Journal
CHEMISTRY OF MATERIALS
Volume 24, Issue 24, Pages 4717-4724Publisher
AMER CHEMICAL SOC
DOI: 10.1021/cm303005d
Keywords
lithium ion batteries; cathode materials; LiMnPO4; vanadium doping
Funding
- Landesgraduiertenforderung Saarland
- Carl-Zeiss foundation
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In this paper we report on the increase of grain conductivity in the potential cathode material LiMnPO4 by means of vanadium doping by 1-2 orders of magnitude. We found that up to 20% of phosphorus in LiMnPO4 can be replaced by vanadium. The allocation of vanadium was investigated by a Rietveld analysis of high quality laboratory X-ray diffraction (XRD) data and Extended X-ray Absorption Fine Structure (EXAFS)/X-ray Absorption Near Edge Structure (XANES) measurements of the samples. Calculations of the electronic structure by means of density functional theory (DFT) help to understand an observed increase in conductivity, which is likely to be of electronic nature. We suggest that it is attributed to energetically low lying d-levels of vanadium, which above 0 K cause a partial formation of mixed-valence Mn2+/Mn3+.
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