Defect-Engineered ZIF-Derived Non-Pt Cathode Catalyst at 1.5 mg cm-2 Loading for Proton Exchange Membrane Fuel Cells.

Due to the sluggish kinetics of the oxygen reduction reaction (ORR) by non-Pt based catalyst, high loading of catalyst is required to achieve satisfactory fuel cell performance, which inevitably leads to the increase of the catalyst layer thickness with serious mass transport resistance. Herein, a defective zeolitic imidazolate framework (ZIF) derived Co/Fe-N-C catalyst with small mesopores (2-4 nm) and high density of CoFe atomic active sites are prepared by regulating the Fe dosage and pyrolysis temperature. Molecular dynamics simulation and electrochemical tests indicate that > 2 nm mesopores show insignificant influence on the diffusion process of O2 and H2 O molecules, leading to the high utilization of active sites and low mass transport resistance. The proton exchange membrane fuel cell (PEMFC) shows a high-power density of 755 mW cm-2 with only 1.5 mg cm-2 of non-Pt catalyst in the cathode. No apparent performance loss caused by concentration difference can be observed, in particular in the high current density region (1 A cm-2 ). This work emphasizes the importance of small mesopore design in the Co/Fe-N-C catalyst, which is anticipated to provide essential guidance for the application of non-Pt catalysts.

Fast Current-Driven Synthesis of ZIF-Derived Catalyst Layers for High-Performance Zn-Air Battery.

As a core component, the catalyst layer (CL) is widely used in fuel cell, metal-air battery, and other energy conversion devices. Herein, a highly efficient method for CL preparation via fast current-driven synthesis followed by pyrolysis is proposed. Compared with previously reported fabrication procedures of zeolite imidazolate frameworks (ZIF)-based CLs, this method directly deposits the ZIF precursor onto the conductive substrate in a very short time (≤15 min). The self-supporting CL, converted from ZIF membrane by simple single-step pyrolysis, is assembled with the gas diffusion layer to obtain cathode. Electrochemical tests exhibit a small potential gap (0.83 V) between the oxygen reduction and evolution reactions, as well as high performance and excellent stability for Zn-air battery (241 mW cm-2 at 390 mA cm-2 ), due to the unique design of a bi-continuous framework (interconnected pores and long carbon nanotubes) and Co-based active sites. This work may provide new directions for the fast fabrication of non-platinum group metal CLs for metal-air batteries or fuel cell applications.

Space Confinement to Regulate Ultrafine CoPt Nanoalloy for Reliable Oxygen Reduction Reaction Catalyst in PEMFC.

A Co-based zeolitic imidazolate framework (ZIF-67) derived catalyst with ultrafine CoPt nanoalloy particles is designed via a two-step space confinement method, to achieve a robust oxygen reduction reaction (ORR) performance for proton exchange membrane fuel cell (PEMFC). The core-shell structure of ZIF-67 (core) and SiO2 (shell) is carefully adjusted to inhibit the agglomeration of Co nanoparticles. In the subsequent adsorption-annealing process, the in situ formed graphene shell on the surface of Co nanoparticles further protects metal particles from coalescence, leading to the ultrafine CoPt nanoalloy (average diameter is 2.61 nm). Benefitting from the high utilization of Pt metal, the mass activity of CoPt nanoalloy catalyst reaches 681.8 mA mgPt -1 at 0.9 V versus RHE according to the rotating disk electrode test in 0.1 m HClO4 solution. The CoPt nanoalloy-based PEMFC provides a high maximum power density of 2.22 W cm-2 (H2 /O2 ) and 0.923 W cm-2 (H2 /air). Simultaneously, it shows good stability in the long-time dynamic test at low humidity, due to the robust CoPt@graphene core-shell nanostructure. This work provides a viable strategy for designing Pt-based nanoalloy catalysts with ultrafine metal particles and high stability.

Recent Insights on Catalyst Layers for Anion Exchange Membrane Fuel Cells.

Anion exchange membrane fuel cells (AEMFCs) performance have significantly improved in the last decade (>1 W cm-2 ), and is now comparable with that of proton exchange membrane fuel cells (PEMFCs). At high current densities, issues in the catalyst layer (CL, composed of catalyst and ionomer), like oxygen transfer, water balance, and microstructural evolution, play important roles in the performance. In addition, CLs for AEMFCs have different requirements than for PEMFCs, such as chemical/physical stability, reaction mechanism, and mass transfer, because of different conductive media and pH environment. The anion exchange ionomer (AEI), which is the soluble or dispersed analogue of the anion exchange membrane (AEM), is required for hydroxide transport in the CL and is normally handled separately with the electrocatalyst during the electrode fabrication process. The importance of the AEI-catalyst interface in maximizing the utilization of electrocatalyst and fuel/oxygen transfer process must be carefully investigated. This review briefly covers new concepts in the complex AEMFC catalyst layer, before a detailed discussion on advances in CLs based on the design of AEIs and electrocatalysts. The importance of the structure-function relationship is highlighted with the aim of directing the further development of CLs for high-performance AEMFC.

Mass Transfer in a Co/N/C Catalyst Layer for the Anion Exchange Membrane Fuel Cell.

Developing highly efficient non-noble metal catalysts for the cathode of fuel cells is an urgent requirement for reducing the cost. Although the intrinsic activity of non-noble metal materials has been greatly improved, the fuel cell performance is also determined by the mass transfer within the catalyst layer (CL), particularly at high current density. Electrochemical impedance spectroscopy (EIS) combined with rotating disk electrode (RDE) analysis is a powerful tool to quantitatively analyze the influence of the structural properties on CL performance. Here, Co/N/C CLs with gradient pore structures are constructed based on the controllable synthesis of zeolitic imidazolate framework (ZIF)-derived catalyst. The influences of the carbon support, active site, and catalyst loading are comprehensively studied by EIS in different regions (kinetic and mixed-diffusion). The results indicate that a high micro-/mesopore ratio is beneficial to increasing the density of active sites while reducing the mass-transfer efficiency. Inversely, abundant mesopores promote mass transfer, but they result in low active site density. By carefully adjusting the pore structure and chemical composition of the ZIF-derived catalyst, the Co/N/C CL shows a low mass-transfer resistance (95.5 Ω at 0.75 V vs RHE). This work demonstrates the importance of mass transfer within the fuel cell CL, beyond seeking only high activity.

Hierarchically Porous Co-N-C Cathode Catalyst Layers for Anion Exchange Membrane Fuel Cells.

As a new class of metal-nitrogen-carbon (M-N-C) material with 3 D microstructure, zeolitic imidazolate frameworks (ZIFs) are used to synthesize highly active electrocatalysts for the oxygen reduction reaction, as substitutes for commercial Pt/C in anion exchange membrane fuel cells. However, to form an effective catalyst layer (CL), the relationship between the microstructure of the ZIF-derived catalyst and the fuel cell performance must be investigated. In this work, a hierarchically porous CL based on the carbon black (CB)-controlled synthesis of a Co-based ZIF (denoted as ZIF-CB-700) is constructed to optimize the triple-phase boundary (TPB) and mass transfer. The power density at 40 °C of ZIF-CB-700 (95.4 mW cm-2 ) as cathode catalyst is about 4 times higher than that of the catalyst synthesized in the absence of CB and is comparable to that of the commercial 60 % Pt/C catalyst (112.0 mW cm-2 ). Both online and offline measurements suggest that the morphology and microstructure of the CL is crucial to form an active TPB region, dominating the fuel cell performance rather than only the high catalyst activity.