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Lithium Insertion into Li2MoO4: Reversible Formation of (Li3Mo)O4 with a Disordered Rock-Salt Structure
Chemistry of Materials ( IF 7.2 ) Pub Date : 2015-06-10 00:00:00 , DOI: 10.1021/acs.chemmater.5b01633 D. Mikhailova 1, 2, 3 , A. Voss 2 , S. Oswald 2 , A. A. Tsirlin 4 , M. Schmidt 3 , A. Senyshyn 5 , J. Eckert 2, 6 , H. Ehrenberg 1
Chemistry of Materials ( IF 7.2 ) Pub Date : 2015-06-10 00:00:00 , DOI: 10.1021/acs.chemmater.5b01633 D. Mikhailova 1, 2, 3 , A. Voss 2 , S. Oswald 2 , A. A. Tsirlin 4 , M. Schmidt 3 , A. Senyshyn 5 , J. Eckert 2, 6 , H. Ehrenberg 1
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During Li-insertion in some complex transition metal molybdates with a NASICON structure, which serve as cathodes in Li-ion rechargeable cells, a formation of a cubic rock-salt-type phase was often detected between 1 and 2 V vs Li+/Li. Detailed information about elemental composition and stability of this compound was missing, and suggestions were made toward a solid solution composed of lithium oxide and two-valence transition metal oxide MO with M a 3d element. In the present work, we showed that Li2MoO4 with a phenacite-type structure without any additional transition metal can reversibly accommodate Li-ions at room temperature with the formation of the NaCl-type compound. Reversible Li-incorporation into the Li2MoO4 structure is accompanied by a reduction of Mo ions and changes in their oxygen coordination. Li-ions are shifted from a tetrahedral to an octahedral site, resulting in the formation of a cubic (Li3Mo)O4 framework with a random distribution of Li and Mo on one site. This mixed occupancy is remarkable because of significant charge and size differences between Li+ and Mo5+. The novel compound shows Li-deficiency at least up to xLi = 0.2, which can be deduced from charge flow in the galvanostatic cycling of the electrochemical cells with a (Li3Mo)O4 cathode between 1.5 and 2.75 V vs Li+/Li. An increase in the cell potential above 3 V leads to the oxidation of (Li3Mo)O4 back to Li2MoO4 with phenacite-type structure. The reaction of (Li3Mo)O4 to Li2MoO4 also occurs upon a short exposure to air.
中文翻译：
锂插入Li 2 MoO 4：具有无序岩石盐结构的（Li 3 Mo）O 4的可逆形成
在具有NASICON结构的某些复杂的过渡金属钼酸盐中插入锂时，锂离子可充电电池中用作阴极，通常在1-2 V vs. Li + / Li之间检测到立方岩盐型相的形成。。缺少有关该化合物的元素组成和稳定性的详细信息，并提出了由氧化锂和具有M a 3d元素的二价过渡金属氧化物MO组成的固溶体的建议。在目前的工作中，我们显示了具有方铅石型结构且没有任何其他过渡金属的Li 2 MoO 4可以在室温下可逆地容纳锂离子，并形成NaCl型化合物。可逆Li掺入Li 2 MoO 4中其结构伴随着Mo离子的减少和其氧配位的变化。锂离子从四面体位置转移到八面体位置，导致形成立方（Li 3 Mo）O 4构架，其中Li和Mo随机分布在一个位置上。由于Li +和Mo 5+之间的显着电荷和尺寸差异，这种混合占用非常显着。该新型化合物显示出的Li缺陷至少不超过x Li = 0.2，这可以从具有1.5至2.75 V vs（Li +）的（Li 3 Mo）O 4阴极的电化学电池的恒电流循环中的电荷流推导出来。/李 高于3V的电池电势的增加导致（Li 3 Mo）O 4氧化回到具有方铅矿型结构的Li 2 MoO 4。（Li 3 Mo）O 4与Li 2 MoO 4的反应也发生在短暂暴露于空气中时。
更新日期：2015-06-10
中文翻译：
锂插入Li 2 MoO 4：具有无序岩石盐结构的（Li 3 Mo）O 4的可逆形成
在具有NASICON结构的某些复杂的过渡金属钼酸盐中插入锂时，锂离子可充电电池中用作阴极，通常在1-2 V vs. Li + / Li之间检测到立方岩盐型相的形成。。缺少有关该化合物的元素组成和稳定性的详细信息，并提出了由氧化锂和具有M a 3d元素的二价过渡金属氧化物MO组成的固溶体的建议。在目前的工作中，我们显示了具有方铅石型结构且没有任何其他过渡金属的Li 2 MoO 4可以在室温下可逆地容纳锂离子，并形成NaCl型化合物。可逆Li掺入Li 2 MoO 4中其结构伴随着Mo离子的减少和其氧配位的变化。锂离子从四面体位置转移到八面体位置，导致形成立方（Li 3 Mo）O 4构架，其中Li和Mo随机分布在一个位置上。由于Li +和Mo 5+之间的显着电荷和尺寸差异，这种混合占用非常显着。该新型化合物显示出的Li缺陷至少不超过x Li = 0.2，这可以从具有1.5至2.75 V vs（Li +）的（Li 3 Mo）O 4阴极的电化学电池的恒电流循环中的电荷流推导出来。/李 高于3V的电池电势的增加导致（Li 3 Mo）O 4氧化回到具有方铅矿型结构的Li 2 MoO 4。（Li 3 Mo）O 4与Li 2 MoO 4的反应也发生在短暂暴露于空气中时。
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