Li+ intercalation in isostructural Li2VO3 and Li2VO2F with O2- and mixed O2-/F- anions

被引:72
|
作者
Chen, Ruiyong [1 ,2 ]
Ren, Shuhua [2 ]
Yavuz, Murat [1 ,3 ,4 ]
Guda, Alexander A. [5 ]
Shapovalov, Viktor [5 ]
Witter, Raiker [2 ,6 ]
Fichtner, Maximilian [1 ,2 ]
Hahn, Horst [1 ,2 ,7 ]
机构
[1] Helmholtz Inst Ulm Electrochem Energy Storage, D-89081 Ulm, Germany
[2] Karlsruhe Inst Technol, Inst Nanotechnol, D-76021 Karlsruhe, Germany
[3] Karlsruhe Inst Technol, Inst Appl Mat, D-76021 Karlsruhe, Germany
[4] Tech Univ Darmstadt, Mat Sci, D-64287 Darmstadt, Germany
[5] Southern Fed Univ, Int Res Ctr Smart Mat, Rostov Na Donu 344090, Russia
[6] Tallinn Univ Technol, Technomedicum, EE-19086 Tallinn, Estonia
[7] Tech Univ Darmstadt, Inst Mat Sci, Joint Res Lab Nanomat, D-64287 Darmstadt, Germany
关键词
LITHIUM-ION BATTERIES; ROCK-SALT PHASE; CATHODE MATERIALS; ELECTROCHEMICAL PERFORMANCE; STRUCTURAL REFINEMENT; POWDER DIFFRACTION; HIGH-CAPACITY; MECHANISMS; ELECTRODES; STORAGE;
D O I
10.1039/c5cp02505b
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
Mixed-anion materials for Li-ion batteries have been attracting attention in view of their tunable electrochemical properties. Herein, we compare two isostructural (Fm (3) over barm) model intercalation materials Li2VO3 and Li2VO2F with O2- and mixed O2-/F- anions, respectively. Synchrotron X-ray diffraction and pair distribution function data confirm large structural similarity over long-range and at the atomic scale for these materials. However, they show distinct electrochemical properties and kinetic behaviour arising from the different anion environments and the consequent difference in cationic electrostatic repulsion. In comparison with Li2VO3 with an active V4+/5+ redox reaction, the material Li2VO2F with oxofluoro anions and the partial activity of V3+/5+ redox reaction favor higher theoretical capacity (460 mA h g(-1) vs. 230 mA h g(-1)), higher voltage (2.5 V vs. 2.2 V), lower polarization (0.1 V vs. 0.3 V) and faster Li+ chemical diffusion (similar to 10(-9) cm(2) s(-1) vs. similar to 10(-11) cm(2) s(-1)). This work not only provides insights into the understanding of anion chemistry, but also suggests the rational design of new mixed-anion battery materials.
引用
收藏
页码:17288 / 17295
页数:8
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