Spectroscopic Evidence of Surface Li-Depletion of Lithium Transition-Metal Phosphates

The surface chemistries of carefully synthesized, phase pure lithium transition-metal phosphates LiTMPO4 (TM = Fe, Mn, Co, Ni) have been determined using a combination of surface spectroscopic techniques. Results obtained with X-ray photoelectron spectroscopy, Raman spectroscopy, and soft X-ray abso...

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Published inACS applied energy materials Vol. 3; no. 3; pp. 2856 - 2866
Main Authors Zhang, Yin, Alarco, Jose A, Nerkar, Jawahar Y, Best, Adam S, Snook, Graeme A, Talbot, Peter C, Cowie, Bruce C. C
Format Journal Article
LanguageEnglish
Published American Chemical Society 23.03.2020
Subjects
surface mixed oxidation
lithium ion battery
lithium transition metal phosphates
Li-depletion
surface properties
surface characterization
soft X-ray spectroscopy
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Summary:The surface chemistries of carefully synthesized, phase pure lithium transition-metal phosphates LiTMPO4 (TM = Fe, Mn, Co, Ni) have been determined using a combination of surface spectroscopic techniques. Results obtained with X-ray photoelectron spectroscopy, Raman spectroscopy, and soft X-ray absorption spectroscopy indicate the presence of surface Li-depletion and mixed chemical states of transition-metal (TM) ions across the family. The extent of surface TM mixed chemical states has been found responsible for changes in color and optical absorption edge positions, which are often used to validate electronic band structure calculations. These characteristics are common in many complex metal oxide ceramics and may not be unique to lithium metal phosphate battery materials.
ISSN:2574-0962
2574-0962
DOI:10.1021/acsaem.9b02489