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

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:
 [1] ;  [2] ;  [1] ;  [3] ; ORCiD logo [1]
  1. Univ. of Waterloo, ON (Canada). Dept. of Chemistry and the Waterloo Inst. of Nanotechnology
  2. DuPoint Science and Innovation, DE (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Publication Date:
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.
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.
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.
@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}
}