using the Pd-C/NF electrode.This is because the electrochemical surface areas of two binderfree electrodes are much smaller than the Pd/C-based electrodes,since the specific area of Pd/C nanoparticles is much larger.

On the role of Zn and Fe doping in nitrogen-carbon electrocatalysts for oxygen reduction

Zn is a frequently used and sometimes even an inevitably involved element (when zeolitic imidazolate framework-8 (ZIF-8) is adopted as the precursor) for preparing high-performance Fe-N-C oxygen reduction reaction (ORR) catalysts. However, how the Zn element affects the physicochemical architecture of the catalysts, how it enhances the catalytic activity and whether Zn atoms serve as the active centers remain unclear. Herein, we proposed a novel route that adopted pyrrole as the precursor and flexibly controlled the addition of exogenous Zn and Fe dopants before pyrrole polymerization. In this way, a series of nitrogen-carbon catalysts with or without Zn or Fe doping were synthesized. The detailed characterization revealed the role of Zn and Fe doping in the catalyst morphology, pore structure, active site configurations, ORR catalytic activity and fuel cell performance. Importantly, the findings revealed that Zn doping has little effect on the ORR mechanism and pathway. It enhances ORR activity primarily by increasing the number of active sites via introducing more micro- and meso-pores, rather than by creating new active sites. While Fe doping participated in forming both pores and active site centers. Moreover, the catalyst that co-doped with Zn and Fe atoms (Zn-FeNC), synthesized via this simple and template-free route we proposed, presented a unique hollow and hierarchical pore structure with highly boosted ORR activity. It exhibited a 40 mV higher E 1/2 value than Pt/C in alkaline media, along with a rapid current response in air-cathode of the direct formate fuel cell. These results are valuable in guiding the synthesis of high-performance Fe-N-C catalysts.