A Review of Carbon-Composited Materials as Air-Electrode Bifunctional Electrocatalysts for Metal–Air Batteries

AbstractMetal–air batteries (MABs), particularly rechargeable MABs, have gained renewed interests as a potential energy storage/conversion solution due to their high specific energy, low cost, and safety. The development of MABs has, however, been considerably hampered by its relatively low rate capability and its lack of efficient and stable air catalysts in which the former stems mainly from the sluggish kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) and the latter stems from the corrosion/oxidation of carbon materials in the presence of oxygen and high electrode potentials. In this review, various carbon-composited bifunctional electrocatalysts are reviewed to summarize progresses in the enhancement of ORR/OER and durability induced by the synergistic effects between carbon and other component(s). Catalyst mechanisms of the reaction processes and associated performance enhancements as well as technical challenges hindering commercialization are also analyzed. To facilitate further research and development, several research directions for overcoming these challenges are also proposed

Conductive Polymer and Nanoparticle-Promoted Polymer Hybrid Coatings for Metallic Bipolar Plates in Proton Membrane Exchange Water Electrolysis

Proton exchange membrane water electrolysis (PEMWE) is a green hydrogen production technology with great development prospects. As an important part of PEMWE, bipolar plates (BPs) play an important role and put forward special requirements due to the harsh environments on both the anode and cathode. Recently, metal-based BPs, particularly stainless steel and titanium BPs have attracted much attention from researchers all over the world because of their advantages of high corrosion resistance, low resistivity, high thermal conductivity, and low permeability. However, these metallic BPs are still prone to being oxidized and are facing with hydrogen embrittlement problems in the PEMWE working environment, which would result in reduced output power and premature failure of the PEMWE stack. In order to reduce the corrosion rate and maintain low interfacial contact resistance, the surface modification of the metallic BPs with protective coatings, such as precious metals (e.g., Au, Pt, etc.) and metal nitrides/carbides, etc., have been extensively investigated. However, the above-mentioned coating materials are restricted by the high-cost materials, complex equipment, and the complicated operation process. In this review, the surface modification of metallic BPs based on silane treatment, conductive polymers, e.g., polyaniline (PANI) and polypyrrole (PPy) as well as some nanoparticles-promoted polymer hybrid coatings which have been investigated for PEMWE, are summarized and reviewed. As for the silane treatment, the dense silane can not only effectively enhance the corrosion resistance but also improve the adhesion between the substrate and the conductive polymers. As for PANI and PPy, the typical value of corrosion current density of a PANI coating is 5.9 μA cm−2, which is significantly lower than 25.68 μA cm−2 of the bare metal plate. The introduction of nanosized conductive particles in PANI can further reduce the corrosion current density to 0.15 μA cm−2. However, further improvement in the electrical conductivity is still desired to decrease the interface contact resistance (ICR) to be lower than 10 mΩ cm2. In addition, serious peeling off of the coating during long-term operation also needs to be solved. Typically, the conductive polymer reinforced by graphene, noble metals, and their compounds in the form of nanoparticle-promoted polymer hybrid coatings could be a good choice to obtain higher corrosion resistance, durability, and conductivity and to extend the service life of PEMWE. Especially, nanoparticle-promoted polymer hybrid coatings consisting of polymers and conductive noble metals or nitrides/carbides can be controlled to balance the conductivity and mechanical properties. Due to the advantages of a simple preparation process, low cost, and large-scale production, nanoparticle-promoted polymer hybrid coatings have gradually become a research hotspot. This review is believed to enrich the knowledge of the large-scale preparation process and applications of BPs for PEMWE

Robust Porous TiN Layer for Improved Oxygen Evolution Reaction Performance

The poor reversibility and slow reaction kinetics of catalytic materials seriously hinder the industrialization process of proton exchange membrane (PEM) water electrolysis. It is necessary to develop high-performance and low-cost electrocatalysts to reduce the loss of reaction kinetics. In this study, a novel catalyst support featured with porous surface structure and good electronic conductivity was successfully prepared by surface modification via a thermal nitriding method under ammonia atmosphere. The morphology and composition characterization-confirmed that a TiN layer with granular porous structure and internal pore-like defects was established on the Ti sheet. Meanwhile, the conductivity measurements showed that the in-plane electronic conductivity of the as-developed material increased significantly to 120.8 S cm−1. After IrOx was loaded on the prepared TiN-Ti support, better dispersion of the active phase IrOx, lower ohmic resistance, and faster charge transfer resistance were verified, and accordingly, more accessible catalytic active sites on the catalytic interface were developed as revealed by the electrochemical characterizations. Compared with the IrOx/Ti, the as-obtained IrOx/TiN-Ti catalyst demonstrated remarkable electrocatalytic activity (η10 mA cm−2 = 302 mV) and superior stability (overpotential degradation rate: 0.067 mV h−1) probably due to the enhanced mass adsorption and transport, good dispersion of the supported active phase IrOx, increased electronic conductivity and improved corrosion resistance provided by the TiN-Ti support

Ordered Porous TiO₂@C Layer as an Electrocatalyst Support for Improved Stability in PEMFCs

Proton exchange membrane fuel cells (PEMFCs) are the most promising clean energy source in the 21st century. In order to achieve a high power density, electrocatalytic performance, and electrochemical stability, an ordered array structure membrane electrode is highly desired. In this paper, a new porous Pt-TiO₂@C ordered integrated electrode was prepared and applied to the cathode of a PEMFC. The utilization of the TiO₂@C support can significantly decrease the loss of catalyst caused by the oxidation of the carbon from the conventional carbon layer due to the strong interaction of TiO₂ and C. Furthermore, the thin carbon layer coated on TiO₂ provides the rich active sites for the Pt growth, and the ordered support and catalyst structure reduces the mass transport resistance and improves the stability of the electrode. Due to its unique structural characteristics, the ordered porous Pt-TiO₂@C array structure shows an excellent catalytic activity and improved Pt utilization. In addition, the as-developed porous ordered structure exhibits superior stability after 3000 cycles of accelerated durability test, which reveals an electrochemical surface area decay of less than 30%, considerably lower than that (i.e., 80%) observed for the commercial Pt/C.Applied Science, Faculty ofNon UBCChemical and Biological Engineering, Department ofReviewedFacultyResearche

Stainless Steel-Supported Amorphous Nickel Phosphide/Nickel as an Electrocatalyst for Hydrogen Evolution Reaction

Recently, nickel phosphides (Ni-P) in an amorphous state have emerged as potential catalysts with high intrinsic activity and excellent electrochemical stability for hydrogen evolution reactions (HER). However, it still lacks a good strategy to prepare amorphous Ni-P with rich surface defects or structural boundaries, and it is also hard to construct a porous Ni-P layer with favorable electron transport and gas–liquid transport. Herein, an integrated porous electrode consisting of amorphous Ni-P and a Ni interlayer was successfully constructed on a 316L stainless steel felt (denoted as Ni-P/Ni-316L). The results demonstrated that the pH of the plating solution significantly affected the grain size, pore size and distribution, and roughness of the cell-like particle surface of the amorphous Ni-P layer. The Ni-P/Ni-316L prepared at pH = 3 presented the richest surface defects or structural boundaries as well as porous structure. As expected, the as-developed Ni-P/Ni-316L demonstrated the best kinetics, with η10 of 73 mV and a Tafel slope of ca. 52 mV dec-1 for the HER among all the electrocatalysts prepared at various pH values. Furthermore, the Ni-P/Ni-316L exhibited comparable electrocatalytic HER performance and better durability than the commercial Pt (20 wt%)/C in a real water electrolysis cell, indicating that the non-precious metal-based Ni-P/Ni-316L is promising for large-scale processing and practical use

Ordered SnO2@C Flake Array as Catalyst Support for Improved Electrocatalytic Activity and Cathode Durability in PEMFCs

Pt-SnO₂@C-ordered flake array was developed on carbon paper (CP) as an integrated cathode for proton exchange membrane fuel cell through a facile hydrothermal method. In the integrated cathode, Pt nanoparticles were deposited uniformly with a small particle size on the SnO₂@C/CP support. Electrochemical impedance spectroscopy analysis revealed lower impedance in a potential range of 0.3–0.5 V for the ordered electrode structure. An electrochemically active surface area and oxygen reduction peak potential determined by cyclic voltammetry measurement verified the synergistic effect between Pt and SnO₂, which enhanced the electrochemical catalytic activity. Besides, compared with the commercial carbon-supported Pt catalyst, the as-developed SnO₂@C/CP-supported Pt catalyst demonstrated better stability, most likely due to the positive interaction between SnO₂ and the carbon coating layer.Applied Science, Faculty ofNon UBCChemical and Biological Engineering, Department ofReviewedFacult

Cost-Effective Fabrication of Modified Palygorskite-Reinforced Rigid Polyurethane Foam Nanocomposites

Integration of nanoclay minerals into rigid polyurethane foams (RPUFs) is a cost-effective solution to enhance foam’s performance via environmental protection technology. In this work, palygorskite/RPUFs nanocomposites (Pal/RPUFNs) with excellent mechanical properties and thermal stability were prepared via a one-step method, using 4,4’-diphenylmethane diisocyanate and polyether polyol as the starting materials, coupled with Pal modified by silane coupling agent KH570. The effects of the modified Pal on the mechanics, morphology, and thermal properties of the nanocomposites were studied systematically. When the content of the modified Pal was 8 wt% of polyether polyol, the elastic modulus and compressive strength of the Pal/RPUFNs were increased by ca. 131% and 97%, respectively. The scanning electron microscopy images indicated that the addition of the modified Pal significantly decreased the cell diameter of the Pal/RPUFNs. The results of thermogravimetric and derivative thermogravimetry analyses revealed that the addition of the modified Pal increased the thermal weight loss central temperature of the Pal/RPUFNs, showing better thermal stability in comparison with the pure RPUFs. A self-made evaluation device was used to estimate the thermal insulation ability of the Pal/RPUFNs. It was found that the small cell size and uniform cellular structure were keys to improving the thermal insulation performance of the RPUFs. The prepared Pal/RPUFNs are expected to have great potential in the field of building insulation.Applied Science, Faculty ofNon UBCChemical and Biological Engineering, Department ofReviewedFacultyResearche

Preparation and Performance Study of the Anodic Catalyst Layer via Doctor Blade Coating for PEM Water Electrolysis

The membrane electrode assembly (MEA) is the core component of proton exchange membrane (PEM) water electrolysis cell, which provides a place for water decomposition to generate hydrogen and oxygen. The microstructure, thickness, IrO2 loading as well as the uniformity and quality of the anodic catalyst layer (ACL) have great influence on the performance of PEM water electrolysis cell. Aiming at providing an effective and low-cost fabrication method for MEA, the purpose of this work is to optimize the catalyst ink formulation and achieve the ink properties required to form an adherent and continuous layer with doctor blade coating method. The ink formulation (e.g., isopropanol/H2O of solvents and solids content) were adjusted, and the doctor blade thickness was optimized. The porous structure and the thickness of the doctor blade coating ACL were further confirmed with the in-plane and the cross-sectional SEM analyses. Finally, the effect of the ink formulation and the doctor blade thickness of the ACL on the cell performance were characterized in a PEM electrolyzer under ambient pressure at 80 °C. Overall, the optimized doctor blade coating ACL showed comparable performance to that prepared with the spraying method. It is proved that the doctor blade coating is capable of high-uniformity coating