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Heavy-Fermion Behavior and Electrochemistry of Li_(1.27)Mn_(1.73)O4

机译:Li_(1.27)Mn_(1.73)O4的重费米子行为与电化学

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摘要

The spinel of nominal composition Li4Mn5O_(12) has been prepared by the wet chemistry technique and characterized by structural analysis (X-ray diffractometry, Raman spectroscopy), magnetic properties including electron spin resonance (ESR), and thermal properties (specific heat). Both structural and magnetic analyses reveal that the physical and electrochemical properties are importantly influenced by the presence of Li2MnO3 impurity phase. The presence of this additional phase reduces the average oxidation state of manganese according to a disproportionation reaction so that the final composition of the spinel phase is Li_(3.8)Mn_(5.2)O_(12) (or Li_(1.27)Mn_(1.73)O4). Because of the important geometric frustration of the magnetic interactions and dilution of the antiferromagnetic interactions, no magnetic ordering is observed in the temperature range investigated. The anomalous magnetic properties, including the Dysonian profile of the ESR line, show that the material is metallic. The Sommerfeld constant is 308 mJ/(K2) per mole of Li1.27Mn1.73O4, which shows that this material belongs to the class of heavy-fermion systems like L1V2O4 or LiTi204. These heavy fermions are the minority-spin t_g↓ electrons of Mn~(3+) ions that have an reduced effective masse m/m_0 = 467. The electrochemical properties show that the specific capacity of Li_(3.8)Mn_(5.2)O_(12) at charge rate 1C is 163 mA h/g, a large value that is possibility due to the to insert Li up to the composition Li_(6.8)Mn_(5.2)O_(12). The origin of the disproportionation, and the flat voltage in the lithiation process, are discussed in the framework of the stability of the Mott insulator phase with respect to the metallic phase.
机译:标称成分的尖晶石Li4Mn5O_(12)采用湿化学技术制备,并通过结构分析(X射线衍射法、拉曼光谱)、包括电子自旋共振(ESR)在内的磁性、热性能(比热)进行了表征。结构和磁性分析均表明,Li2MnO3杂质相的存在对物理和电化学性能有重要影响。根据歧化反应,这种附加相的存在降低了锰的平均氧化态,因此尖晶石相的最终组成为Li_(3.8)Mn_(5.2)O_(12)(或Li_(1.27)Mn_(1.73)O4)。由于磁相互作用的重要几何挫折和反铁磁相互作用的稀释,在所研究的温度范围内没有观察到磁有序。异常的磁性,包括ESR线的Dysonian轮廓,表明该材料是金属的。索末菲常数为每摩尔Li308 Mn1.27Mn1.73O4的308 mJ / (K2),这表明该材料属于重费米子系统类,如L1V2O4或LiTi204。这些重费米子是 Mn~(3+) 离子的少数自旋 t_g↓ 电子,其有效质量降低 m/m_0 = 467。电化学性质表明,Li_(3.8)Mn_(5.2)O_(12)在充电速率1C时的比容量为163 mA h/g,这是一个较大的值,这是由于将Li插入到组合物Li_(6.8)Mn_(5.2)O_(12).歧化的起源和锂化过程中的平坦电压在莫特绝缘体相相对于金属相的稳定性框架内进行了讨论。

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