Preparation and evaluation of advanced electrocatalysts for phosphoric acid fuel cells

Results are presented for hydrogen oxidation and hydrogen oxidation poisoned by carbon monoxide at levels between 0 and 30%. Due to the high activities that are now being observed for our platinum based electrocatalysts, the hydrogen concentrations were reduced to 10% levels in the gas supplies. Perturbation techniques were used to determine that a mechanism for the efficient operation of our porous gas diffusion electrodes is diffusion of the carbon monoxide out of the electrode structure through the electrolyte film on the electro-catalyst. A survey of the literature on platinum group materials (PGM) was carried out so that an identification of successful electrocatalysts could be made. Two PGM electrocatalysts were prepared and performance data for hydrogen oxidation in hot phosphoric acid in the presence of high carbon monoxide concentrations showed that they matched the best platinum on carbon electrocatalysts but with an electrocatalyst cost that was half of the platinum catalyst cost

Preparation and evaluation of advanced electrocatalysts for phosphoric acid fuel cells

Two cooperative phenomena are required the development of highly efficient porous electrocatalysts: (1) is an increase in the electrocatalytic activity of the catalyst particle; and (2) is the availability of that electrocatalyst particle for the electromechanical reaction. The two processes interact with each other so that improvements in the electrochemical activity must be coupled with improvements in the availability of the electrocatalyst for reaction. Cost effective and highly reactive electrocatalysts were developed. The utilization of the electrocatalyst particles in the porous electrode structures was analyzed. It is shown that a large percentage of the electrocatalyst in anode structures is not utilized. This low utilization translates directly into a noble metal cost penalty for the fuel cell

????????? ??????????????? ?????? ??????????????? ?????? ???????????????

Department of Energy Engineering (Battery Science and Technology)The continuous throng in demand for high energy density rechargeable batteries innovatively drives technological development in cell design as well as electrochemically active materials. In that perspective metal-free batteries consisting of a flowing seawater as a cathode active material were introduced. However, the electrochemical performance of the seawater battery was restrained by NASICON (Na3Zr2Si2PO12) ceramic solid electrolyte. Here, we demonstrate a new class of fibrous nanomat hard-carbon (FNHC) anode/1D (one-dimensional) bucky paper (1DBP) cathode hybrid electrode architecture in seawater battery based on 1D building block-interweaved hetero-nanomat frameworks. Differently from conventional slurry-cast electrodes, exquisitely designed hybrid hetero-nanomat electrodes are fabricated through concurrent dual electrospraying and electrospinning for the anode, vacuum-assisted infiltration for the cathode. HC nanoparticles are closely embedded in the spatially reinforced polymeric nanofiber/CNT hetero-nanomat skeletons that play a crucial role in constructing 3D-bicontinuous ion/electron transport pathways and allow to eliminate heavy metallic aluminum foil current collectors. Eventually the FNHC/1DBP seawater full cell, driven by aforementioned physicochemical uniqueness, shows exceptional improvement in electrochemical performance (Energy density = 693 Wh kg-1), (Power density = 3341 W kg-1) removing strong stereotype of ceramic solid electrolyte, which beyond those achievable with innovative next generation battery technologies.ope

Fabrication of bifunctional membrane electrode assemblies for unitised regenerative polymer electrolyte fuel cells

Bifunctional membrane electrode assemblies have been fabricated using a screen printing technique, which demonstrate a repeatable and stable operation to cell current and voltages. This approach lends itself to a rapid, low-cost and repeatable fabrication process for bifunctional catalytic electrodes in polymer electrolyte membrane fuel cells and electrolysers

Dynamic Potential-Ph Diagrams Application to Electrocatalysts for Water Oxidation

The construction and use of "dynamic potential-pH diagrams" (DPPDs), that are intended to extend the usefulness of thermodynamic Pourbaix diagrams to include kinetic considerations is described. As an example, DPPDs are presented for the comparison of electrocatalysts for water oxidation, i.e., the oxygen evolution reaction (OER), an important electrochemical reaction because of its key role in energy conversion devices and biological systems (water electrolyses, photoelectrochemical water splitting, plant photosynthesis). The criteria for obtaining kinetic data are discussed and a 3-D diagram, which shows the heterogeneous electron transfer kinetics of an electrochemical system as a function of pH and applied potential is presented. DPPDs are given for four catalysts: IrO(2), Co(3)O(4), Co(3)O(4) electrodeposited in a phosphate medium (Co-Pi) and Pt, allowing a direct comparison of the activity of different electrode materials over a broad range of experimental conditions (pH, potential, current density). In addition, the experimental setup and the factors affecting the accurate collection and presentation of data (e. g., reference electrode system, correction of ohmic drops, bubble formation) are discussed.Ministry of Education, University and Research PRIN 2008PF9TWZ, 2008N7CYL5Universita degli Studi di MilanoNational Science Foundation CHE-0808927Robert A. Welch Foundation F-0021Center for Electrochemistr

Designing materials for electrochemical carbon dioxide recycling

Electrochemical carbon dioxide recycling provides an attractive approach to synthesizing fuels and chemical feedstocks using renewable energy. On the path to deploying this technology, basic and applied scientific hurdles remain. Integrating catalytic design with mechanistic understanding yields scientific insights and progresses the technology towards industrial relevance. Catalysts must be able to generate valuable carbon-based products with better selectivity, lower overpotentials and improved current densities with extended operation. Here, we describe progress and identify mechanistic questions and performance metrics for catalysts that can enable carbon-neutral renewable energy storage and utilization

Electrooxidation of a cobalt based steel in LiOH: a non-noble metal based electro-catalyst suitable for durable water-splitting in an acidic milieu

The use of proton exchange membrane (PEM) electrolyzers is the method of choice for the conversion of solar energy when frequently occurring changes of the current load are an issue. However, this technique requires electrolytes with low pH. All oxygen evolving electrodes working durably and actively in acids contain IrOx. Due to their scarcity and high acquisition costs, noble elements like Pt, Ru and Ir need to be replaced by earth abundant elements. We have evaluated a cobalt containing steel for use as an oxygen-forming electrode in H2SO4. We found that the dissolving of ingredients out of the steel electrode at oxidative potential in sulfuric acid, which is a well-known, serious issue, can be substantially reduced when the steel is electro-oxidized in LiOH prior to electrocatalysis. Under optimized synthesis conditions a cobalt-containing tool steel was rendered into a durable oxygen evolution reaction (OER) electrocatalyst (weight loss: 39 mug mm-2 after 50 000 s of chronopotentiometry at pH 1) that exhibits overpotentials down to 574 mV at 10 mA cm-2 current density at pH 1. Focused ion beam SEM FIB-SEM) was successfully used to create a structure-stability relationship