Approaching Better Cycleability of LiCoPO4 by Vanadium Modification
Full article
| Общее |
Language:
Английский,
Genre:
Full article,
Status:
Published,
Source type:
Original
|
| Journal |
Journal of Materials Science and Engineering (A & B)
ISSN: 2161-6213
, E-ISSN: 2161-6221
|
| Output data |
Year: 2016,
Volume: 213,
Pages: 105-113
Pages count
: 9
DOI:
10.1016/j.mseb.2016.04.013
|
| Authors |
Kosova N.V.
1
,
Podgornova O.A.
1
,
Bobrikov I.A.
2
,
Kaichev V.V.
3,4
,
Bukhtiyarov A.V.
3
|
| Affiliations |
| 1 |
Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Sciences, 18 Kutateladze, 630128 Novosibirsk, Russia
|
| 2 |
Joint Institute for Nuclear Research, 6 Joliot-Curie, 141980 Dubna, Russia
|
| 3 |
Boreskov’ Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, 5 pr. Lavrent’eva, 630090 Novosibirsk, Russia
|
| 4 |
Novosibirsk State University, 2 Pirogova, 630090 Novosibirsk, Russia
|
|
Funding (2)
|
1
|
The Ministry of Education and Science of the Russian Federation
|
14.621.21.0004 (RFMEFI62114X0004)
|
|
2
|
Russian Foundation for Basic Research
|
14-03-01082
|
A series of (1 − y)LiCoPO4·yLi3V2(PO4)3 with 0 ≤ y ≤ 1 was prepared via mechanochemically assisted carbothermal reduction at 750 °C. Structure and electrochemistry were studied by a complex of physico-chemical methods including XRD, NPD, FTIR, NEXAFS, TEM, EDX STEM, and galvanostatic cycling. It has been shown that only a small amount of V ions incorporates into the LiCoPO4 structure. The other V ions form monoclinic Li3V2(PO4)3. Incorporated V ions are in a mixed oxidation state and predominantly substitute for Co2+. The compensation mechanism for supervalent V ions substitution in LiCoPO4 involves the lithium vacancies formation. The as-prepared (1 − y)LiCoPO4·yLi3V2(PO4)3 with low y show the enhanced electrochemical behavior compared to pure LiCoPO4, especially in the 4.0–5.0 V range, due to a suitable amount of structural defects, which improve ionic and electronic conductivity, and to the presence of the Li-conductive Li3V2(PO4)3 on the surface of the LiCoPO4 particles promoting the deliverance of the Li ions from the electrolyte to the (0 1 0) facet.