The Electrochemical Sodiation of Sb Investigated by Operando X-ray Absorption and Sb-121 Mossbauer Spectroscopy: What Does One Really Learn?

被引：20

作者：

Darwiche, Ali ^{[1
]}

Fehse, Marcus ^{[2
,3
,4
]}

Mahmoud, Abdelfattah ^{[5
]}

La Fontaine, Camille ^{[6
]}

Fraisse, Bernard ^{[1
]}

Hermann, Raphael P. ^{[7
]}

Doublet, Marie-Liesse ^{[1
,4
]}

Monconduit, Laure ^{[1
,4
,8
]}

Sougrati, Moulay T. ^{[1
,4
,8
]}

Ben Yahia, Mouna ^{[1
,4
]}

Stievano, Lorenzo ^{[2
,4
,8
]}

机构：

[1] Univ Montpellier, CNRS, ICGM, F-34095 Montpellier, France

[2] ESRF European Synchrotron, Dutch Belgian DUBBLE, F-38043 Grenoble, France

[3] Delft Univ Technol, Fac Sci Appl, NL-2600 AA Delft, Netherlands

[4] Univ Picardie Jules Verne, Alistore European Res Inst, F-80039 Amiens, France

[5] Univ Liege, Inst Chem B6, CESAM, GreenMat, B-4000 Liege, Belgium

[6] St Aubin, Synchrotron Soleil, F-91192 Gif Sur Yvette, France

[7] Oak Ridge Natl Lab, Mat Sci & Technol Div, Oak Ridge, TN 37813 USA

[8] CNRS, Reseau Sur Stockage Elect Energie RS2E, F-80039 Amiens, France

来源：

BATTERIES-BASEL | 2018年 / 4卷 / 02期

关键词：

X-ray absorption spectroscopy; Mossbauer spectroscopy; DFT calculations; chemometrics; MCR-ALS; Na-ion batteries; alloy reaction; Sb;

D O I：

10.3390/batteries4020025

中图分类号：

O646 [电化学、电解、磁化学];

学科分类号：

081704 ;

摘要：

In this study, we want to highlight the assets and restrictions of X-ray absorption spectroscopy (XAS) and Mossbauer spectroscopy for investigating the mechanism of the electrochemical reaction of antimony electrode materials vs. Na. For this, operando XAS was carried out during the first one and a half cycles, and the whole set of measured data was analysed using a statistical-chemometric approach, while low temperature Mossbauer spectroscopy measurements were carried out ex situ on selected samples stopped at different points of the electrochemical reaction. Complementary ab initio calculations were performed to support the experimental findings. Both techniques show that, upon the first sodiation, most Sb reacts with Na to form disordered Na3Sb. This step is accompanied by the formation of amorphous Sb as an intermediate. Upon inversion of the current Na3Sb is desodiated and an amorphous Sb phase, distinct from the pristine bulk Sb state, is gradually formed. However, both XAS and Mossbauer spectroscopy were unable to spot the formation of intermediate NaxSb phases, which were evinced in previous works by operando Pair Distribution Function analyses. The results shown here clearly assign such failure to the intrinsic inability of both techniques to identify these intermediates.

引用

页数：15