Journal article
Aliovalent Substitution of V3+ for Co2+ in LiCoPO4 by a Low-Temperature Microwave-Assisted Solvothermal Process
Chemistry of materials, Vol.28(6), pp.1847-1853
03/22/2016
DOI: 10.1021/acs.chemmater.5b05042
Abstract
Electrical and ionic conductivity has proven to be a major limiting factor in the adoption of high-voltage polyanion cathode materials, specifically LiMPO4 (M = Mn, Co, Ni). While the aliovalent substitution of V3+ for Fe2+ in LiFePO4 has been shown recently, no conclusive evidence is available for aliovalent substitutions in the analogous LiCoPO4. This study presents a low-temperature microwave-assisted solvothermal synthesis and characterization of aliovalently substituted LiCo1–3x/2Vx□x/2PO4 for x ≤ 0.07. The as synthesized LiCo1–3x/2Vx□x/2PO4 samples belonging to the Pn21a space group are transformed to the Pnma polymorph via calcination in an inert atmosphere at 525 °C. The LiCo1–3x/2Vx□x/2PO4 samples are characterized with scanning electron microscopy, X-ray diffraction, Rietveld refinement, inductively coupled plasma optical emissions spectroscopy, Raman and infrared spectroscopy, galvanostatic charge/discharge, electrochemical impedance spectroscopy, and cyclic voltammetry. Unlike the prior reports of aliovalent substitution via high-temperature methods, the LiCo1–3x/2Vx□x/2PO4 samples presented here experienced a systematic decrease in the unit cell volume with increasing vanadium substitution. The electrochemical performance and cyclability of LiCo1–3x/2Vx□x/2PO4 is greatly improved compared to the unsubstituted LiCoPO4.
Details
- Title: Subtitle
- Aliovalent Substitution of V3+ for Co2+ in LiCoPO4 by a Low-Temperature Microwave-Assisted Solvothermal Process
- Creators
- Karl J Kreder - Materials Science and Engineering Program & Department of Mechanical Engineering, The University of Texas at Austin, Austin, Texas 78712, United StatesGaurav Assat - Materials Science and Engineering Program & Department of Mechanical Engineering, The University of Texas at Austin, Austin, Texas 78712, United StatesArumugam Manthiram - Materials Science and Engineering Program & Department of Mechanical Engineering, The University of Texas at Austin, Austin, Texas 78712, United States
- Resource Type
- Journal article
- Publication Details
- Chemistry of materials, Vol.28(6), pp.1847-1853
- DOI
- 10.1021/acs.chemmater.5b05042
- ISSN
- 0897-4756
- eISSN
- 1520-5002
- Grant note
- DOI: 10.13039/100000928, name: Welch Foundation, award: F-1254; DOI: 10.13039/100006177, name: Vehicle Technologies Program, award: DEAC0205CH11231
- Language
- English
- Date published
- 03/22/2016
- Academic Unit
- Obstetrics and Gynecology; Urology
- Record Identifier
- 9984051897202771
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