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Title: Identification of dopant site and its effect on electrochemical activity in Mn-doped lithium titanate

Doped metal oxide materials are commonly used for applications in energy storage and conversion, such as batteries and solid oxide fuel cells. The knowledge of the electronic properties of dopants and their local environment is essential for understanding the effects of doping on the electrochemical properties. Using a combination of x-ray absorption near-edge structure spectroscopy (XANES) experiment and theoretical modeling we demonstrate that in the dilute (1 at .%) Mn-doped lithium titanate (Li 4/3Ti 5/3O 4, or LTO) the dopant Mn 2+ ions reside on tetrahedral (8a) sites. First-principles Mn K-edge XANES calculations revealed the spectral signature of the tetrahedrally coordinated Mn as a sharp peak in the middle of the absorption edge rise, caused by the 1s → 4 p transition, and it is important to include the effective electron-core hole Coulomb interaction in order to calculate the intenisty of this peak accurately. Finally, this dopant location can explain the impedance of Li migration through the LTO lattice during the charge-discharge process, and, as a result, the observed remarkable 20% decrease in electrochemical capacity of the 1% Mn-doped LTO compared to pristine LTO.
Authors:
 [1] ;  [2] ;  [3] ;  [4] ;  [4] ;  [5] ;  [5] ;  [6] ;  [2] ;  [7]
  1. Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
  4. Weizmann Inst. of Science, Rehovot (Israel). Dept. of Materials and Interfaces
  5. Brookhaven National Lab. (BNL), Upton, NY (United States). Sustainable Energy Technologies Dept.
  6. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Materials Measurement Science Division
  7. Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division
Publication Date:
Report Number(s):
BNL-210811-2018-JAAM
Journal ID: ISSN 2475-9953; PRMHAR
Grant/Contract Number:
SC0012704; AC02-98CH10886; AC02-05CH11231; SC0012673; 16–039
Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 2; Journal Issue: 12; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY
OSTI Identifier:
1488846
Alternate Identifier(s):
OSTI ID: 1488636

Singh, Harishchandra, Topsakal, Mehmet, Attenkofer, Klaus, Wolf, Tamar, Leskes, Michal, Duan, Yandong, Wang, Feng, Vinson, John, Lu, Deyu, and Frenkel, Anatoly I. Identification of dopant site and its effect on electrochemical activity in Mn-doped lithium titanate. United States: N. p., Web. doi:10.1103/PhysRevMaterials.2.125403.
Singh, Harishchandra, Topsakal, Mehmet, Attenkofer, Klaus, Wolf, Tamar, Leskes, Michal, Duan, Yandong, Wang, Feng, Vinson, John, Lu, Deyu, & Frenkel, Anatoly I. Identification of dopant site and its effect on electrochemical activity in Mn-doped lithium titanate. United States. doi:10.1103/PhysRevMaterials.2.125403.
Singh, Harishchandra, Topsakal, Mehmet, Attenkofer, Klaus, Wolf, Tamar, Leskes, Michal, Duan, Yandong, Wang, Feng, Vinson, John, Lu, Deyu, and Frenkel, Anatoly I. 2018. "Identification of dopant site and its effect on electrochemical activity in Mn-doped lithium titanate". United States. doi:10.1103/PhysRevMaterials.2.125403.
@article{osti_1488846,
title = {Identification of dopant site and its effect on electrochemical activity in Mn-doped lithium titanate},
author = {Singh, Harishchandra and Topsakal, Mehmet and Attenkofer, Klaus and Wolf, Tamar and Leskes, Michal and Duan, Yandong and Wang, Feng and Vinson, John and Lu, Deyu and Frenkel, Anatoly I.},
abstractNote = {Doped metal oxide materials are commonly used for applications in energy storage and conversion, such as batteries and solid oxide fuel cells. The knowledge of the electronic properties of dopants and their local environment is essential for understanding the effects of doping on the electrochemical properties. Using a combination of x-ray absorption near-edge structure spectroscopy (XANES) experiment and theoretical modeling we demonstrate that in the dilute (1 at .%) Mn-doped lithium titanate (Li4/3Ti5/3O4, or LTO) the dopant Mn2+ ions reside on tetrahedral (8a) sites. First-principles Mn K-edge XANES calculations revealed the spectral signature of the tetrahedrally coordinated Mn as a sharp peak in the middle of the absorption edge rise, caused by the 1s → 4 p transition, and it is important to include the effective electron-core hole Coulomb interaction in order to calculate the intenisty of this peak accurately. Finally, this dopant location can explain the impedance of Li migration through the LTO lattice during the charge-discharge process, and, as a result, the observed remarkable 20% decrease in electrochemical capacity of the 1% Mn-doped LTO compared to pristine LTO.},
doi = {10.1103/PhysRevMaterials.2.125403},
journal = {Physical Review Materials},
number = 12,
volume = 2,
place = {United States},
year = {2018},
month = {12}
}

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