Records |
Author |
Sathiya, M.; Abakumov, A.M.; Foix, D.; Rousse, G.; Ramesha, K.; Saubanère, M.; Doublet, M. .; Vezin, H.; Laisa, C.P.; Prakash, A.S.; Gonbeau, D.; Van Tendeloo, G.; Tarascon, J.M. |
Title |
Origin of voltage decay in high-capacity layered oxide electrodes |
Type |
A1 Journal article |
Year |
2015 |
Publication |
Nature materials |
Abbreviated Journal |
Nat Mater |
Volume |
14 |
Issue |
14 |
Pages |
230-238 |
Keywords |
A1 Journal article; Electron microscopy for materials research (EMAT) |
Abstract |
Although Li-rich layered oxides (Li1+xNiyCozMn1−x−y−zO2 > 250 mAh g−1) are attractive electrode materials providing energy densities more than 15% higher than todays commercial Li-ion cells, they suffer from voltage decay on cycling. To elucidate the origin of this phenomenon, we employ chemical substitution in structurally related Li2RuO3 compounds. Li-rich layered Li2Ru1−yTiyO3 phases with capacities of ~240 mAh g−1 exhibit the characteristic voltage decay on cycling. A combination of transmission electron microscopy and X-ray photoelectron spectroscopy studies reveals that the migration of cations between metal layers and Li layers is an intrinsic feature of the chargedischarge process that increases the trapping of metal ions in interstitial tetrahedral sites. A correlation between these trapped ions and the voltage decay is established by expanding the study to both Li2Ru1−ySnyO3 and Li2RuO3; the slowest decay occurs for the cations with the largest ionic radii. This effect is robust, and the finding provides insights into new chemistry to be explored for developing high-capacity layered electrodes that evade voltage decay. |
Address |
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Corporate Author |
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Thesis |
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Publisher |
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Place of Publication |
London |
Editor |
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Language ![sorted by Language field, descending order (down)](img/sort_desc.gif) |
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Wos |
000348600200024 |
Publication Date |
2014-12-01 |
Series Editor |
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Series Title |
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Abbreviated Series Title |
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Series Volume |
|
Series Issue |
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Edition |
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ISSN |
1476-1122;1476-4660; |
ISBN |
|
Additional Links |
UA library record; WoS full record; WoS citing articles |
Impact Factor |
39.737 |
Times cited |
395 |
Open Access |
|
Notes |
246791 Countatoms; 312483 Esteem2; esteem2_ta |
Approved |
Most recent IF: 39.737; 2015 IF: 36.503 |
Call Number |
c:irua:132555 c:irua:132555 |
Serial |
2528 |
Permanent link to this record |
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Author |
McCalla, E.; Prakash, A.S.; Berg, E.; Saubanere, M.; Abakumov, A.M.; Foix, D.; Klobes, B.; Sougrati, M.T.; Rousse, G.; Lepoivre, F.; Mariyappan, S.; Doublet, M.L.; Gonbeau, D.; Novak, P.; Van Tendeloo, G.; Hermann, R.P.; Tarascon, J.M.; |
Title |
Reversible Li-intercalation through oxygen reactivity in Li-rich Li-Fe-Te oxide materials |
Type |
A1 Journal article |
Year |
2015 |
Publication |
Journal of the electrochemical society |
Abbreviated Journal |
J Electrochem Soc |
Volume |
162 |
Issue |
162 |
Pages |
A1341-A1351 |
Keywords |
A1 Journal article; Electron microscopy for materials research (EMAT) |
Abstract |
Lithium-rich oxides are a promising class of positive electrode materials for next generation lithium-ion batteries, and oxygen plays a prominent role during electrochemical cycling either by forming peroxo-like species and/or by irreversibly forming oxygen gas during first charge. Here, we present Li-Fe-Te-O materials which show a tremendous amount of oxygen gas release. This oxygen release accounts for nearly all the capacity during the first charge and results in vacancies as seen by transmission electron microscopy. There is no oxidation of either metal during charge but significant changes in their environments. These changes are particularly extreme for tellurium. XRD and neutron powder diffraction both show limited Changes during cycling and no appreciable change in lattice parameters. A density functional theory study of this material is performed and demonstrates that the holes created on some of the oxygen atoms upon oxidation are partially stabilized through the formation of shorter O-O bonds, i.e. (O-2)(n-) species which on further delithiation show a spontaneous O-2 de-coordination from the cationic network and migration to the now empty lithium layer. The rate limiting step during charge is undoubtedly the diffusion of oxygen either out along the lithium layer or via columns of oxygen atoms. (C) 2015 The Electrochemical Society. All rights reserved. |
Address |
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Corporate Author |
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Thesis |
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Publisher |
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Place of Publication |
New York, N.Y. |
Editor |
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Language ![sorted by Language field, descending order (down)](img/sort_desc.gif) |
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Wos |
000355643700030 |
Publication Date |
2015-04-29 |
Series Editor |
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Series Title |
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Abbreviated Series Title |
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Series Volume |
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Series Issue |
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Edition |
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ISSN |
0013-4651;1945-7111; |
ISBN |
|
Additional Links |
UA library record; WoS full record; WoS citing articles |
Impact Factor |
3.259 |
Times cited |
23 |
Open Access |
|
Notes |
|
Approved |
Most recent IF: 3.259; 2015 IF: 3.266 |
Call Number |
c:irua:126445 |
Serial |
2903 |
Permanent link to this record |