Thermal Stability of Li2O2 and Li2O for Li-Air Batteries: In Situ XRD and XPS Studies

被引：301

作者：

Yao, Koffi P. C. ^{[1
,2
]}

Kwabi, David G. ^{[1
,2
]}

Quinlan, Ronald A. ^{[3
]}

Mansour, Azzam N. ^{[3
]}

Grimaud, Alexis ^{[2
]}

Lee, Yueh-Lin ^{[2
]}

Lu, Yi-Chun ^{[2
,4
]}

Shao-Horn, Yang ^{[1
,2
,4
]}

机构：

[1] MIT, Dept Mech Engn, Cambridge, MA 02139 USA

[2] MIT, Electrochem Energy Lab, Cambridge, MA 02139 USA

[3] USN, Ctr Surface Warfare, Carderock Div, West Bethesda, MD 20817 USA

[4] MIT, Dept Mat Sci & Engn, Cambridge, MA 02139 USA

来源：

JOURNAL OF THE ELECTROCHEMICAL SOCIETY | 2013年 / 160卷 / 06期

关键词：

LITHIUM PEROXIDE; LI-O-2; BATTERY; ELECTRONIC-STRUCTURE; DISCHARGE; OXIDE;

D O I：

10.1149/2.069306jes

中图分类号：

O646 [电化学、电解、磁化学];

学科分类号：

081704 ;

摘要：

Understanding the thermal stability of major reaction products, Li2O2 (space group P6(3)/mmc) and Li2O (space group Fm (3) over barm) is critical to improve the safety characteristics of Li-air batteries. The changes in the crystal structure and surface chemistry of Li2O2 and Li2O were examined as a function of temperature via in situ X-ray diffraction (XRD) and in situ X-ray photoelectron spectroscopy (XPS). Significant decreases in the lattice parameters and the c/a ratio of Li2O2 were found at 280 degrees C and higher. These structural changes can be attributed to the transformation of Li2O2 to Li2O2-delta, which is supported by density functional theory calculations. Upon further heating to 700 degrees C, a lithium-deficient Li2-delta O phase appeared at 300 degrees C and gradually became stoichiometric upon further heating to similar to 550 degrees C. XPS measurements of Li2O2 revealed that Li2O appeared on the surface starting at 250 degrees C, which is in agreement with the onset temperature of phase transformation as detected by XRD. In addition, the growth of Li2CO3 on the surface was found at 250 degrees C, which can be attributed to chemical reactions between Li2O2/Li2O and carbon-containing species (e.g. hydrocarbons) present in the XPS chamber. This finding highlights the challenges of developing stable carbon-based oxygen electrode for Li-air batteries. (C) 2013 The Electrochemical Society. All rights reserved.

引用

页码：A824 / A831

页数：8

共 50 条

[1]

[Anonymous], 1998, J PHYS CHEM REF DATA

[2] Microstructure of LiCoO2 with and without "AIPO4" nanoparticle coating:: Combined STEM and XPS studies [J].

Appapillai, Anjuli T. ;

Mansour, Azzam N. ;

Cho, Jaephil ;

Shao-Horn, Yang .

CHEMISTRY OF MATERIALS, 2007, 19 (23) :5748-5757

[3] HIGH-RESOLUTION MONOCHROMATED XPS OF POLY(METHYL METHACRYLATE) THIN-FILMS ON A CONDUCTING SUBSTRATE [J].

BEAMSON, G ;

BUNN, A ;

BRIGGS, D .

SURFACE AND INTERFACE ANALYSIS, 1991, 17 (02) :105-115

[4] PROJECTOR AUGMENTED-WAVE METHOD [J].

BLOCHL, PE .

PHYSICAL REVIEW B, 1994, 50 (24) :17953-17979

[5]

Bruce PG, 2012, NAT MATER, V11, P19, DOI [10.1038/nmat3191, 10.1038/NMAT3191]

[6] DEFECT STRUCTURES AND IONIC TRANSPORT IN LITHIUM-OXIDE [J].

CHADWICK, AV ;

FLACK, KW ;

STRANGE, JH ;

HARDING, J .

SOLID STATE IONICS, 1988, 28 :185-188

[7] Li-O2 Battery with a Dimethylformamide Electrolyte [J].

Chen, Yuhui ;

Freunberger, Stefan A. ;

Peng, Zhangquan ;

Barde, Fanny ;

Bruce, Peter G. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (18) :7952-7957

[8] On the structure of lithium peroxide, Li2O2 [J].

Cota, LG ;

de la Mora, P .

ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE CRYSTAL ENGINEERING AND MATERIALS, 2005, 61 :133-136

[9] α-MnO2 nanowires:: A catalyst for the O2 electrode in rechargeable lithium batteries [J].

Debart, Aurelie ;

Paterson, Allan J. ;

Bao, Jianli ;

Bruce, Peter G. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2008, 47 (24) :4521-4524

[10] DEFECT ENERGETICS IN OXIDE MATERIALS FROM 1ST PRINCIPLES [J].

DEVITA, A ;

GILLAN, MJ ;

LIN, JS ;

PAYNE, MC ;

STICH, I ;

CLARKE, LJ .

PHYSICAL REVIEW LETTERS, 1992, 68 (22) :3319-3322

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