skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Exploring Highly Reversible 1.5-Electron Reactions (V3+/V4+/V5+) in Na3VCr(PO4)3 Cathode for Sodium-Ion Batteries

Journal Article · · ACS Applied Materials and Interfaces
 [1];  [2];  [1];  [1];  [1];  [1];  [1];  [3];  [2];  [4];  [1];  [1]
  1. Xiamen Univ., Xiamen (People's Republic of China)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. National High Magnetic Field Lab., Tallahassee, FL (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States); Stanford Univ., Stanford, CA (United States)
+ Show Author Affiliations

The development of highly reversible multielectron reaction per redox center in sodium super ionic conductor-structured cathode materials is desired to improve the energy density of sodium-ion batteries. Here, we investigated more than one-electron storage of Na in Na3VCr(PO4)3. Combining a series of advanced characterization techniques such as ex situ 51V solid-state nuclear magnetic resonance, X-ray absorption near-edge structure, and in situ X-ray diffraction, we reveal that V3+/V4+ and V4+/V5+ redox couples in the materials can be accessed, leading to a 1.5-electron reaction. It is also found that a light change on the local electronic and structural states or phase change could be observed after the first cycle, resulting in the fast capacity fade at room temperature. As a result, we also showed that the irreversibility of the phase changes could be largely suppressed at low temperature, thus leading to a much improved electrochemical performance.

Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
National Key Research and Development Program of China; National Natural Science Foundation of China (NSFC); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1460535
Journal Information:
ACS Applied Materials and Interfaces, Vol. 9, Issue 50; ISSN 1944-8244
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 96 works
Citation information provided by
Web of Science

References (24)

Promise and reality of post-lithium-ion batteries with high energy densities journal March 2016
Polyanion-Type Electrode Materials for Sodium-Ion Batteries journal January 2017
Phosphate Framework Electrode Materials for Sodium Ion Batteries journal January 2017
Molybdenum Substituted Vanadyl Phosphate ε-VOPO 4 with Enhanced Two-Electron Transfer Reversibility and Kinetics for Lithium-Ion Batteries journal April 2016
Sodium Extraction from NASICON-Structured Na 3 MnTi(PO 4 ) 3 through Mn(III)/Mn(II) and Mn(IV)/Mn(III) Redox Couples journal September 2016
Alkaline Excess Strategy to NASICON-Type Compounds towards Higher-Capacity Battery Electrodes journal January 2016
Enhanced high-rate performance of manganese substituted Na 3 V 2 (PO 4 ) 3 /C as cathode for sodium-ion batteries journal May 2016
Effect of aluminum doping on carbon loaded Na3V2(PO4)3 as cathode material for sodium-ion batteries journal October 2015
Effect of Iron Substitution in the Electrochemical Performance of Na 3 V 2 (PO 4 ) 3 as Cathode for Na-Ion Batteries journal January 2015
Benefits of Chromium Substitution in Na 3 V 2 (PO 4 ) 3 as a Potential Candidate for Sodium-Ion Batteries journal April 2015
Nanoflake-Assembled Hierarchical Na 3 V 2 (PO 4 ) 3 /C Microflowers: Superior Li Storage Performance and Insertion/Extraction Mechanism journal February 2015
An all-solid state NASICON sodium battery operating at 200 °C journal February 2014
The First Report on Excellent Cycling Stability and Superior Rate Capability of Na 3 V 2 (PO 4 ) 3 for Sodium Ion Batteries journal November 2012
Strong Impact of the Oxygen Content in Na 3 V 2 (PO 4 ) 2 F 3– y O y (0 ≤ y ≤ 0.5) on Its Structural and Electrochemical Properties journal October 2016
Electrochemical Na Extraction/Insertion of Na 3 V 2 O 2 x (PO 4 ) 2 F 3–2 x journal December 2013
7 Li and 51 V MAS NMR Study of the Electrochemical Behavior of Li 1+ x V 3 O 8 journal July 2004
V IV Disproportionation Upon Sodium Extraction From Na 3 V 2 (PO 4 ) 2 F 3 Observed by Operando X-ray Absorption Spectroscopy and Solid-State NMR journal February 2017
Superior Electrochemical Performance and Storage Mechanism of Na 3 V 2 (PO 4 ) 3 Cathode for Room-Temperature Sodium-Ion Batteries journal October 2012
A Powder Neutron Diffraction Investigation of the Two Rhombohedral NASICON Analogues:  γ-Na 3 Fe 2 (PO 4 ) 3 and Li 3 Fe 2 (PO 4 ) 3 journal February 2000
Relationship between Phase Transition Involving Cationic Exchange and Charge–Discharge Rate in Li 2 FeSiO 4 journal January 2014
A new phenomenon in sodium batteries: Voltage step due to solvent interaction journal September 2014
Subzero-Temperature Cathode for a Sodium-Ion Battery journal June 2016
A Honeycomb-Layered Oxide Cathode for Sodium-Ion Batteries with Suppressed P3-O1 Phase Transition journal November 2016
Insights into the Effects of Zinc Doping on Structural Phase Transition of P2-Type Sodium Nickel Manganese Oxide Cathodes for High-Energy Sodium Ion Batteries journal August 2016

Cited By (9)

Towards High-Performance Aqueous Sodium-Ion Batteries: Stabilizing the Solid/Liquid Interface for NASICON-Type Na 2 VTi(PO 4 ) 3 using Concentrated Electrolytes journal April 2018
Research Progress in Multielectron Reactions in Polyanionic Materials for Sodium‐Ion Batteries journal October 2018
High Capacity and High‐Rate NASICON‐Na 3.75 V 1.25 Mn 0.75 (PO 4 ) 3 Cathode for Na‐Ion Batteries via Modulating Electronic and Crystal Structures journal December 2019
Three Electron Reversible Redox Reaction in Sodium Vanadium Chromium Phosphate as a High‐Energy‐Density Cathode for Sodium‐Ion Batteries journal January 2020
A NASICON‐Type Positive Electrode for Na Batteries with High Energy Density: Na 4 MnV(PO 4 ) 3 journal August 2018
Ultralong‐Life Chloride Ion Batteries Achieved by the Synergistic Contribution of Intralayer Metals in Layered Double Hydroxides journal November 2019
Possible high-potential ilmenite type N a 1 M O 3   ( M = V – Ni ) cathodes realized by dominant oxygen redox reaction journal January 2020
Rational Architecture Design Enables Superior Na Storage in Greener NASICON-Na 4 MnV(PO 4 ) 3 Cathode journal June 2018
A High‐Energy NASICON‐Type Cathode Material for Na‐Ion Batteries journal March 2020

Similar Records

Related Subjects

25 ENERGY STORAGE
NASICON
NMR
XAS
low temperature
multielectron reaction
sodium-ion batteries
structural evolution