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      Fabrication of (Co,Mn) 3O 4/rGO Composite for Lithium Ion Battery Anode by a One-Step Hydrothermal Process with H 2O 2 as Additive

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          Abstract

          Binary transition metal oxides have been regarded as one of the most promising candidates for high-performance electrodes in energy storage devices, since they can offer high electrochemical activity and high capacity. Rational designing nanosized metal oxide/carbon composite architectures has been proven to be an effective way to improve the electrochemical performance. In this work, the (Co,Mn) 3O 4 spinel was synthesized and anchored on reduced graphene oxide (rGO) nanosheets using a facile and single hydrothermal step with H 2O 2 as additive, no further additional calcination required. Analysis showed that this method gives a mixed spinel, i.e. (Co,Mn) 3O 4, having 2 + and 3 + Co and Mn ions in both the octahedral and tetrahedral sites of the spinel structure, with a nanocubic morphology roughly 20 nm in size. The nanocubes are bound onto the rGO nanosheet uniformly in a single hydrothermal process, then the as-prepared (Co,Mn) 3O 4/rGO composite was characterized as the anode materials for Li-ion battery (LIB). It can deliver 1130.6 mAh g -1 at current density of 100 mA g -1 with 98% of coulombic efficiency after 140 cycles. At 1000 mA g -1, the capacity can still maintain 750 mAh g -1, demonstrating excellent rate capabilities. Therefore, the one-step process is a facile and promising method to fabricate metal oxide/rGO composite materials for energy storage applications.

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          Mn3O4-graphene hybrid as a high-capacity anode material for lithium ion batteries.

          We developed two-step solution-phase reactions to form hybrid materials of Mn(3)O(4) nanoparticles on reduced graphene oxide (RGO) sheets for lithium ion battery applications. Selective growth of Mn(3)O(4) nanoparticles on RGO sheets, in contrast to free particle growth in solution, allowed for the electrically insulating Mn(3)O(4) nanoparticles to be wired up to a current collector through the underlying conducting graphene network. The Mn(3)O(4) nanoparticles formed on RGO show a high specific capacity up to ∼900 mAh/g, near their theoretical capacity, with good rate capability and cycling stability, owing to the intimate interactions between the graphene substrates and the Mn(3)O(4) nanoparticles grown atop. The Mn(3)O(4)/RGO hybrid could be a promising candidate material for a high-capacity, low-cost, and environmentally friendly anode for lithium ion batteries. Our growth-on-graphene approach should offer a new technique for the design and synthesis of battery electrodes based on highly insulating materials.
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            Graphene and graphene-based materials for energy storage applications.

            With the increased demand in energy resources, great efforts have been devoted to developing advanced energy storage and conversion systems. Graphene and graphene-based materials have attracted great attention owing to their unique properties of high mechanical flexibility, large surface area, chemical stability, superior electric and thermal conductivities that render them great choices as alternative electrode materials for electrochemical energy storage systems. This Review summarizes the recent progress in graphene and graphene-based materials for four energy storage systems, i.e., lithium-ion batteries, supercapacitors, lithium-sulfur batteries and lithium-air batteries. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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              Preparation of nitrogen-doped graphene sheets by a combined chemical and hydrothermal reduction of graphene oxide.

              Nitrogen-doped graphene sheets were prepared through a hydrothermal reduction of colloidal dispersions of graphite oxide in the presence of hydrazine and ammonia at pH of 10. The effect of hydrothermal temperature on the structure, morphology, and surface chemistry of as-prepared graphene sheets were investigated though XRD, N(2) adsorption, solid-state (13)C NMR, SEM, TEM, and XPS characterizations. Oxygen reduction and nitrogen doping were achieved simultaneously under the hydrothermal reaction. Up to 5% nitrogen-doped graphene sheets with slightly wrinkled and folded feature were obtained at the relative low hydrothermal temperature. With the increase of hydrothermal temperature, the nitrogen content decreased slightly and more pyridinic N incorporated into the graphene network. Meanwhile, a jellyfish-like graphene structure was formed by self-organization of graphene sheets at the hydrothermal temperature of 160 °C. Further increase of the temperature to 200 °C, graphene sheets could self-aggregate into agglomerate particles but still contained doping level of 4 wt % N. The unique hydrothermal environment should play an important role in the nitrogen doping and the jellyfish-like graphene formation. This simple hydrothermal method could provide the synthesis of nitrogen-doped graphene sheets in large scale for various practical applications.
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                Author and article information

                Contributors
                Role: Editor
                Journal
                PLoS One
                PLoS ONE
                plos
                plosone
                PLoS ONE
                Public Library of Science (San Francisco, CA USA )
                1932-6203
                27 October 2016
                2016
                : 11
                : 10
                : e0164657
                Affiliations
                [1 ]School of Civil and Environmental Engineering, Harbin Institute of Technology Shenzhen Graduate School, Shenzhen, China
                [2 ]IoT Application Technology Center of NDT, Shenzhen Graduate School, Harbin Institute of Technology, Shenzhen, China
                [3 ]School of Materials Science and Engineering, Harbin Institute of Technology Shenzhen Graduate School, Shenzhen Key Laboratory of Advanced Materials, Shenzhen, China
                Beihang University, CHINA
                Author notes

                Competing Interests: The authors have declared that no competing interests exist.

                • Conceptualization: JC.

                • Data curation: JC LD.

                • Formal analysis: ZL YC JC LD.

                • Funding acquisition: ZL JW.

                • Investigation: ZL YC JC LD.

                • Methodology: ZL YC JC.

                • Project administration: ZL JW.

                • Supervision: JW.

                • Writing – original draft: ZL YC JC.

                • Writing – review & editing: JW.

                Article
                PONE-D-16-26510
                10.1371/journal.pone.0164657
                5082892
                27788161
                47b74e4a-dfa5-4cbb-b3f3-ee1d8aad4e9d
                © 2016 Li et al

                This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

                History
                : 2 July 2016
                : 28 September 2016
                Page count
                Figures: 4, Tables: 1, Pages: 11
                Funding
                Funded by: Shenzhen Peacock Plan Program
                Award ID: KQCX20140521144358003
                Award Recipient :
                Funded by: Fundamental Research Program of Shenzhen
                Award ID: JCYJ20140417172417144
                Award Recipient :
                Funded by: International Collaboration Program of Shenzhen
                Award ID: GJHZ20150312114008636
                Award Recipient :
                Funded by: Shenzhen Technology Innovation Program—Technology Development Projects
                Award ID: CXZZ20140904154839135
                Award Recipient :
                The work was supported by Shenzhen Peacock Plan Program (KQCX20140521144358003), Fundamental Research Program of Shenzhen (JCYJ20140417172417144), International Collaboration Program of Shenzhen (GJHZ20150312114008636), and Innovative group for high-performance lithium-ion power batteries R&D and industrialization of Guangdong Province (Grant No. 2013N079), Shenzhen Technology Innovation Program—Technology Development Projects (Grant No. CXZZ20140904154839135).
                Categories
                Research Article
                Physical Sciences
                Materials Science
                Materials by Attribute
                Nanomaterials
                Engineering and Technology
                Nanotechnology
                Nanomaterials
                Physical Sciences
                Materials Science
                Materials by Structure
                Composite Materials
                Engineering and Technology
                Electronics
                Electrodes
                Anodes
                Physical Sciences
                Chemistry
                Chemical Elements
                Lithium
                Physical Sciences
                Chemistry
                Electrochemistry
                Engineering and Technology
                Manufacturing Processes
                Heat Treatment
                Research and Analysis Methods
                Spectrum Analysis Techniques
                Electron Beam Spectrum Analysis Techniques
                X-Ray Photoelectron Spectroscopy
                Engineering and Technology
                Nanotechnology
                Nanoparticles
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                All relevant data are within the paper and its Supporting Information files.

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