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Review Article Chem Soc Rev Fig. 30 (a) TEM images of pristine, sodiated, and desodiated states of SnO2 nanowire. (b) STEM Z-contrast image showing the reaction front of the SnO2 nanowire (left) and schematic drawing showing the morphology evolution of the SnO2 nanowire upon Na insertion and extraction (right). (Reproduced with permission from ref. 383, Copyright 2013 American Chemical Society.) (c) Ex situ XRD profiles of SnO (top) and SnO2/C (bottom) electrodes over the first charge/discharge cycle. (d) Cycle life of SnO, SnO2, and SnO2/C electrodes. (Reprinted from ref. 386, Copyright 2015, with permission from Elsevier.) (e) Cycling performance of SnO2/NG and SnO2/G composites at a current density of 20 mA g1. (Reproduced with permission from ref. 390, Copyright 2015 The Royal Society of Chemistry.) (f) Cycling performance of the binder-free CuO nanorod array (CAN) electrode at a high current density of 200 mA g1. (Reproduced from ref. 392 with permission, Copyright 2014 Wiley-VCH Verlag GmbH & Co. KGaA.) (g) In situ observation of the sodiation process in CuO nanowires using TEM. (Reproduced with permission from ref. 394, Copyright 2015 The Royal Society of Chemistry.) View Article Online SnO showed better electrochemical performances, which implies that the Sn : O ratio and the respective Sn : Na2O ratio in the converted electrode play important roles in delivering the capacity (Fig. 30d). Recently, a strategy to overcome such failures and maximize the utilization of the high theoretical capacity of SnO2 (B782 mA h g1) has been introduced such as composite anodes with porous carbon, MWCNTs, and graphene.384–390 Xie et al. synthesized SnO2 with nitrogen-doped graphene nanohybrids via an in situ hydrothermal method and this composite anode delivered an initial reversible capacity of 339 mA h g1 at 20 mA g1 and excellent capacity retentions even at a high current density of 640 mA g1 390 (Fig. 30e). 3.2.1.4. Copper oxide. Copper-based oxide materials have also been proposed due to the Earth’s abundant distribution, chemical stability, and high theoretical capacity.391–396 Klein et al. reported that Cu2O can be applicable and thereby exhibited a high capacity of B600 mA h g1 at 0.1C.243 Yuan et al. proposed flexible and porous CuO nanorod arrays by engraving Cu foils. The arrays delivered a high specific capacity of 640 mA h g1 at 20 mA g1 and good cycle retentions over 400 cycles392 (Fig. 30f). Liu et al. demonstrated the morphology change and phase transforma- tions in CuO nanowires during the sodiation process. And, based on the in situ TEM results, Liu et al. suggested detailed conversion mechanisms as follows: 2CuO + 2Na+ + 2e - Cu2O + Na2O, Cu2O + Na2O - NaCuO, 7NaCuO + Na+ + 2e - Na6Cu2O6 + Na2O + 5Cu394 (Fig. 30g). However, similar to the other metal oxides, Cu-based oxides are still hindered by a large volume change during cycling. Recently, to enhance the electronic conductivity and the accommodation of volume variation upon cycling, Lu et al. proposed the micro-nanostructured CuO/C spheres. The as-prepared CuO/C spheres exhibited a high capacity of 402 mA h g1 after 600 cycles at a current density of 200 mA g1 and superior rate capabilities.395 3.2.2 Transition metal sulfide (TMS) based anode materials. Transition metal sulfide (TMS) materials have attracted tremen- dous attention as promising sodium storage materials with high theoretical capacity through electrochemical conversion reactions as well as use of transition metal oxides. In addition, compared to related transition metal oxides, transition metal 3574 | Chem. Soc. Rev., 2017, 46, 3529--3614 This journal is © The Royal Society of Chemistry 2017 Open Access Article. Published on 28 March 2017. Downloaded on 7/1/2019 3:41:21 AM. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.PDF Image | Sodium-ion batteries present and future
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