Stabilization of Lithium Transition Metal Silicates in the Olivine Structure

Sun, Xiaoqi; Tripathi, Rajesh; Popov, Guerman; Balasubramanian, Mahalingam; Nazar, Linda F.

doi:10.1021/acs.inorgchem.7b01453

Title: Stabilization of Lithium Transition Metal Silicates in the Olivine Structure

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Abstract

While olivine LiFePO₄ shows amongst the best electrochemical properties of Li-ion positive electrodes with respect to rate behavior owing to facile Li⁺ migration pathways in the framework, replacing the [PO₄] ^3- polyanion with a silicate [SO₄] ^4- moitie in olivine is desirable. This would allow additional balancing alkali content and hence electron transfer, and increase the capacity. We demonstrate the first stabilization of a lithium transition-metal silicate (as a pure silicate) in the olivine structure type. Using LiInSiO₄ and LiScSiO₄ as the parent materials, transition metal (Mn, Fe, Co) substitutions on the In/Sc site were investigated by computational modelling via atomic scale simulation. Transition metal substitution was found to be only favourable for Co, a finding confirmed by the successful solid state synthesis of olivine LixInyCo_2-x-ySiO₄. Finally, the stabilization of the structure was achieved by entropy provided by cation disorder.

Authors:

Sun, Xiaoqi ^[1]; Tripathi, Rajesh ^[2]; Popov, Guerman ^[1]; Balasubramanian, Mahalingam ^[3];

^[1]

Univ. of Waterloo, ON (Canada). Dept. of Chemistry and the Waterloo Inst. of Nanotechnology
DuPoint Science and Innovation, DE (United States)
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Publication Date:: Fri Jul 28 00:00:00 EDT 2017

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Natural Science and Engineering Research Council of Canada

OSTI Identifier:: 1393479

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: Inorganic Chemistry

Additional Journal Information:: Journal Volume: 56; Journal Issue: 16; Journal ID: ISSN 0020-1669

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Sun, Xiaoqi, Tripathi, Rajesh, Popov, Guerman, Balasubramanian, Mahalingam, and Nazar, Linda F. Stabilization of Lithium Transition Metal Silicates in the Olivine Structure.  United States: N. p., 2017. 
Web.  doi:10.1021/acs.inorgchem.7b01453.

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                    Sun, Xiaoqi, Tripathi, Rajesh, Popov, Guerman, Balasubramanian, Mahalingam, & Nazar, Linda F. Stabilization of Lithium Transition Metal Silicates in the Olivine Structure.  United States.  https://doi.org/10.1021/acs.inorgchem.7b01453

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                    Sun, Xiaoqi, Tripathi, Rajesh, Popov, Guerman, Balasubramanian, Mahalingam, and Nazar, Linda F. Fri .  
"Stabilization of Lithium Transition Metal Silicates in the Olivine Structure".  United States.  https://doi.org/10.1021/acs.inorgchem.7b01453.  https://www.osti.gov/servlets/purl/1393479.

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@article{osti_1393479,

  title        = {Stabilization of Lithium Transition Metal Silicates in the Olivine Structure},

  author       = {Sun, Xiaoqi and Tripathi, Rajesh and Popov, Guerman and Balasubramanian, Mahalingam and Nazar, Linda F.},

  abstractNote = {While olivine LiFePO4 shows amongst the best electrochemical properties of Li-ion positive electrodes with respect to rate behavior owing to facile Li+ migration pathways in the framework, replacing the [PO4] 3- polyanion with a silicate [SO4] 4- moitie in olivine is desirable. This would allow additional balancing alkali content and hence electron transfer, and increase the capacity. We demonstrate the first stabilization of a lithium transition-metal silicate (as a pure silicate) in the olivine structure type. Using LiInSiO4 and LiScSiO4 as the parent materials, transition metal (Mn, Fe, Co) substitutions on the In/Sc site were investigated by computational modelling via atomic scale simulation. Transition metal substitution was found to be only favourable for Co, a finding confirmed by the successful solid state synthesis of olivine LixInyCo2-x-ySiO4. Finally, the stabilization of the structure was achieved by entropy provided by cation disorder.},

  doi          = {10.1021/acs.inorgchem.7b01453},

  journal      = {Inorganic Chemistry},

  number       = 16,

  volume       = 56,

  place        = {United States},

  year         = {Fri Jul 28 00:00:00 EDT 2017},

  month        = {Fri Jul 28 00:00:00 EDT 2017}

}

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