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      Simple synthesis of highly catalytic carbon-free MnCo 2O 4@Ni as an oxygen electrode for rechargeable Li–O 2 batteries with long-term stability

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          Abstract

          An effective integrated design with a free standing and carbon-free architecture of spinel MnCo 2O 4 oxide prepared using facile and cost effective hydrothermal method as the oxygen electrode for the Li–O 2 battery, is introduced to avoid the parasitic reactions of carbon and binder with discharge products and reaction intermediates, respectively. The highly porous structure of the electrode allows the electrolyte and oxygen to diffuse effectively into the catalytically active sites and hence improve the cell performance. The amorphous Li 2O 2 will then precipitate and decompose on the surface of free-standing catalyst nanorods. Electrochemical examination demonstrates that the free-standing electrode without carbon support gives the highest specific capacity and the minimum capacity fading among the rechargeable Li–O 2 batteries tested. The Li-O 2 cell has demonstrated a cyclability of 119 cycles while maintaining a moderate specific capacity of 1000 mAh g −1. Furthermore, the synergistic effect of the fast kinetics of electron transport provided by the free-standing structure and the high electro-catalytic activity of the spinel oxide enables excellent performance of the oxygen electrode for Li-O 2 cells.

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          An improved high-performance lithium-air battery.

          Although dominating the consumer electronics markets as the power source of choice for popular portable devices, the common lithium battery is not yet suited for use in sustainable electrified road transport. The development of advanced, higher-energy lithium batteries is essential in the rapid establishment of the electric car market. Owing to its exceptionally high energy potentiality, the lithium-air battery is a very appealing candidate for fulfilling this role. However, the performance of such batteries has been limited to only a few charge-discharge cycles with low rate capability. Here, by choosing a suitable stable electrolyte and appropriate cell design, we demonstrate a lithium-air battery capable of operating over many cycles with capacity and rate values as high as 5,000 mAh g(carbon)(-1) and 3 A g(carbon)(-1), respectively. For this battery we estimate an energy density value that is much higher than those offered by the currently available lithium-ion battery technology.
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            Covalent Hybrid of Spinel Manganese-Cobalt Oxide and Gra-phene as Advanced Oxygen Reduction Electrocatalysts

            Through direct nanoparticle nucleation and growth on nitrogen doped, reduced graphene oxide sheets and cation substitution of spinel Co3O4 nanoparticles, a manganese-cobalt spinel MnCo2O4/graphene hybrid was developed as a highly efficient electrocatalyst for oxygen reduction reaction (ORR) in alkaline conditions. Electrochemical and X-ray near edge structure (XANES) investigations revealed that the nucleation and growth method for forming inorganic-nanocarbon hybrid results in covalent coupling between spinel oxide nanoparticles and N-doped reduced graphene oxide (N-rmGO) sheets. Carbon K-edge and nitrogen K-edge XANES showed strongly perturbed C-O and C-N bonding in the N-rmGO sheet, suggesting the formation of C-O-metal and C-N-metal bonds between N-doped graphene oxide and spinel oxide nanoparticles. Co L-edge and Mn L-edge XANES suggested substitu-tion of Co3+ sites by Mn3+, which increased the activity of the catalytic sites in the hybrid materials, further boosting the ORR activity compared to the pure cobalt oxide hybrid. The covalently bonded hybrid afforded much greater activity and durability than the physi-cal mixture of nanoparticles and carbon materials including N-rmGO. At the same mass loading, the MnCo2O4/N-graphene hybrid can outperform Pt/C in ORR current density at medium overpotentials with superior stability to Pt/C in alkaline solutions.
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              Porous graphene nanoarchitectures: an efficient catalyst for low charge-overpotential, long life, and high capacity lithium-oxygen batteries.

              The electrochemical performance of lithium-oxygen (Li-O2) batteries awaits dramatic improvement in the design of porous cathode electrodes with sufficient spaces to accommodate the discharge products and discovery of effective cathode catalysts to promote both oxygen reduction reactions and oxygen evolution reactions. Herein, we report the synthesis of porous graphene with different pore size architectures as cathode catalysts for Li-O2 batteries. Porous graphene materials exhibited significantly higher discharge capacities than that of nonporous graphene. Furthermore, porous graphene with pore diameter around 250 nm showed the highest discharge capacity among the porous graphene with the small pores (about 60 nm) and large pores (about 400 nm). Moreover, we discovered that addition of ruthenium (Ru) nanocrystals to porous graphene promotes the oxygen evolution reaction. The Ru nanocrystal-decorated porous graphene exhibited an excellent catalytic activity as cathodes in Li-O2 batteries with a high reversible capacity of 17,700 mA h g(-1), a low charge/discharge overpotential (about 0.355 V), and a long cycle life up to 200 cycles (under the curtaining capacity of 1000 mAh g(-1)). The novel porous graphene architecture inspires the development of high-performance Li-O2 batteries.
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                Author and article information

                Journal
                Sci Rep
                Sci Rep
                Scientific Reports
                Nature Publishing Group
                2045-2322
                21 August 2015
                2015
                : 5
                : 13266
                Affiliations
                [1 ]Department of Material Science and Engineering, Chonnam National University , 77, Yongbongro, Bukgu, Gwangju 500-757, South Korea
                [2 ]Central Research Center, Doosan Heavy Industries & Construction Co., 22, Doosan volvoro, Seongsangu, Changwon 642-792, Gyeongsangnamdo, South Korea
                [3 ]Department of Chemical and Environmental Engineering, Yale University , New Haven, Connecticut 06520-8286, United States
                Author notes
                Article
                srep13266
                10.1038/srep13266
                4543937
                26292965
                46fab281-c1b7-4d3a-bd27-0c18141f884d
                Copyright © 2015, Macmillan Publishers Limited

                This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/

                History
                : 29 April 2015
                : 23 July 2015
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