Electrochemical Na Extraction/Insertion of Na3V2O2x(PO4)2F3-2x

被引：117

作者：

Serras, Paula ^{[1
]}

Palomares, Veronica ^{[1
]}

Alonso, Javier ^{[2
]}

Sharma, Neeraj ^{[3
]}

Miguel Lopez del Amo, Juan ^{[4
]}

Kubiak, Pierre ^{[4
]}

Luisa Fdez-Gubieda, Maria ^{[2
,5
]}

Rojo, Teofilo ^{[1
,4
]}

机构：

[1] Univ Pais Vasco UPV EHU, Dept Quim Inorgan, Bilbao, Spain

[2] BCMaterials, Derio, Spain

[3] Univ New S Wales, Sch Chem, Sydney, NSW 2052, Australia

[4] CIC ENERGIGUNE, Minano 01510, Spain

[5] Univ Pais Vasco UPV EHU, Dept Elect & Elect, Bilbao, Spain

来源：

CHEMISTRY OF MATERIALS | 2013年 / 25卷 / 24期

关键词：

sodium ion batteries; electrochemistry; mixed valence sodium vanadium fluorophosphate; X-ray diffraction and X-ray absorption near edge structure; BOND-VALENCE PARAMETERS; SODIUM-ION; CATHODE MATERIALS; BATTERIES; SPECTRA; VOLTAGE;

D O I：

10.1021/cm403679b

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：

A mixed-valence V3+/V4+ composite material belonging to the Na3V2O2x(PO4)2F(3-2)/C family is synthesized and the electrochemical Na extraction/insertion mechanism is determined using a combination of high-resolution synchrotron X-ray diffraction (XRD) data, X-ray absorption spectroscopy (XAS), Na-23 and F-19 solid state nuclear magnetic resonance (NMR), double titration (for the elucidation of the vanadium oxidation state), and electrochemical measurements. The vanadium oxidation state is found to be +3.8 for the as-prepared sample. Detailed analysis of the cathode structural evolution illustrated that the V4+/V5+ couple is active in this compound during electrochemical cycling between 2.8 V and 4.3 V. This study demonstrates how the sodium-ion extraction and insertion pathways in cathode materials can be followed (and verified) using several experimental techniques, especially when multiple potential oxidation states are present in the parent compound.

引用

页码：4917 / 4925

页数：9

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