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Electrochemical tuning of olivine-type lithium transition-metal phosphates as efficient water oxidation catalysts

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      Abstract

      Electrochemical lithium tuning of olivine-type lithium transition metal phosphates results in greatly enhanced oxygen evolution catalytic activity.

      Abstract

      The oxygen evolution reaction is of paramount importance in clean energy generation and storage. While the common approach in search of active, durable and cost-effective oxygen evolution catalysts involves the development of novel materials, it is equally important to tune the properties of existing materials so as to improve their catalytic performance. Here, we demonstrate the general efficacy of electrochemical lithium tuning in organic electrolyte on enhancing the oxygen evolution catalytic activity of olivine-type lithium transition metal phosphates, a widely-researched family of cathode materials in lithium ion batteries. By continuously extracting lithium ions out of lithium transition metal phosphates, the materials exhibited significantly enhanced water oxidation catalytic activity. Particularly, the electrochemically delithiated Li(Ni,Fe)PO 4 nanoparticles anchored on reduced graphene oxide sheets afforded outstanding performance, generating a current density of 10 mA cm −2 at an overpotential of only 0.27 V for over 24 h without degradation in 0.1 M KOH, outperforming the commercial precious metal Ir catalysts.

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      Most cited references 54

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      Nanostructured materials for advanced energy conversion and storage devices.

      New materials hold the key to fundamental advances in energy conversion and storage, both of which are vital in order to meet the challenge of global warming and the finite nature of fossil fuels. Nanomaterials in particular offer unique properties or combinations of properties as electrodes and electrolytes in a range of energy devices. This review describes some recent developments in the discovery of nanoelectrolytes and nanoelectrodes for lithium batteries, fuel cells and supercapacitors. The advantages and disadvantages of the nanoscale in materials design for such devices are highlighted.
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        In situ formation of an oxygen-evolving catalyst in neutral water containing phosphate and Co2+.

        The utilization of solar energy on a large scale requires its storage. In natural photosynthesis, energy from sunlight is used to rearrange the bonds of water to oxygen and hydrogen equivalents. The realization of artificial systems that perform "water splitting" requires catalysts that produce oxygen from water without the need for excessive driving potentials. Here we report such a catalyst that forms upon the oxidative polarization of an inert indium tin oxide electrode in phosphate-buffered water containing cobalt (II) ions. A variety of analytical techniques indicates the presence of phosphate in an approximate 1:2 ratio with cobalt in this material. The pH dependence of the catalytic activity also implicates the hydrogen phosphate ion as the proton acceptor in the oxygen-producing reaction. This catalyst not only forms in situ from earth-abundant materials but also operates in neutral water under ambient conditions.
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          Lithium batteries and cathode materials.

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            Author and article information

            Affiliations
            [1 ]Department of Materials Science and Engineering
            [2 ]Stanford University
            [3 ]Stanford
            [4 ]USA
            [5 ]Department of Applied Physics
            [6 ]Stanford Institute for Materials and Energy Sciences
            Journal
            EESNBY
            Energy & Environmental Science
            Energy Environ. Sci.
            Royal Society of Chemistry (RSC)
            1754-5692
            1754-5706
            2015
            2015
            : 8
            : 6
            : 1719-1724
            10.1039/C5EE01290B
            © 2015
            Product
            Self URI (article page): http://xlink.rsc.org/?DOI=C5EE01290B

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