What Triggers Oxygen Loss in Oxygen Redox Cathode Materials?

被引：186

作者：

House, Robert A. ^{[1
]}

Maitra, Urmimala ^{[1
,8
]}

Jin, Liyu ^{[1
]}

Lozano, Juan G. ^{[1
]}

Somerville, James W. ^{[1
]}

Rees, Nicholas H. ^{[3
]}

Naylor, Andrew J. ^{[4
]}

Duda, Laurent C. ^{[5
]}

Massel, Felix ^{[5
]}

Chadwick, Alan V. ^{[6
]}

Ramos, Silvia ^{[6
]}

Pickup, David M. ^{[6
]}

McNally, Daniel E. ^{[7
]}

Lu, Xingye ^{[7
]}

Schmitt, Thorsten ^{[7
]}

Roberts, Matthew R. ^{[1
]}

Bruce, Peter G. ^{[1
,2
,3
]}

机构：

[1] Univ Oxford, Dept Mat, Parks Rd, Oxford OX1 3PH, England

[2] Univ Oxford, Faraday Inst, Mansfield Rd, Oxford OX1 3TA, England

[3] Univ Oxford, Dept Chem, Mansfield Rd, Oxford OX1 3TA, England

[4] Uppsala Univ, Dept Chem, Angstrom Lab, Box 538, SE-75121 Uppsala, Sweden

[5] Uppsala Univ, Dept Phys & Astron, Div Mol & Condensed Matter Phys, Box 516, S-75120 Uppsala, Sweden

[6] Univ Kent, Sch Phys Sci, Canterbury CT2 7NH, Kent, England

[7] Paul Scherrer Inst, Swiss Light Source, Photon Sci Div, CH-5232 Villigen, Switzerland

[8] Justus Liebig Univ Giessen, Inst Phys Chem, Heinrich Buff Ring 17,Room B48, D-35392 Giessen, Germany

来源：

CHEMISTRY OF MATERIALS | 2019年 / 31卷 / 09期

基金：

英国工程与自然科学研究理事会;

关键词：

POSITIVE ELECTRODE MATERIAL; ION BATTERIES; CHARGE-COMPENSATION; LITHIUM BATTERIES; HIGH-VOLTAGE; CHEMISTRY; CAPACITY; PARTICIPATION; DIFFRACTION; MECHANISMS;

D O I：

10.1021/acs.chemmater.9b00227

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

It is possible to increase the charge capacity of transition metal (TM) oxide cathodes in alkali-ion batteries by invoking redox reactions on the oxygen. However, oxygen loss often occurs. To explore what affects oxygen loss in oxygen redox materials, we have compared two analogous Na-ion cathodes, P2-Na0.67Mg0.28Mn0.72O2 and P2-Na0.78Li0.25Mn0.75O2. On charging to 4.5 V, >0.4e(-) are removed from the oxide ions of these materials, but neither compound exhibits oxygen loss. Li is retained in P2-Na0.78Li0.25Mn0.25O2 but displaced from the TM to the alkali metal layers, showing that vacancies in the TM layers, which also occur in other oxygen redox compounds that exhibit oxygen loss such as Li[Li0.2Ni0.2Mn0.6]O-2, are not a trigger for oxygen loss. On charging at 5 V, P2-Na0.78Li0.25Mn0.75O2 exhibits oxygen loss, whereas P2-Na0.67Mg0.28Mn0.72O2 does not. Under these conditions, both Na+ and Li+ are removed from P2-Na0.78Li0.25Mn0.75O2, resulting in underbonded oxygen (fewer than 3 cations coordinating oxygen) and surface-localized O loss. In contrast, for P2-Na0.67Mg0.28Mn0.72O2, oxygen remains coordinated by at least 2 Mn4+ and 1 Mg2+ ions, stabilizing the oxygen and avoiding oxygen loss.

引用

页码：3293 / 3300

页数：8

共 35 条

[1] Demonstrating oxygen loss and associated structural reorganization in the lithium battery cathode Li[Ni0.2Li0.2Mn0.6]O2 [J].

Armstrong, A. Robert ;

Holzapfel, Michael ;

Novak, Petr ;

Johnson, Christopher S. ;

Kang, Sun-Ho ;

Thackeray, Michael M. ;

Bruce, Peter G. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (26) :8694-8698

[2] Direct evidence for high Na+ mobility and high voltage structural processes in P2-Nax[LiyNizMn1-y-z]O2 (x, y, z ≤ 1) cathodes from solid- state NMR and DFT calculations [J].

Clement, R. J. ;

Xu, J. ;

Middlemiss, D. S. ;

Alvarado, J. ;

Ma, C. ;

Meng, Y. S. ;

Grey, C. P. .

JOURNAL OF MATERIALS CHEMISTRY A, 2017, 5 (08) :4129-4143

[3] Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode [J].

de Boisse, Benoit Mortemard ;

Liu, Guandong ;

Ma, Jiangtao ;

Nishimura, Shin-ichi ;

Chung, Sai-Cheong ;

Kiuchi, Hisao ;

Harada, Yoshihisa ;

Kikkawa, Jun ;

Kobayashi, Yoshio ;

Okubo, Masashi ;

Yamada, Atsuo .

NATURE COMMUNICATIONS, 2016, 7

[4] Improving Energy Density and Structural Stability of Manganese Oxide Cathodes for Na-Ion Batteries by Structural Lithium Substitution [J].

de la Llave, Ezequiel ;

Talaie, Elahe ;

Levi, Elena ;

Nayak, Prasant Kumar ;

Dixit, Mudit ;

Rao, Penki Tirupathi ;

Hartmann, Pascal ;

Chesneau, Hartmann Frederick ;

Major, Dan Thomas ;

Greenstein, Miri ;

Aurbach, Doron ;

Nazar, Linda F. .

CHEMISTRY OF MATERIALS, 2016, 28 (24) :9064-9076

[5] STRUCTURAL CLASSIFICATION AND PROPERTIES OF THE LAYERED OXIDES [J].

DELMAS, C ;

FOUASSIER, C ;

HAGENMULLER, P .

PHYSICA B & C, 1980, 99 (1-4) :81-85

[6] Exploring reversible oxidation of oxygen in a manganese oxide [J].

Du, Ke ;

Zhu, Jinyou ;

Hu, Guorong ;

Gao, Hongcai ;

Li, Yutao ;

Goodenough, John B. .

ENERGY & ENVIRONMENTAL SCIENCE, 2016, 9 (08) :2575-2577

[7] Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides [J].

Gent, William E. ;

Lim, Kipil ;

Liang, Yufeng ;

Li, Qinghao ;

Barnes, Taylor ;

Ahn, Sung-Jin ;

Stone, Kevin H. ;

McIntire, Mitchell ;

Hong, Jihyun ;

Song, Jay Hyok ;

Li, Yiyang ;

Mehta, Apurva ;

Ermon, Stefano ;

Tyliszczak, Tolek ;

Kilcoyne, David ;

Vine, David ;

Park, Jin-Hwan ;

Doo, Seok-Kwang ;

Toney, Michael F. ;

Yang, Wanli ;

Prendergast, David ;

Chueh, William C. .

NATURE COMMUNICATIONS, 2017, 8

[8] Oxygen Release and Its Effect on the Cycling Stability of LiNixMnyCozO2 (NMC) Cathode Materials for Li-Ion Batteries [J].

Jung, Roland ;

Metzger, Michael ;

Maglia, Filippo ;

Stinner, Christoph ;

Gasteiger, Hubert A. .

JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2017, 164 (07) :A1361-A1377

[9] Electrochemical and structural properties of xLi2M'O3•(1-x)LiMn0.5Ni0.5O2 eIectrodes for lithium batteries (M' = Ti, Mn, Zr; 0 ≤ x ≤ 0.3) [J].

Kim, JS ;

Johnson, CS ;

Vaughey, JT ;

Thackeray, MM ;

Hackney, SA .

CHEMISTRY OF MATERIALS, 2004, 16 (10) :1996-2006

[10] Reversible Oxygen Participation to the Redox Processes Revealed for Li1.20Mn0.54Co0.13Ni0.13O2 [J].

Koga, Hideyuki ;

Croguennec, Laurence ;

Menetrier, Michel ;

Douhil, Kais ;

Belin, Stephanie ;

Bourgeois, Lydie ;

Suard, Emmanuelle ;

Weill, Francois ;

Delmas, Claude .

JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2013, 160 (06) :A786-A792

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