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

Literature Information

Publication Date 2019-04-15
DOI 10.1039/C9CP00408D
Impact Factor 3.676
Authors

Azeem Banday, Mahboob Ali, Raghvendra Pandey, Sevi Murugavel


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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, an active cathode material, by varying the crystallite sizes. We find that about 17% lithium ion vacancy concentration leads to an enhancement in electronic conductivity of about two orders of magnitude at 313 K with respect to our initial crystallite size. We attribute the enhanced electronic conductivity to the lithium ion vacancy concentration in addition to the reduced hopping length. The lithium ion vacancies are the source of polarons in LiFePO4, which increases with decreasing crystallite size due to the surface energy kinetics. The substantial increase in the polaronic sites (Fe3+) at a lower crystallite size leads to a reduction in lattice parameters including the unit cell volume. The analysis of temperature dependent dc conductivity within the framework of the Mott model of polaron conduction enables us to quantify the various physical parameters associated with polaron hopping in LiFePO4.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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