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Direct evidence for the influence of lithium ion vacancies on polaron transport in nanoscale LiFePO4

Abstract

Improving the electronic conductivity in lithium-based compounds can considerably impact the design of rechargeable batteries. Here, we explore the influence of lithium ion vacancies on the electronic conductivity of LiFePO4, a promising cathode material, by varying the crystallite sizes. We find that about 7% lithium ion vacancies concentration leads to enhancement of two orders of magnitude in electronic conductivity at 313 K with respect to our initial crystallite size. We attribute the enhanced electronic conductivity is due to lithium ion vacancies concentrations in addition to the reduced hopping length. The lithium ion vacancies are the source of polarons in LiFePO4, which increases with decreasing the crystallite size due to the surface energy kinetics. The substantial increase in the polaronic sites (Fe3+) at lower crystallite size leads to the reduction in lattice parameters including the unit cell volume. The analysis of temperature dependent dc conductivity within the framework of Mott model of polaron conduction, we are able to quantify the various physical parameters associated with polaron hopping in LiFePO4.

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Publication details

The article was received on 22 Jan 2019, accepted on 15 Apr 2019 and first published on 15 Apr 2019


Article type: Paper
DOI: 10.1039/C9CP00408D
Citation: Phys. Chem. Chem. Phys., 2019, Accepted Manuscript

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    Direct evidence for the influence of lithium ion vacancies on polaron transport in nanoscale LiFePO4

    A. Banday , M. Ali, R. Pandey and M. Sevi, Phys. Chem. Chem. Phys., 2019, Accepted Manuscript , DOI: 10.1039/C9CP00408D

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