Observation of electrochemically active Fe3+/Fe4+ in LiCo0.8Fe0.2MnO4 by in situ Mossbauer spectroscopy and X-ray absorption spectroscopy

被引：16

作者：

Draeger, Christoph ^{[1
]}

Sigel, Florian ^{[1
]}

Witte, Ralf ^{[2
]}

Kruk, Robert ^{[2
]}

Pfaffmann, Lukas ^{[1
]}

Mangold, Stefan ^{[3
]}

Mereacre, Valeriu ^{[1
]}

Knapp, Michael ^{[1
,4
]}

Ehrenberg, Helmut ^{[1
,4
]}

Indris, Sylvio ^{[1
,4
]}

机构：

[1] KIT, IAM, D-76344 Eggenstein Leopoldshafen, Germany

[2] KIT, Inst Nanotechnol INT, D-76344 Eggenstein Leopoldshafen, Germany

[3] KIT, Inst Photon Sci & Synchrotron Radiat IPS, D-76344 Eggenstein Leopoldshafen, Germany

[4] Helmholtz Inst Ulm Electrochem Energy Storage HIU, Helmholtzstr 11, D-89081 Ulm, Germany

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2019年 / 21卷 / 01期

关键词：

LI-ION BATTERIES; CATHODE MATERIALS; SPINEL; DIFFRACTION; OXIDES;

D O I：

10.1039/c8cp06177g

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：

LiCo0.8Fe0.2MnO4 has been investigated as an active material for the positive electrode in lithium-ion batteries (LIBs) with a discharge potential of around 5 V (vs. Li+|Li). After synthesis by a Pechini based sol-gel route, the structural and morphological properties have been investigated by X-ray diffraction, scanning electron microscopy, Li-7 MAS NMR spectroscopy, and Fe-57 Mossbauer spectroscopy. With galvanostatic cycling, it was possible to obtain a specific discharge capacity of 117 mA h g(-1), which is more than 80% of the theoretical capacity. The lithium extraction/insertion mechanism has been characterized by in situ synchrotron powder diffraction. The reversible oxidation process of Fe3+ to Fe4+ has been observed by in situ Mossbauer spectroscopy and in situ XAS measurements.

引用

页码：89 / 95

页数：7

共 29 条

[1] Electrochemical, 6Li MAS NMR, and X-ray and neutron diffraction study of LiCoxFeyMn2-(x+y)O4 spinel oxides for high-voltage cathode materials [J].

Alcántara, R ;

Jaraba, M ;

Lavela, P ;

Tirado, JL .

CHEMISTRY OF MATERIALS, 2003, 15 (05) :1210-1216

[2] LiMn2-yCOyO4 (0 ≤ y ≤1) intercalation compounds synthesized from wet-chemical route [J].

Amdouni, N ;

Gendron, F ;

Mauger, A ;

Zarrouk, H ;

Julien, CM .

MATERIALS SCIENCE AND ENGINEERING B-SOLID STATE MATERIALS FOR ADVANCED TECHNOLOGY, 2006, 129 (1-3) :64-75

[3] 3d-Transition metal doped spinels as high-voltage cathode materials for rechargeable lithium-ion batteries [J].

Bhaskar, Aiswarya ;

Mikhailova, Daria ;

Kiziltas-Yavuz, Niluefer ;

Nikolowski, Kristian ;

Oswald, Steffen ;

Bramnik, Natalia N. ;

Ehrenberg, Helmut .

PROGRESS IN SOLID STATE CHEMISTRY, 2014, 42 (04) :128-148

[4] Nanoscale spinel LiFeTiO4 for intercalation pseudocapacitive Li+ storage [J].

Chen, Ruiyong ;

Knapp, Michael ;

Yavuz, Murat ;

Ren, Shuhua ;

Witte, Ralf ;

Heinzmann, Ralf ;

Hahn, Horst ;

Ehrenberg, Helmut ;

Indris, Sylvio .

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2015, 17 (02) :1482-1488

[5] Structural Evolution of Li2Fe1-yMnySiO4 (y=0, 0.2, 0.5, 1) Cathode Materials for Li-Ion Batteries upon Electrochemical Cycling [J].

Chen, Ruiyong ;

Heinzmann, Ralf ;

Mangold, Stefan ;

Chakravadhanula, V. S. Kiran ;

Hahn, Horst ;

Indris, Sylvio .

JOURNAL OF PHYSICAL CHEMISTRY C, 2013, 117 (02) :884-893

[6] Delithiation/relithiation process of LiCoMnO4 spinel as 5 V electrode material [J].

Draeger, Christoph ;

Sigel, Florian ;

Indris, Sylvio ;

Mikhailova, Darla ;

Pfaffmann, Lukas ;

Knapp, Michael ;

Ehrenberg, Helmut .

JOURNAL OF POWER SOURCES, 2017, 371 :55-64

[7] The new Material Science Powder Diffraction beamline at ALBA Synchrotron [J].

Fauth, F. ;

Peral, I. ;

Popescu, C. ;

Knapp, M. .

POWDER DIFFRACTION, 2013, 28 :S360-S370

[8] IMPROVED CAPACITY RETENTION IN RECHARGEABLE 4V LITHIUM LITHIUM MANGANESE OXIDE (SPINEL) CELLS [J].

GUMMOW, RJ ;

DEKOCK, A ;

THACKERAY, MM .

SOLID STATE IONICS, 1994, 69 (01) :59-67

[9]

Gutlich P., 1970, CHEM UNSERER ZEIT, V4, P133, DOI [10.1002/ciuz.19700040502, DOI 10.1002/CIUZ.19700040502]

[10] A novel high-throughput setup for in situ powder diffraction on coin cell batteries [J].

Herklotz, Markus ;

Weiss, Jonas ;

Ahrens, Eike ;

Yavuz, Murat ;

Mereacre, Liuda ;

Kiziltas-Yavuz, Niluefer ;

Draeger, Christoph ;

Ehrenberg, Helmut ;

Eckert, Juergen ;

Fauth, Francois ;

Giebeler, Lars ;

Knapp, Michael .

JOURNAL OF APPLIED CRYSTALLOGRAPHY, 2016, 49 :340-345

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