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Title: Influence of lithium vacancies on the polaronic transport in olivine phosphate structure

Journal Article · · Journal of Applied Physics
DOI:https://doi.org/10.1063/1.4939958· OSTI ID:22494952
; ;  [1]
  1. Department of Physics and Astrophysics, University of Delhi, Delhi 110 007 (India)

Intercalation and deintercalation of lithium ions in cathode materials are of principal to the operation of current rechargeable lithium ion batteries. The performance of lithium ion batteries highly relies on the active cathode material which includes cell potential, power/energy density, capacity, etc. An important issue in this class of material is to resolve the factors governing the electron and ion transport in olivine phosphate structure. In this class of material, there is still an open debate on the mechanism of charge transport including both polarons and lithium ions. On the one hand, this is due to the large disparity between the experimental results and the theoretical model predictions. On the other hand, this is also due to the lack of precise experimental measurement without any parasitic phases in a given cathode material. Here, we present the polaronic conduction in lithiated triphylite LiFePO{sub 4} (LFP) and delithiated heterosite FePO{sub 4} (FP) by means of broadband ac impedance spectroscopy over wide range temperatures and frequency. It is found that the LFP phase possess two orders of higher polaronic conductivity than FP phase despite having similar mobility of polarons in both phases. We show that the differences in the polaronic conductivity of two phases are due to the significant differences in concentration of polarons. It is found that the formation energy of polarons in individual phases is mainly determined by the corresponding defect state associated with it. The temperature dependent dc conductivity has been analyzed within the framework of Mott model of polaronic conduction and explored the origin of polaronic conduction mechanism in this class of material.

OSTI ID:
22494952
Journal Information:
Journal of Applied Physics, Vol. 119, Issue 4; Other Information: (c) 2016 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-8979
Country of Publication:
United States
Language:
English