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首页> 外文期刊>Chemistry: A European journal >Clewlike ZnV_2O_4Hollow Spheres: Nonaqueous Sol-Gel Synthesis,Formation Mechanism, and Lithium Storage Properties
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Clewlike ZnV_2O_4Hollow Spheres: Nonaqueous Sol-Gel Synthesis,Formation Mechanism, and Lithium Storage Properties

机译：团状ZnV_2O_4空心球：非水溶胶-凝胶合成，形成机理及储锂性能

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摘要

Hollow ZnV_2O_4micro-spheres with a clewlike feature weresynthesized by reacting zinc nitratehexahydrate and ammonium metavana-date in benzyl alcohol at 180°C for thefirst time. GC–MS analysis revealedthat the organic reactions that occurredin this study were rather different fromthose in benzyl alcohol based nonaqu-eous sol–gel systems with metal alkox-ides, acetylacetonates, and acetates asthe precursors. Time-dependent experi-ments revealed that the growth mecha-nism of the clewlike ZnV2O4 hollowmicrospheres might involve a uniquemultistep pathway. First, the generationand self-assembly of ZnO nanosheetsinto metastable hierarchical micro-spheres as well as the generation of VO2 particles took place quickly. Then,clewlike ZnV2O4 hollow spheres weregradually produced by means of a re-peating reaction–dissolution (RD) pro-cess. In this process, the outside ZnOnanosheets of hierarchical micro-spheres would first react with neighbor-ing vanadium ions and benzyl alcoholand also serve as the secondary nuclea-tion sites for the subsequently formedZnV_2O_4nanocrystals. With the reactionproceeding, the interior ZnO woulddissolve and then spontaneously diffuseoutwards to nucleate as ZnO nanocrys-tals on the preformed ZnV_2O_4nano-wires. These renascent ZnO nanocrys-tals would further react with VO_2andbenzyl alcohol, ultimately resulting inthe final formation of a hollow spatialstructure. The lithium storage ability ofclewlike ZnV_2O_4hollow microsphereswas studied. When cycled at 50 mA in the voltage range of 0.01-3 V, thispeculiarly structured ZnV_2O_4electrodedelivered an initial reversible capacityof 548 mAh and exhibited almoststable cycling performance to maintaina capacity of 524 mAh g~(-1)over 50cycles. This attractive lithium storageperformance suggests that the resultingclewlike ZnV_2O_4hollow spheres arepromising for lithium-ion batteries.
机译：硝酸锌六水合锌与偏钒酸铵在苄醇中于180℃反应，合成了具有团状特征的空心ZnV_2O_4微球。 GC-MS分析表明，该研究中发生的有机反应与以金属烷氧基化物，乙酰丙酮化物和乙酸盐为前体的基于苯甲醇的非水溶胶-凝胶体系中的有机反应完全不同。随时间变化的实验表明，线状ZnV2O4空心微球的生长机理可能涉及独特的多步路径。首先，ZnO纳米片材的生成和自组装成亚稳态的分层微球以及VO2粒子的生成很快。然后，通过重复反应-溶解（RD）过程，逐渐产生了类似cle状的ZnV2O4空心球。在此过程中，分层微球的外部Znanoanosheets将首先与相邻的钒离子和苯甲醇反应，并且还充当随后形成的ZnV_2O_4纳米晶体的次级核化位点。随着反应的进行，内部的ZnO会溶解，然后自发向外扩散，并在预先形成的ZnV_2O_4纳米线上以ZnO纳米晶的形式成核。这些新生的ZnO纳米晶体将进一步与VO_2和苯甲醇反应，最终导致最终形成中空的空间结构。研究了类ZnV_2O_4空心微球的储锂能力。当在0.01-3 V的电压范围内以50 mA的电流循环时，这种特殊结构的ZnV_2O_4电极可提供548 mAh的初始可逆容量，并在50个循环中表现出几乎稳定的循环性能，以维持524 mAh g〜（-1）的容量。这种吸引人的锂存储性能表明，所得的类似类ZnV_2O_4空心球有望用于锂离子电池。

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