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Role of disorder in limiting the true multi-electron redox in ε-LiVOPO 4
Authors:
Jatinkumar
Rana
(Binghamton University)
,
Yong
Shi
(Binghamton University)
,
Mateusz J.
Zuba
(Binghamton University)
,
Kamila M
Wiaderek
(Argonne National Laboratory)
,
Jun
Feng
(Binghamton University)
,
Hui
Zhou
(Binghamton University)
,
Jia
Ding
(Binghamton University)
,
Tianpin
Wu
(Advanced Photon Source)
,
Giannantonio
Cibin
(Diamond Light Source)
,
Mahalingam
Balasubramanian
(Advanced Photon Source)
,
Frederick O.
Omenya
(Binghamton University)
,
Natasha
Chernova
(Binghamton University)
,
Karena W.
Chapman
(Argonne National Laboratory)
,
M. Stanley
Whittingham
(Binghamton University)
,
Louis F. J.
Piper
(Binghamton University)
Co-authored by industrial partner:
No
Type:
Journal Paper
Journal:
Journal Of Materials Chemistry A
State:
Published (Approved)
Published:
September 2018
Diamond Proposal Number(s):
18423
Abstract: Recent advances in materials syntheses have enabled ε-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.
Diamond Keywords: Batteries; Lithium-ion
Subject Areas:
Chemistry,
Materials,
Energy
Instruments:
B18-Core EXAFS
Other Facilities: Advanced Photon Source
Added On:
25/09/2018 11:21
Discipline Tags:
Energy Storage
Energy
Physical Chemistry
Energy Materials
Chemistry
Materials Science
Technical Tags:
Spectroscopy
X-ray Absorption Spectroscopy (XAS)