Stabilization of Lithium Transition Metal Silicates in the Olivine Structure

doi:10.1021/acs.inorgchem.7b01453

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

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While olivine LiFePO ₄ 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 [PO ₄] ^3- polyanion with a silicate [SO ₄] ^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 LiInSiO ₄ and LiScSiO ₄ 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-ySiO ₄. 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] ;

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:: 2017-07-28

Grant/Contract Number:: AC02-06CH11357

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)

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

Sponsoring Org:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Natural Science and Engineering Research Council of Canada

Country of Publication:: United States

Language:: English

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

OSTI Identifier:: 1393479


                    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.,  
        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.  doi:10.1021/acs.inorgchem.7b01453.

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                    Sun, Xiaoqi, Tripathi, Rajesh, Popov, Guerman, Balasubramanian, Mahalingam, and Nazar, Linda F. 2017.  
        "Stabilization of Lithium Transition Metal Silicates in the Olivine Structure".  United States.  
        doi: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         = {2017},

  month        = {7}

}

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Free Publicly Accessible Full Text
Accepted Manuscript (DOE)
Publisher's Version of Record
10.1021/acs.inorgchem.7b01453
https://doi.org/10.1021/acs.inorgchem.7b01453

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

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