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Title: Visualization of structural evolution and phase distribution of a lithium vanadium oxide (Li1.1V3O8) electrode via an operando and in situ energy dispersive X-ray diffraction technique

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/c7cp02239e· OSTI ID:1376157
 [1];  [2];  [3];  [1];  [4];  [5];  [6];  [7];  [8]; ORCiD logo [7]
  1. Stony Brook Univ., NY (United States). Department of Materials Science and Engineering
  2. Stony Brook Univ., NY (United States). Dept. of Chemistry
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Energy Sciences Directorate
  4. Rensselaer Polytechnic Inst., Troy, NY (United States). Department of Materials Science and Engineering
  5. Rensselaer Polytechnic Inst., Troy, NY (United States). Department of Materials Science and Engineering and Center for Materials, Devices, and Integrated Systems
  6. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  7. Stony Brook Univ., NY (United States). Department of Materials Science and Engineering and Department of Chemistry
  8. Stony Brook Univ., NY (United States). Department of Materials Science and Engineering and Department of Chemistry; Brookhaven National Lab. (BNL), Upton, NY (United States). Energy Sciences Directorate
+ Show Author Affiliations

We present Li1+nV3O8 (n = 0–0.2) has been extensively investigated as a cathode material for Li ion batteries because of its superior electrochemical properties including high specific energy and good rate capability. In this paper, a synchrotron based energy dispersive X-ray diffraction (EDXRD) technique was employed to profile the phase transitions and the spatial phase distribution of a Li1.1V3O8 electrode during electrochemical (de)lithiation in situ and operando. As annealing temperature during the preparation of the Li1.1V3O8 material has a strong influence on the morphology and crystallinity, and consequently influences the electrochemical outcomes of the material, Li1.1V3O8 materials prepared at two different temperatures, 500 and 300°C (LVO500 and LVO300), were employed in this study. The EDXRD spectra of LVO500 and LVO300 cells pre-discharged at C/18, C/40 and C/150 were recorded in situ, and phase localization and relative intensity of the peaks were compared. For cells discharged at the C/18 rate, although α and β phases were distributed uniformly within the LVO500 electrode, they were localized on two sides of the LVO300 electrode. Discharging rates of C/40 and C/150 led to homogeneous β phase formation in both LVO500 and LVO300 electrodes. Furthermore, the phase distribution as a function of position and (de)lithiation extent was mapped operando as the LVO500 cell was (de)lithiated. In conclusion, the operando data indicate that (1) the lithiation reaction initiated from the side of the electrode facing the Li anode and proceeded towards the side facing the steel can, (2) during discharge the phase transformation from a Li-poor to a Li-rich α phase and the formation of a β phase can proceed simultaneously in the electrode after the first formation of a β phase, and (3) the structural evolution occurring during charging is not the reverse of that during discharge and takes place homogenously throughout the electrode.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012704; SC0012673; AC02-06CH11357
OSTI ID:
1376157
Report Number(s):
BNL-114114-2017-JA
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Vol. 19, Issue 21; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 20 works
Citation information provided by
Web of Science

References (42)

Rechargeable Lithium/Vanadium Oxide Cells Utilizing 2Me-THF∕LiAsF[sub 6] journal January 1981
Energy Dispersive X-ray Diffraction (EDXRD) of Li 1.1 V 3 O 8 Electrochemical Cell journal January 2017
The Origin of Capacity Fading upon Lithium Cycling in Li[sub 1.1]V[sub 3]O[sub 8] journal January 2005
Electrochemical Reduction of Silver Vanadium Phosphorus Oxide, Ag 2 VO 2 PO 4 : The Formation of Electrically Conductive Metallic Silver Nanoparticles journal October 2009
Tracking inhomogeneity in high-capacity lithium iron phosphate batteries journal February 2015
Carbon nanotube–metal oxide composite electrodes for secondary lithium-based batteries journal June 2012
Operando identification of the point of [Mn2]O4 spinel formation during γ-MnO2 discharge within batteries journal July 2016
Graphene Nanoribbon/V 2 O 5 Cathodes in Lithium-Ion Batteries journal June 2014
Spray-Drying Synthesis and Electrochemical Performance of Lithium Vanadates as Positive Electrode Materials for Lithium Batteries journal January 2008
Ultrathin Na 1.1 V 3 O 7.9 Nanobelts with Superior Performance as Cathode Materials for Lithium-Ion Batteries journal August 2013
Structural properties of Li1+xV3O8 upon lithium insertion at ambient and high temperature journal March 1998
Structural characterization of Li1+xV3O8 insertion electrodes by single-crystal X-ray diffraction journal August 1993
A combined X-ray and neutron Rietveld study of the chemically lithiated electrode materials Li2.7V3O8 and Li4.8V3O8 journal January 2005
A soft chemistry synthesis and electrochemical properties of LiV3O8 as cathode material for lithium secondary batteries journal May 2005
Layered Lithium Vanadium Fluorophosphate, Li 5 V(PO 4 ) 2 F 2 : A 4 V Class Positive Electrode Material for Lithium-Ion Batteries journal July 2008
Lithium Intercalation into Vanadium Pentoxide:  a Theoretical Study journal August 1999
Phase Transition, Electrochemistry, and Structural Studies of High Rate Li x V 3 O 8 Cathode with Nanoplate Morphology journal October 2013
Redox Behavior of Vanadium Oxide Nanotubes As Studied by X-ray Photoelectron Spectroscopy and Soft X-ray Absorption Spectroscopy journal August 2003
Facile synthesis of cookies-shaped LiV3O8 cathode materials with good cycling performance for lithium-ion batteries journal January 2014
Novel chemical method for synthesis of LiV3O8 nanorods as cathode materials for lithium ion batteries journal January 2004
Interconnected mesoporous V 2 O 5 electrode: impact on lithium ion insertion rate journal January 2016
Electrochemical reduction of an Ag 2 VO 2 PO 4 particle: dramatic increase of local electronic conductivity journal January 2015
Effects of different chelating agents on the composition, morphology and electrochemical properties of LiV3O8 crystallites synthesized via sol–gel method journal May 2013
Vanadium Oxide−PANI Nanocomposite-Based Macroscopic Fibers: 1D Alcohol Sensors Bearing Enhanced Toughness journal September 2008
Large-scale synthesis of Li1.2V3O8 as a cathode material for lithium secondary battery via a soft chemistry route journal February 2009
Hetaerolite Profiles in Alkaline Batteries Measured by High Energy EDXRD journal November 2014
Li x V 2 O 5 /LiV 3 O 8 nanoflakes with significantly improved electrochemical performance for Li-ion batteries journal January 2014
Lithium Insertion into Vanadium Oxide Nanotubes: Electrochemical and Structural Aspects journal December 2005
Novel Method for Synthesis of γ-Lithium Vanadium Oxide as Cathode Materials in Lithium Ion Batteries journal November 1999
Synthesis and characterization of sodium vanadium oxide gels: the effects of water (n) and sodium (x) content on the electrochemistry of NaxV2O5·nH2O journal January 2011
Li∕Li[sub 1+x]V[sub 3]O[sub 8] Secondary Batteries journal January 1985
Carbon nanotube substrate electrodes for lightweight, long-life rechargeable batteries journal January 2011
Electrochemical reduction of Ag 2 VP 2 O 8 composite electrodes visualized via in situ energy dispersive X-ray diffraction (EDXRD): unexpected conductive additive effects journal January 2015
Investigation of Structural Evolution of Li 1.1 V 3 O 8 by In Situ X-ray Diffraction and Density Functional Theory Calculations journal February 2017
Graphene-nanosheet-wrapped LiV3O8 nanocomposites as high performance cathode materials for rechargeable lithium-ion batteries journal March 2016
Mapping the Inhomogeneous Electrochemical Reaction Through Porous LiFePO 4 -Electrodes in a Standard Coin Cell Battery journal March 2015
Solid solutions Li1+xV3O8 as cathodes for high rate secondary Li batteries journal August 1984
Aqueous rechargeable lithium batteries using NaV 6 O 15 nanoflakes as high performance anodes journal January 2014
In Situ Energy Dispersive X-ray Diffraction Study of Prototype LiMnO4- and LiFePO4-Based Coin Cell Batteries journal April 2013
The reaction current distribution in battery electrode materials revealed by XPS-based state-of-charge mapping journal January 2016
Reversible Lithium Storage at Highly Populated Vacant Sites in an Amorphous Vanadium Pentoxide Electrode journal October 2014
Manganese Vanadium Oxide Nanotubes:  Synthesis, Characterization, and Electrochemistry journal November 2001

Cited By (3)

High capacity vanadium oxide electrodes: effective recycling through thermal treatment journal January 2019
A prototype handheld X-ray diffraction instrument journal October 2018
Operando Study of LiV 3 O 8 Cathode: Coupling EDXRD Measurements to Simulations journal January 2018

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