The stability of the SEI layer, surface composition and the oxidation state of transition metals at the electrolyte-cathode interface impacted by the electrochemical cycling: X-ray photoelectron spectroscopy investigation

被引:112
作者
Cherkashinin, Gennady [1 ]
Nikolowski, Kristian [2 ,3 ]
Ehrenberg, Helmut [2 ,3 ]
Jacke, Susanne [1 ]
Dimesso, Lucangelo [1 ]
Jaegermann, Wolfram [1 ,4 ]
机构
[1] Tech Univ Darmstadt, Dept Mat Sci, Surface Sci Inst, D-64287 Darmstadt, Germany
[2] Tech Univ Darmstadt, Dept Mat Sci, D-64287 Darmstadt, Germany
[3] Karlsruhe Inst Technol, Inst Appl Mat, D-76344 Eggenstein Leopoldshafen, Germany
[4] Tech Univ Darmstadt, Ctr Smart Interfaces, D-64287 Darmstadt, Germany
关键词
LITHIUM-ION BATTERIES; HIGH-POWER; LI; SPECTRA; PERFORMANCE; LICOO2; PHOTOEMISSION; CAPACITY; XPS; LI(NI1/3CO1/3MN1/3)O-2;
D O I
10.1039/c2cp41134b
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
The stability of the valence state of the 3d transition metal ions and the stoichiometry of LiMO2 (M = Co, Ni, Mn) layered oxides at the surface-electrolyte interface plays a crucial role in energy storage applications. The surface oxidation/reduction of the cations caused by the contact of the solids to air or to the electrolyte results in the blocking of the Li-transport through the interface that leads to the fast batteries deterioration. The influence of the end-of-charge voltage on the chemical composition and the oxidation state of 3d transition metal ions, as well as the stability of the solid-electrolyte interface formed during the electrochemical Li-deintercalation/intercalation of the LiCoO2 and Li(Ni,Mn,Co)O-2, have been investigated by X-ray photoelectron spectroscopy. While the chemical composition of the solid-electrolyte interface is similar for both layered oxide surfaces, the electrochemical cycling to some critical voltage values leads to the disappearance of the interface. By the analysis of the shape of the 2p and 3s photoelectron emissions we show that the formation of the solid-electrolyte interface layer correlates with the partial reduction of the trivalent Co ions at the electrolyte-LiCoO2 interface and the amount of the Co2+ ions is increased as the solid-electrolyte interface vanishes. In contrast, the Mn4+, Co3+ and Ni2+ ions of the Li(Ni,Mn,Co)O-2 are stable at the interface under the electrochemical cycling to higher end-of-charge voltage. A correlation between deterioration of the LiCoO2 and Li(Ni,Mn,Co)O-2 batteries and the change of electronic structure at the surface/interface after the electrochemical cycling has been found. The dissolution of the solid-electrolyte interface layer might be the reason for the fast deterioration of the Li-ion batteries.
引用
收藏
页码:12321 / 12331
页数:11
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