Revealing Defects in Crystalline Lithium-Ion Battery Electrodes by Solid-State NMR: Applications to LiVPO4F

详细信息    查看全文

• 作者：Robert J. Messinger ; Michel M茅n茅trier ; Elodie Salager ; Adrien Boulineau ; Mathieu Duttine ; Dany Carlier ; Jean-Marcel Ateba Mba ; Laurence Croguennec ; Christian Masquelier ; Dominique Massiot ; Micha毛l Deschamps
• 刊名：Chemistry of Materials
• 出版年：2015
• 出版时间：August 11, 2015
• 年：2015
• 卷：27
• 期：15
• 页码：5212-5221
• 全文大小：500K
• ISSN：1520-5002

文摘

Identifying and characterizing defects in crystalline solids is a challenging problem, particularly for lithium-ion intercalation materials, which often exhibit multiple stable oxidation and spin states as well as local ordering of lithium and charges. Here, we reveal the existence of characteristic lithium defect environments in the crystalline lithium-ion battery electrode LiVPO₄F and establish the relative subnanometer-scale proximities between them. Well-crystallized LiVPO₄F samples were synthesized with the expected tavorite-like structure, as established by X-ray diffraction (XRD) and scanning transmission electron microscopy (STEM) measurements. Solid-state ⁷Li nuclear magnetic resonance (NMR) spectra reveal unexpected paramagnetic ⁷Li environments that can account for up to 20% of the total lithium content. Multidimensional and site-selective solid-state ⁷Li NMR experiments using finite-pulse radio frequency-driven recoupling (fp-RFDR) establish unambiguously that the unexpected lithium environments are associated with defects within the LiVPO₄F crystal structure, revealing the existence of dipole鈥揹ipole-coupled defect pairs. The lithium defects exhibit local electronic environments that are distinct from lithium ions in the crystallographic LiVPO₄F site, which result from altered oxidation and/or spin states of nearby paramagnetic vanadium atoms. The results provide a general strategy for identifying and characterizing lithium defect environments in crystalline solids, including paramagnetic materials with short ⁷Li NMR relaxation times on the order of milliseconds.