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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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          A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles.

          The efficiency of many energy storage technologies, such as rechargeable metal-air batteries and hydrogen production from water splitting, is limited by the slow kinetics of the oxygen evolution reaction (OER). We found that Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ) (BSCF) catalyzes the OER with intrinsic activity that is at least an order of magnitude higher than that of the state-of-the-art iridium oxide catalyst in alkaline media. The high activity of BSCF was predicted from a design principle established by systematic examination of more than 10 transition metal oxides, which showed that the intrinsic OER activity exhibits a volcano-shaped dependence on the occupancy of the 3d electron with an e(g) symmetry of surface transition metal cations in an oxide. The peak OER activity was predicted to be at an e(g) occupancy close to unity, with high covalency of transition metal-oxygen bonds.
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            An advanced Ni-Fe layered double hydroxide electrocatalyst for water oxidation.

            Highly active, durable, and cost-effective electrocatalysts for water oxidation to evolve oxygen gas hold a key to a range of renewable energy solutions, including water-splitting and rechargeable metal-air batteries. Here, we report the synthesis of ultrathin nickel-iron layered double hydroxide (NiFe-LDH) nanoplates on mildly oxidized multiwalled carbon nanotubes (CNTs). Incorporation of Fe into the nickel hydroxide induced the formation of NiFe-LDH. The crystalline NiFe-LDH phase in nanoplate form is found to be highly active for oxygen evolution reaction in alkaline solutions. For NiFe-LDH grown on a network of CNTs, the resulting NiFe-LDH/CNT complex exhibits higher electrocatalytic activity and stability for oxygen evolution than commercial precious metal Ir catalysts.
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              Co3O4 Nanocrystals on Graphene as a Synergistic Catalyst for Oxygen Reduction Reaction

              Catalysts for oxygen reduction and evolution reactions are at the heart of key renewable energy technologies including fuel cells and water splitting. Despite tremendous efforts, developing oxygen electrode catalysts with high activity at low costs remains a grand challenge. Here, we report a hybrid material of Co3O4 nanocrystals grown on reduced graphene oxide (GO) as a high-performance bi-functional catalyst for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). While Co3O4 or graphene oxide alone has little catalytic activity, their hybrid exhibits an unexpected, surprisingly high ORR activity that is further enhanced by nitrogen-doping of graphene. The Co3O4/N-doped graphene hybrid exhibits similar catalytic activity but superior stability to Pt in alkaline solutions. The same hybrid is also highly active for OER, making it a high performance non-precious metal based bi-catalyst for both ORR and OER. The unusual catalytic activity arises from synergetic chemical coupling effects between Co3O4 and graphene.
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                Author and article information

                Journal
                EESNBY
                Energy & Environmental Science
                Energy Environ. Sci.
                Royal Society of Chemistry (RSC)
                1754-5692
                1754-5706
                2015
                2015
                : 8
                : 6
                : 1719-1724
                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
                Article
                10.1039/C5EE01290B
                f30eed18-6db4-4b12-85ea-30a6e9a4dba3
                © 2015
                History

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