Role of disorder in limiting the true multi-electron redox in ε-LiVOPO4

被引：24

作者：

Rana, Jatinkumar ^{[1
]}

Shi, Yong ^{[1
]}

Zuba, Mateusz J. ^{[1
]}

Wiaderek, Kamila M. ^{[2
]}

Feng, Jun ^{[1
]}

Zhou, Hui ^{[1
]}

Ding, Jia ^{[1
]}

Wu, Tianpin ^{[2
]}

Cibin, Giannantonio ^{[3
]}

Balasubramanian, Mahalingam ^{[2
]}

Omenya, Fredrick ^{[1
]}

Chernova, Natasha A. ^{[1
]}

Chapman, Karena W. ^{[4
]}

Whittingham, M. Stanley ^{[1
]}

Piper, Louis F. J. ^{[1
]}

机构：

[1] SUNY Binghamton, NorthEast Ctr Chem Energy Storage NECCES, Binghamton, NY 13902 USA

[2] Argonne Natl Lab, Adv Photon Source, Xray Sci Div, Argonne, IL 60439 USA

[3] Diamond Light Source Ltd, Diamond House,Harwell Sci & Innovat Campus, Didcot OX11 0DE, Oxon, England

[4] SUNY Stony Brook, Dept Chem, Stony Brook, NY 11974 USA

来源：

JOURNAL OF MATERIALS CHEMISTRY A | 2018年 / 6卷 / 42期

关键词：

POSITIVE-ELECTRODE MATERIALS; LITHIUM BATTERIES; CRYSTAL-STRUCTURE; CATHODE MATERIAL; LIVOPO4; VANADYL; ELECTROCHEMISTRY; EPSILON-VOPO4; PHOSPHATES; GENERATION;

D O I：

10.1039/c8ta06469e

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：

Recent advances in materials syntheses have enabled epsilon-LiVOPO4 to deliver capacities approaching, and in some cases exceeding the theoretical value of 305 mA h g(-1) for 2Li intercalation, despite its poor electronic and ionic conductivity. However, not all of the capacity corresponds to the true electrochemical intercalation/deintercalation reactions as evidenced upon systematic tracking of V valence through combined operando and rate-dependent ex situ X-ray absorption study presented herein. Structural disorder and defects introduced in the material by high-energy ball milling impede kinetics of the high-voltage V5+/V4+ redox more severely than the low-voltage V4+/V3+ redox, promoting significant side reaction contributions in the high-voltage region, irrespective of cycling conditions. The present work emphasizes the need for nanoengineering of active materials without compromising their bulk structural integrity in order to fully utilize high-energy density of multi-electron cathode materials.

引用

页码：20669 / 20677

页数：9

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