Crystal Chemistry of Electrochemically and Chemically Lithiated Layered αI-LiVOPO4

He, Guang; Bridges, Craig A.; Manthiram, Arumugam

doi:10.1021/acs.chemmater.5b02609

Title: Crystal Chemistry of Electrochemically and Chemically Lithiated Layered α_I-LiVOPO₄

Journal Article · Mon Sep 14 00:00:00 EDT 2015 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.5b02609· OSTI ID:1265668

He, Guang ^[1]; Bridges, Craig A. ^[2]; Manthiram, Arumugam ^[1]

Univ. of Texas, Austin, TX (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

LiVOPO₄ is an attractive cathode for lithium-ion batteries with a high operating voltage and the potential to achieve the reversible insertion of two lithium ions between VOPO₄ and Li₂VOPO₄. Among the three known forms of LiVOPO₄ (α, β, and αI), the α_I-LiVOPO₄ has a layered structure that could promote better ionic mobility and reversibility than others. However, a comprehensive study of its lithiated product is not available as αI-LiVOPO₄ is metastable and difficult to prepare by conventional approaches. We present here a facile synthesis of highly crystalline αI-LiVOPO₄ and α_I-LiVOPO₄/rGO nanocomposite by a microwave-assisted solvothermal method and its electrochemical/chemical lithiation. The LiVOPO₄/rGO cathodes exhibit a high reversible capacity of 225 mAh g^–1, indicating the insertion of more than one lithium into VOPO₄. Both electrochemical and chemical lithiation imply a solid-solution reaction mechanism on inserting the second lithium into α_I-LiVOPO₄, but a two-phase reaction feature could also occur under certain conditions such as insufficient time for equilibration of Li⁺ diffusion in the structure. The fully lithiated new α_I-Li₂VOPO₄ phase was characterized by combined Rietveld refinement of neutron diffraction and X-ray diffraction data and by bond-valence sum maps. The results suggest that αI-Li₂VOPO₄ retains the tetragonal P4/nmm symmetry of the parent α_I-LiVOPO₄ structure, where the second lithium ions are located in the lithium layers rather than in the VOPO₄ layers

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1265668

Journal Information:: Chemistry of Materials, Vol. 27, Issue 19; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 40 works

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Title: Crystal Chemistry of Electrochemically and Chemically Lithiated Layered αI-LiVOPO4

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Title: Crystal Chemistry of Electrochemically and Chemically Lithiated Layered α_I-LiVOPO₄