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      Bifunctional Oxygen Electrocatalyst of Mesoporous Ni/NiO Nanosheets for Flexible Rechargeable Zn–Air Batteries

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          Highlights

          • An oxygen electrocatalyst consisting of Ni nanoparticles interpenetrated in porous NiO nanosheets was successfully synthesized.

          • The liquid Zn–air battery reveals a large open-circuit potential of 1.47 V, the maximum power density at 225 mW cm −2, and excellent device stability of over 120 h.

          • The flexible solid-like rechargeable Zn–air battery shows excellent stability (no evident weakening after 240 cycles) and bendability.

          Electronic supplementary material

          The online version of this article (10.1007/s40820-020-0406-6) contains supplementary material, which is available to authorized users.

          Abstract

          One approach to accelerate the stagnant kinetics of both the oxygen reduction and evolution reactions (ORR/OER) is to develop a rationally designed multiphase nanocomposite, where the functions arising from each of the constituent phases, their interfaces, and the overall structure are properly controlled. Herein, we successfully synthesized an oxygen electrocatalyst consisting of Ni nanoparticles purposely interpenetrated into mesoporous NiO nanosheets (porous Ni/NiO). Benefiting from the contributions of the Ni and NiO phases, the well-established pore channels for charge transport at the interface between the phases, and the enhanced conductivity due to oxygen-deficiency at the pore edges, the porous Ni/NiO nanosheets show a potential of 1.49 V (10 mA cm −2) for the OER and a half-wave potential of 0.76 V for the ORR, outperforming their noble metal counterparts. More significantly, a Zn–air battery employing the porous Ni/NiO nanosheets exhibits an initial charging–discharging voltage gap of 0.83 V (2 mA cm −2), specific capacity of 853 mAh g Zn −1 at 20 mA cm −2, and long-time cycling stability (120 h). In addition, the porous Ni/NiO-based solid-like Zn–air battery shows excellent electrochemical performance and flexibility, illustrating its great potential as a next-generation rechargeable power source for flexible electronics.

          Electronic supplementary material

          The online version of this article (10.1007/s40820-020-0406-6) contains supplementary material, which is available to authorized users.

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          Most cited references52

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          Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts.

          Nitrogen (N)-doped carbon materials exhibit high electrocatalytic activity for the oxygen reduction reaction (ORR), which is essential for several renewable energy systems. However, the ORR active site (or sites) is unclear, which retards further developments of high-performance catalysts. Here, we characterized the ORR active site by using newly designed graphite (highly oriented pyrolitic graphite) model catalysts with well-defined π conjugation and well-controlled doping of N species. The ORR active site is created by pyridinic N. Carbon dioxide adsorption experiments indicated that pyridinic N also creates Lewis basic sites. The specific activities per pyridinic N in the HOPG model catalysts are comparable with those of N-doped graphene powder catalysts. Thus, the ORR active sites in N-doped carbon materials are carbon atoms with Lewis basicity next to pyridinic N.
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            Nanoscale nickel oxide/nickel heterostructures for active hydrogen evolution electrocatalysis.

            Active, stable and cost-effective electrocatalysts are a key to water splitting for hydrogen production through electrolysis or photoelectrochemistry. Here we report nanoscale nickel oxide/nickel heterostructures formed on carbon nanotube sidewalls as highly effective electrocatalysts for hydrogen evolution reaction with activity similar to platinum. Partially reduced nickel interfaced with nickel oxide results from thermal decomposition of nickel hydroxide precursors bonded to carbon nanotube sidewalls. The metal ion-carbon nanotube interactions impede complete reduction and Ostwald ripening of nickel species into the less hydrogen evolution reaction active pure nickel phase. A water electrolyzer that achieves ~20 mA cm(-2) at a voltage of 1.5 V, and which may be operated by a single-cell alkaline battery, is fabricated using cheap, non-precious metal-based electrocatalysts.
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              Ultrathin Iron-Cobalt Oxide Nanosheets with Abundant Oxygen Vacancies for the Oxygen Evolution Reaction.

              Electrochemical water splitting is a promising method for storing light/electrical energy in the form of H2 fuel; however, it is limited by the sluggish anodic oxygen evolution reaction (OER). To improve the accessibility of H2 production, it is necessary to develop an efficient OER catalyst with large surface area, abundant active sites, and good stability, through a low-cost fabrication route. Herein, a facile solution reduction method using NaBH4 as a reductant is developed to prepare iron-cobalt oxide nanosheets (Fex Coy -ONSs) with a large specific surface area (up to 261.1 m(2) g(-1) ), ultrathin thickness (1.2 nm), and, importantly, abundant oxygen vacancies. The mass activity of Fe1 Co1 -ONS measured at an overpotential of 350 mV reaches up to 54.9 A g(-1) , while its Tafel slope is 36.8 mV dec(-1) ; both of which are superior to those of commercial RuO2 , crystalline Fe1 Co1 -ONP, and most reported OER catalysts. The excellent OER catalytic activity of Fe1 Co1 -ONS can be attributed to its specific structure, e.g., ultrathin nanosheets that could facilitate mass diffusion/transport of OH(-) ions and provide more active sites for OER catalysis, and oxygen vacancies that could improve electronic conductivity and facilitate adsorption of H2 O onto nearby Co(3+) sites.
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                Author and article information

                Contributors
                gaodq@lzu.edu.cn
                Journal
                Nanomicro Lett
                Nanomicro Lett
                Nano-Micro Letters
                Springer Singapore (Singapore )
                2311-6706
                2150-5551
                9 March 2020
                9 March 2020
                December 2020
                : 12
                : 68
                Affiliations
                [1 ]GRID grid.32566.34, ISNI 0000 0000 8571 0482, Key Laboratory for Magnetism and Magnetic Materials of MOE, Key Laboratory of Special Function Materials and Structure Design of MOE, , Lanzhou University, ; Lanzhou, 730000 People’s Republic of China
                [2 ]GRID grid.185448.4, ISNI 0000 0004 0637 0221, Institute of Chemical and Engineering Sciences, , A*STAR, ; 1 Pesek Road, Jurong Island, 627833 Singapore
                [3 ]GRID grid.4280.e, ISNI 0000 0001 2180 6431, Department of Material Science and Engineering, , National University of Singapore, ; Engineering Drive 3, Singapore, 117575 Singapore
                Article
                406
                10.1007/s40820-020-0406-6
                7770935
                f99d3cf6-37f6-42e5-ab61-c0b7c21b7f80
                © The Author(s) 2020

                Open AccessThis article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 6 December 2019
                : 4 February 2020
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                © The Author(s) 2020

                porous ni/nio,oxygen reduction reaction,oxygen evolution reaction,electrocatalysis,flexible zn–air battery

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