Electrochemical Performance of High‐Valence Mo6+ and Low‐Valence Mn2+ Doped‐ Na3V2(PO4)3@C Cathode for Sodium‐Ion Batteries
- 17 October 2022
- journal article
- research article
- Published by Wiley in Chemphyschem
- Vol. 23 (24) , e202200459
Abstract
The sodium superionic conductor (NASICON)‐Na3V2(PO4)3 (NVP) is an attractive cathode for sodium‐ion batteries, which is still confronted with limited rate performance due to its low electronic conductivity. In this paper, a chemical strategy is adopted to partially replace V3+ of the NVP framework by low‐valence Mn2+ and high‐valence Mo6+ substitution. The crystal structure, sodium‐ion diffusion coefficient and electrochemical performance of Mn−Mo‐doped [Na3.94V0.98Mo0.02Mn(PO4)3@C] cathode were investigated. X‐ray diffraction confirmed the NASICON‐type structure and XPS analysis confirmed the oxidation state of Mn and Mo in doped NVP cathode. The Na ion diffusion processes were inferred from Cyclic Voltammetry (CV), Galvanostatic intermittent titration technique (GITT) and Electrochemical Impedance Spectroscopy (EIS) measurement, which clearly show rapid Na‐ion diffusion in NASICON‐type cathode materials. The Mn−Mo‐substituted NVP shows smoother charge‐discharge profiles, improved rate performance (64.80 mAh/g at 1 C rate), better energy density (308.61 mWh/g) and superior Na‐ion kinetics than that of unsubstituted NVP@C cathode. Their enhanced performance is attributed to large interstitial volume mainly created by high valence Mo6+ and enhanced capacity is attributed to the low valence Mn2+ doping. These results demonstrate that Mn−Mo‐doped NVP cathode is strongly promising cathode material for sodium‐ion batteries.Keywords
Funding Information
- Anusandhan National Research Foundation (000316)
- Anusandhan National Research Foundation (IMPRINT ΙΙ C)
This publication has 41 references indexed in Scilit:
- High valence Mo-doped Na3V2(PO4)3/C as a high rate and stable cycle-life cathode for sodium batteryJournal of Materials Chemistry A, 2017
- Sodium Extraction from NASICON-Structured Na3MnTi(PO4)3 through Mn(III)/Mn(II) and Mn(IV)/Mn(III) Redox CouplesChemistry of Materials, 2016
- Improvement on the high-rate performance of Mn-doped Na3V2(PO4)3/C as a cathode material for sodium ion batteriesRSC Advances, 2016
- Li-ion battery materials: present and futureMaterials Today, 2015
- Glucose-assisted synthesis of Na3V2(PO4)3/C composite as an electrode material for high-performance sodium-ion batteriesJournal of Power Sources, 2014
- Li3V2(PO4)3 cathode materials for lithium-ion batteries: A reviewJournal of Power Sources, 2014
- Synthesis and Battery Studies of Sodium Cobalt Oxides, NaCoO2 CathodesAdvanced Materials Research, 2012
- Electrochemical and Thermal Properties of NASICON Structured Na3V2(PO4)3as a Sodium Rechargeable Battery Cathode: A Combined Experimental and Theoretical StudyJournal of the Electrochemical Society, 2012
- Synthesis and characterization of high-temperature hexagonal P2-Na0.6 MnO2 and its electrochemical behaviour as cathode in sodium cellsJournal of Materials Chemistry, 2002
- Crystal structures and crystal chemistry in the system Na1+xZr2SixP3−xO12Materials Research Bulletin, 1976