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首页> 外文期刊>Crystal growth & design >Exceptional Flux Growth and Chemical Transformation of Metastable Orthorhombic LiMnO2 Cuboids into Hierarchically-Structured Porous H1.6Mn1.6O4 Rods as Li Ion Sieves
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Exceptional Flux Growth and Chemical Transformation of Metastable Orthorhombic LiMnO2 Cuboids into Hierarchically-Structured Porous H1.6Mn1.6O4 Rods as Li Ion Sieves

机译：亚稳态正交各向异性LiMnO2长方体向锂离子筛的分层结构多孔H1.6Mn1.6O4棒的异常通量增长和化学转化

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摘要

Selective lithium uptake from seawater and lake brine is an important challenge in energy and environmental science. H1.6Mn1.6O4 with pseudospinel-type structure is a highly selective adsorbent for Li ions, but it is difficult to prepare large, highly crystalline H1.6Mn1.6O4 crystals with porous structure due to its thermodynamic metastability. Herein we demonstrate simple chemical processes that transform flux-grown, idiomorphic orthorhombic LiMnO2 (o-LiMnO2) cuboids of micrometer size into hierarchically structured H1.6Mn1.6O4 rods. We have optimized the flux growth conditions such as the Mn source, holding temperature, and solute concentration in order to yield large, single-phase o-LiMnO2 particles. The use of MnO under very low solute concentration (1 mol %) and high temperature (1000 degrees C) is critical to obtaining the single-phase, idiomorphic o-LiMnO2 cuboids. The metastability of o-LiMnO2 is confirmed by ab initio density functional theory calculation in comparison with other lithium manganates such as LiMn2O4 and Li2MnO3. The successive calcination and acid treatment allow the transformation of o-LiMnO2 into H1.6Mn1.6O4 rods porous structure. The resultant H1.6Mn1.6O4 shows high Li+ adsorption capacity (similar to 5.6 mmol g(-1)), high Li+/Na+ selectivity, and good durability compared with existing H1.6Mn1.6O4 adsorbents.
机译：从海水和湖盐水中选择性吸收锂是能源和环境科学领域的重要挑战。具有假尖晶石型结构的H1.6Mn1.6O4是对Li离子的高选择性吸附剂，但由于其热力学亚稳定性，难以制备具有多孔结构的大型，高度结晶的H1.6Mn1.6O4晶体。在这里，我们演示了简单的化学过程，该过程将微米级的助熔剂生长的，同质的正交晶LiMnO2（o-LiMnO2）长方体转换为分层结构的H1.6Mn1.6O4棒。我们已经优化了助熔剂的生长条件，例如Mn的来源，保持温度和溶质的浓度，以便产生大的单相o-LiMnO2颗粒。在非常低的溶质浓度（1 mol％）和高温（1000摄氏度）下使用MnO对于获得单相，同构的o-LiMnO2长方体至关重要。通过从头算密度函数理论的计算与其他锰酸锂如LiMn2O4和Li2MnO3相比，证实了o-LiMnO2的亚稳定性。连续的煅烧和酸处理使邻-LiMnO2转变为H1.6Mn1.6O4棒多孔结构。与现有的H1.6Mn1.6O4吸附剂相比，所得的H1.6Mn1.6O4具有高的Li +吸附容量（类似于5.6 mmol g（-1）），高的Li + / Na +选择性和良好的耐久性。

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