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One-Step Catalytic Synthesis of CuO/CuO in Graphitized Porous Carbon Matrix Derived from the Cu-based Metal-Organic Framework for Li- and Na-Ion Batteries A-Young Kim, Min Kyu Kim, Keumnam Cho, Jae-Young Woo, Yongho Lee, Sung-Hwan Han, Dongjin Byun, Wonchang Choi, and Joong Kee Lee ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b05973 • Publication Date (Web): 11 Jul 2016 Downloaded from http://pubs.acs.org on July 12, 2016
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One-Step Catalytic Synthesis of CuO/Cu2O in Graphitized Porous Carbon Matrix Derived from the Cu-based Metal-Organic Framework for Liand Na-Ion Batteries A-Young Kim†,§,‡, Min Kyu Kim†,∥,‡, Keumnam Cho⊥, Jae-Young Woo†, Yongho Lee†, SungHwan Han⊥, Dongjin Byun§, Wonchang Choi†, and Joong Kee Lee*,† †
Center for Energy Convergence Research, Korea Institute of Science and Technology,
Hwarang-ro 14-gil 5, Seongbuk-gu, Seoul 02792, Republic of Korea §
Department of Material Science and Engineering, Korea University, Anam dong 5 ga,
Seongbuk-gu, Seoul 02841, Republic of Korea ∥
Department of Chemical and Biochemical Engineering, Dongguk University, Phil dong 3-
26, Joong-gu, Seoul 04620, Republic of Korea ⊥
Department of Chemisty, Hanyang University, Haegdang-dong 17, Sungdong-ku, Seoul
04763, Republic of Korea *Corresponding author. Tel.:+82 2 958 5252; Fax: +82 2 958 5229; E-mail address:
[email protected] ‡
These authors contributed equally to this article. 1 ACS Paragon Plus Environment
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ABSTRACT: The hybrid composite electrode comprising CuO and Cu2O micronanoparticles in highly graphitized porous carbon matrix (CuO/Cu2O-GPC) has a rational design and is a favorable approach to increase the rate capability and reversible capacity of metal oxide negative materials for Li-ion and Na-ion batteries. The CuO/Cu2O-GPC is synthesized through a Cu-based metal–organic framework via a one-step thermal transformation process. The electrochemical performances of the CuO/Cu2O-GPC negative electrode in Li- and Na-ion batteries are systematically studied, and exhibit excellent capacities of 887.3 mAh g−1 at 60 mA g−1 after 200 cycles in Li-ion battery and 302.9 mAh g−1 at 50 mA g−1 after 200 cycles in Na-ion battery. The high electrochemical stability was obtained via the rational strategy, mainly owing to the synergy effect of the CuO and Cu2O micro-nanoparticles and highly graphitized porous carbon formed by catalytic graphitization of Cu nanoparticles. Owing to the simple one-step thermal transformation process and the resultant high electrochemical performance, the CuO/Cu2O-GPC is one of the prospective negative active materials for rechargeable Li- and Na-ion batteries.
KEYWORDS: one-step catalytic graphitization process, metal-organic framework, copper oxide, lithium-ion secondary battery, graphitized porous carbon, sodium-ion secondary battery
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1. INTRODUCTION In light of the increasing energy demand of various flexible electronics, electricand hybrid-electric vehicles, the improvement of the electrochemical performance of Li-ion secondary batteries have paid close attention as essential energy storage sources.1-3 However, Li resources are limited and are locally distributed globally, which may increase the cost of Li in the near future.4 Na-ion batteries with natural abundance, low-cost of Na, and similarities in the chemistry of Li and Na have attracted significant attention as replacements to Li-ion batteries because of natural abundance, low-cost of Na, and similarities in the chemistry of Li and Na.5-8 Unfortunately, the ionic radius (0.116 nm) and molar mass (22.989 g mol−1) of Na+ ions are larger than those (0.09 nm and 6.941 g mol−1, respectively) of Li+ ions, leading to greater volume and lower specific capacity for Na-ion batteries than for Liion batteries.9 Therefore, to accommodate both Na+ and Li+ ions and to enable reversible insertion/extraction reactions, many researchers have investigated appropriate anode materials for Na-ion batteries.10 Copper oxides, such as CuO and Cu2O, are intriguing owing to abundance, high theoretical capacity, low-cost, safety, and chemical stability.11 However, CuO-based electrode materials meet with large volume change during the conversion and low electrical conductivity; this causes electrode pulverization, leading to rapid capacity fading and decreased cycling stability.12 To address these drawbacks, a lot of researches have been focused on alleviating the volume change through use of various nano-materials and enhancing electrical conductivity through use of carbon coated electrode. To date, various CuO nanostructures, such as porous nanowires,13 three-dimensional nanosheets,14 micronanoparticles,15 and nanoleaves,16 have been fabricated as negative active materials for Li- and Na-ion batteries. These nanostructures can improve the electrochemical 3 ACS Paragon Plus Environment
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performances of the CuO anodes in Li- and Na-ion batteries. However, the rational design and syntheses of porous structures remains a challenge. Metal–organic frameworks (MOFs) materials have been paid significant attention for various applications in catalysis and chemical sensor because of their high porosities, large surface areas, and chemical tunabilities.17,18 Recently, many groups have demonstrated that CuO electrodes with hollow and/or porous structures synthesized from various MOFs enhance the electrochemical performances of Li- and Na-ion batteries. For Liion batteries, Banerjee et al. reported that a CuO nanostructure derived from a MOF showed 495 mAh g−1 at 100 mA g−1 after 40 cycles.19 Wu et al. explained that a porous MOF-derived CuO hollow octahedron reported 470 mAh g−1 at 100 mA g−1 after 100 cycles,20 and Hu et al. demonstrated that CuO/Cu2O composite hollow polyhedron derived from a MOF exhibited 740 mAh g−1 at 100 mA g−1 after 250 cycles.21 For Na-ion batteries, Zhang et al. demonstrated that a porous MOF-derived CuO/Cu2O hollow composite showed capacity of 415 mAh g−1 at 50 mA g−1 after 50 cycles.22 However, these anode materials do not satisfy the commercial requirements for high rate capability and cycle stability. To improve the electrochemical performances further, a carbon-based matrix can be used to decrease the electrode pulverization and increase the electrical conductivity, leading to increased rate capability with the electrochemical stability. Recently, Zhou et al. reported that a CuO/Cu2O nanosphere/graphene as an negative material for Li-ion battery provides good cycling performance and rate capability.23 Lu et al. demonstrated that micronanostructured CuO/C spheres exhibited similar electrochemical performance as an Na-ion battery anode.24 In the carbon composite materials, it is important that the carbon structure influences electrochemical performances of composite material rather than the carbon content.25 The high degree of graphitization is related to the high 4 ACS Paragon Plus Environment
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electronic conductivity, which lead to enhance the electron transfer rate.26 Su et al. reported that highly graphitized carbons could be obtained from MOF-derived carbon due to the catalytic graphitization of metal nanoparticles formed during the pyrolysis of MOFs.27 This process should carry out under relative low temperature (
