Controllable synthesis of LiMnPO4 nanocrystals: Morphology evolution and their size-dependent electrochemical properties
Controllable synthesis of LiMnPO4 nanocrystals: Morphology evolution and their size-dependent electrochemical properties
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LiMnPO4 纳米晶体的可控合成：形态演化及其尺寸依赖性电化学性能
DOI：
10.1016/j.ceramint.2016.02.116
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发表时间：
2016-05
影响因子：
5.2
通讯作者：
Zhongtai Zhang
中科院分区：
文献类型：
--
作者：
Ye Hong;Zilong Tang;Wei Quan;Shitong Wang;Zhongtai Zhang
通过改变EG辅助溶剂热方法中的进料顺序和反应物比例，可控合成了八种具有可调形貌的典型LiMnPO4纳米晶体。研究发现，随着主要 LiOH/H3PO4 比率引起的 OH−浓度降低，LiMnPO4 的主要暴露平面从（010）（纳米纺锤体）演变为（100）（Li-P-Mn 补料序列中的纳米板），以及（010）和（100）（Mn-P-Li 补料序列中的纳米棒）。 OH-浓度的进一步降低几乎不影响纯相LiMnPO4的形成，但会导致形貌发生显着变化，颗粒尺寸明显增加。相应的 LiMnPO4/C 复合材料的电化学性能很大程度上取决于它们的粒径。通过应用 Mn-P-Li 序列和 2.7-3.0 的 LiOH/H3PO4 比例，所制备的 LiMnPO4/C 纳米棒在所有样品中表现出优异的倍率性能（10 C 下超过 105 mA h g−1）和显着的循环稳定性（0.5 C 下 100 次循环后容量保持率高达 93%），因为它们的长度小于沿 [010] 方向 60 nm。结果还证实，确实需要过量的 LiOH 才能产生具有小粒径和有吸引力的电化学性能的 LiMnPO4 晶体。
Eight typical LiMnPO4nanocrystals with tunable morphologies have been controllably synthesized by varying the feeding sequence and the ratio of the reactants in an EG-assisted solvothermal approach. It is found that with the decrease of the OH−concentration induced by the primary LiOH/H3PO4ratio, the predominately exposed planes of LiMnPO4evolve from (010) for nanospindles to (100) for nanoplates in Li–P–Mn feeding sequence, and to both (010) and (100) for nanorods in Mn–P–Li feeding sequence. Further decrease of the OH−concentration hardly affects the formation of pure-phase LiMnPO4but results in significant changes in the morphology with distinctly increased particle size. The electrochemical properties of the corresponding LiMnPO4/C composites are remarkably dependent on their particle size. By applying the Mn–P–Li sequence and the LiOH/H3PO4ratio of 2.7–3.0, the as-prepared LiMnPO4/C nanorods exhibit superior rate capability (more than 105 mA h g−1at 10 C) and remarkable cycling stability (a capacity retention of up to 93% after 100 cycles at 0.5 C) among all the samples, owing to their small length of less than 60 nm along the [010] direction. The results also confirm that excess LiOH amount is indeed required to yield LiMnPO4crystals with small particle size and attractive electrochemical properties.
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