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Title: Y-doped Li 8ZrO 6: A Li-Ion Battery Cathode Material with High Capacity

We study—experimentally and theoretically—the energetics, structural changes, and charge flows during the charging and discharging processes for a new high-capacity cathode material, Li 8ZrO 6 (LZO), which we study both pure and yttrium-doped. We quantum mechanically calculated the stable delithiated configurations, the delithiation energy, the charge flow during delithiation, and the stability of the delithiated materials. We find that Li atoms are easier to extract from tetrahedral sites than octahedral ones. We calculate a large average voltage of 4.04 eV vs Li/Li + for delithiation of the first Li atom in a primitive cell, which is confirmed by galvanostatic charge/discharge cycling data. Energy calculations indicate that topotactic delithiation is kinetically favored over decomposition into Li, ZrO 2, and O 2 during the charging process, although the thermodynamic energy of the topotactic reaction is less favorable. When one or two lithium atoms are extracted from a primitive cell of LZO, its volume and structure change little, whereas extraction of the third lithium greatly distorts the layered structure. The Li 6ZrO 6 and Li 5ZrO 6 delithiation products can be thermodynamically metastable to release of O 2. Experimentally, materials with sufficiently small particle size for efficient delithiation and relithiation were achieved withinmore » an yttrium-doped LZO/carbon composite cathode that exhibited an initial discharge capacity of at least 200 mAh/g over the first 10 cycles, with 142 mAh/g maintained after 60 cycles. Computations predict that during the charging process, the oxygen ion near the Li vacancy is oxidized for both pure LZO and yttrium-doped LZO, which leads to a small-polaron hole.« less
Authors:
 [1] ;  [2] ;  [1] ;  [2] ;  [2] ;  [2] ;  [1]
  1. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry. Chemical Theory Center. Supercomputing Inst.
  2. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry
Publication Date:
Grant/Contract Number:
SC0008662
Type:
Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 137; Journal Issue: 34; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Research Org:
Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE
OSTI Identifier:
1212268
Alternate Identifier(s):
OSTI ID: 1455137

Huang, Shuping, Wilson, Benjamin E., Wang, Bo, Fang, Yuan, Buffington, Keegan, Stein, Andreas, and Truhlar, Donald G.. Y-doped Li8ZrO6: A Li-Ion Battery Cathode Material with High Capacity. United States: N. p., Web. doi:10.1021/jacs.5b04690.
Huang, Shuping, Wilson, Benjamin E., Wang, Bo, Fang, Yuan, Buffington, Keegan, Stein, Andreas, & Truhlar, Donald G.. Y-doped Li8ZrO6: A Li-Ion Battery Cathode Material with High Capacity. United States. doi:10.1021/jacs.5b04690.
Huang, Shuping, Wilson, Benjamin E., Wang, Bo, Fang, Yuan, Buffington, Keegan, Stein, Andreas, and Truhlar, Donald G.. 2015. "Y-doped Li8ZrO6: A Li-Ion Battery Cathode Material with High Capacity". United States. doi:10.1021/jacs.5b04690.
@article{osti_1212268,
title = {Y-doped Li8ZrO6: A Li-Ion Battery Cathode Material with High Capacity},
author = {Huang, Shuping and Wilson, Benjamin E. and Wang, Bo and Fang, Yuan and Buffington, Keegan and Stein, Andreas and Truhlar, Donald G.},
abstractNote = {We study—experimentally and theoretically—the energetics, structural changes, and charge flows during the charging and discharging processes for a new high-capacity cathode material, Li8ZrO6 (LZO), which we study both pure and yttrium-doped. We quantum mechanically calculated the stable delithiated configurations, the delithiation energy, the charge flow during delithiation, and the stability of the delithiated materials. We find that Li atoms are easier to extract from tetrahedral sites than octahedral ones. We calculate a large average voltage of 4.04 eV vs Li/Li+ for delithiation of the first Li atom in a primitive cell, which is confirmed by galvanostatic charge/discharge cycling data. Energy calculations indicate that topotactic delithiation is kinetically favored over decomposition into Li, ZrO2, and O2 during the charging process, although the thermodynamic energy of the topotactic reaction is less favorable. When one or two lithium atoms are extracted from a primitive cell of LZO, its volume and structure change little, whereas extraction of the third lithium greatly distorts the layered structure. The Li6ZrO6 and Li5ZrO6 delithiation products can be thermodynamically metastable to release of O2. Experimentally, materials with sufficiently small particle size for efficient delithiation and relithiation were achieved within an yttrium-doped LZO/carbon composite cathode that exhibited an initial discharge capacity of at least 200 mAh/g over the first 10 cycles, with 142 mAh/g maintained after 60 cycles. Computations predict that during the charging process, the oxygen ion near the Li vacancy is oxidized for both pure LZO and yttrium-doped LZO, which leads to a small-polaron hole.},
doi = {10.1021/jacs.5b04690},
journal = {Journal of the American Chemical Society},
number = 34,
volume = 137,
place = {United States},
year = {2015},
month = {8}
}