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Title: Nanostructured Vanadium Oxide Electrodes for Enhanced Lithium-Ion Intercalation

Abstract

This article summarizes our most recent studies on improved Li+-intercalation properties in vanadium oxides by engineering the nanostructure and interlayer structure. The intercalation capacity and rate are enhanced by almost two orders of magnitude with appropriately fabricated nanostructures. Processing methods for single-crystal V2O5 nanorod arrays, V2O5·nH2O nanotube arrays, and Ni/V2O5·nH2O core/shell nanocable arrays are presented; the morphologies, structures, and growth mechanisms of these nanostructures are discussed. Electrochemical analysis demonstrates that the intercalation properties of all three types of nanostructure exhibit significantly enhanced storage capacity and rate performance compared to the film electrode of vanadium pentoxide. Addition of TiO2 to orthorhombic V2O5 is found to affect the crystallinity, microstructure, and possible interaction force between adjacent layers in V2O5, and subsequently leads to enhanced Li+-intercalation properties in V2O5. The amount of water intercalated in V2O5 is found to have a significant influence on the interlayer spacing and electrochemical performance of V2O5·nH2O. A systematic electrochemical study has demonstrated that the V2O5·0.3H2O film has the optimal water content and exhibits the best Li+-intercalation performance.

Authors:
; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
901767
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Advanced Functional Materials, 16(9):1133–1144
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Wang, Ying, Takahashi, Katsunori, Lee, Kyoungho H., and Cao, Guozhong. Nanostructured Vanadium Oxide Electrodes for Enhanced Lithium-Ion Intercalation. United States: N. p., 2006. Web. doi:10.1002/adfm.200500662.
Wang, Ying, Takahashi, Katsunori, Lee, Kyoungho H., & Cao, Guozhong. Nanostructured Vanadium Oxide Electrodes for Enhanced Lithium-Ion Intercalation. United States. doi:10.1002/adfm.200500662.
Wang, Ying, Takahashi, Katsunori, Lee, Kyoungho H., and Cao, Guozhong. Sun . "Nanostructured Vanadium Oxide Electrodes for Enhanced Lithium-Ion Intercalation". United States. doi:10.1002/adfm.200500662.
@article{osti_901767,
title = {Nanostructured Vanadium Oxide Electrodes for Enhanced Lithium-Ion Intercalation},
author = {Wang, Ying and Takahashi, Katsunori and Lee, Kyoungho H. and Cao, Guozhong},
abstractNote = {This article summarizes our most recent studies on improved Li+-intercalation properties in vanadium oxides by engineering the nanostructure and interlayer structure. The intercalation capacity and rate are enhanced by almost two orders of magnitude with appropriately fabricated nanostructures. Processing methods for single-crystal V2O5 nanorod arrays, V2O5·nH2O nanotube arrays, and Ni/V2O5·nH2O core/shell nanocable arrays are presented; the morphologies, structures, and growth mechanisms of these nanostructures are discussed. Electrochemical analysis demonstrates that the intercalation properties of all three types of nanostructure exhibit significantly enhanced storage capacity and rate performance compared to the film electrode of vanadium pentoxide. Addition of TiO2 to orthorhombic V2O5 is found to affect the crystallinity, microstructure, and possible interaction force between adjacent layers in V2O5, and subsequently leads to enhanced Li+-intercalation properties in V2O5. The amount of water intercalated in V2O5 is found to have a significant influence on the interlayer spacing and electrochemical performance of V2O5·nH2O. A systematic electrochemical study has demonstrated that the V2O5·0.3H2O film has the optimal water content and exhibits the best Li+-intercalation performance.},
doi = {10.1002/adfm.200500662},
journal = {Advanced Functional Materials, 16(9):1133–1144},
number = ,
volume = ,
place = {United States},
year = {Sun Jan 01 00:00:00 EST 2006},
month = {Sun Jan 01 00:00:00 EST 2006}
}
  • Coherent hydrous vanadium pentoxide (V2O5•nH2O) - carbon cryogels (CCs) nanocomposites were synthesized by electrodeposition of vanadium pentoxide onto the porous carbon scaffold which was derived from resorcinol (R) and formaldehyde (F) organic hydrogels. As-fabricated nanocomposites were characterized by scanning electron microscopy (SEM), along with EDAX and nitrogen sorption isotherms which suggested vanadium pentoxide incorporated in the pores of carbon cryogels. The nanocomposites showed much improved discharge capacity and better cyclic stability as compared to hydrous vanadium pentoxide films deposited on platinum foil. The discharge capacity of the nanocomposites reached 280 mAh/g based on the mass of the vandium pentoxide atmore » a current density of 100mA/g and it possessed good cycle stability at different discharge rate. The results demonstrated that electrochemical performances, such as specific discharge capacitance and reversibility of the composite electrode, could be greatly enhanced by the introduction of carbon cryogels (CCs) scaffold with three-dimensionally interconnected porous structure in which V2O5•nH2O homogeneously dispersed.« less
  • V{sub 2}O{sub 5} xerogel films were fabricated by casting V{sub 2}O{sub 5} sols onto fluorine-doped tin oxide (FTO) glass substrates and annealing at 300 C for 3 h in different annealing atmospheres of air and nitrogen. Films prepared in different annealing conditions possess different grain sizes and crystallinity, while the vanadium ion oxidation state also varies, as identified by X-ray absorption spectroscopy. A nitrogen annealing atmosphere induces the presence of defects, such as V{sup 4+} ions, and associated oxygen vacancies. Thus, the presence of defects, whether on the film surface or in the bulk, can be controlled by using airmore » and nitrogen annealing atmospheres in the proper order. Electrochemical impedance analyses reveal enhanced charge-transfer conductivity in films with more V{sup 4+} and oxygen vacancies on the film surface, that is, a film annealed, first, for 0.5 h in air and then for 2.5 h in nitrogen. Lithium-ion intercalation measurements show that, at a charge/discharge current density of 600 mA g{sup -1}, this film possesses a noticeably better lithium-ion storage capability than films without surface defects. This sample starts with an initial discharge capacity of 139 mA h g{sup -1}, and the capacity increases slowly to a maximum value of 156 mA h g{sup -1} in the 15th cycle, followed by a mild capacity degradation in later cycles. After 50 cycles, the discharge capacity is still as high as 136 mA h g{sup -1}. A much improved lithium-ion intercalation capacity and cyclic stability are attributed to V{sup 4+} surface defects and associated oxygen vacancies introduced by N{sub 2} annealing.« less
  • Tailoring nanoarchitecture of materials offers unprecedented opportunities in utilization of their functional properties. Nanostructures of vanadium oxide, synthesized by electrochemical deposition, are studied as a cathode material for rechargeable Na-ion batteries. Ex situ and in situ synchrotron characterizations revealed the presence of an electrochemically responsive bilayered structure with adjustable intralayer spacing that accommodates intercalation of Na{sup +} ions. Sodium intake induces organization of overall structure with appearance of both long- and short-range order, while deintercalation is accompanied with the loss of long-range order, whereas short-range order is preserved. Nanostructured electrodes achieve theoretical reversible capacity for Na{sub 2}V{sub 2}O{sub 5} stoichiometrymore » of 250 mAh/g. The stability evaluation during charge-discharge cycles at room temperature revealed an efficient 3 V cathode material with superb performance: energy density of {approx}760 Wh/kg and power density of 1200 W/kg. These results demonstrate feasibility of development of the ambient temperature Na-ion rechargeable batteries by employment of electrodes with tailored nanoarchitectures.« less
  • Nanomaterials lie at the heart of the fundamental advances in efficient energy storage/conversion and other types of nanodevices in which the surface process and transport kinetics play determining roles. This review describes some recent developments in the synthesis and characterizations of various vanadium oxide nanostructures including nanowires, nanorolls, nanobelts, and ordered arrays of nanorods, nanotubes, and nanocables for significantly enhanced intercalation properties. The major topic of this article is to highlight the lithium ion intercalation properties of nanostructured vanadium oxides for energy storage as well as other applications in sensors, actuators, and transistors.
  • Graphite intercalation compounds of vanadium oxide fluoride, C{sub x}(VOF{sub 3})F, were synthesized in a fluorine atmosphere. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction measurements were used for their structural characterization. These experiments have suggested that cointercalation of fluorine and VOF{sub 3} in the carbon occurs involving local structural modifications and that excess oxygen was present in the graphite layers. The study of electrochemical insertion of lithium was carried out at 25 C in a LiClO{sub 4}-propylene carbonate electrolyte by chronopotentiometry and ac impedance measurements. The interfacial charge-transfer process, associated to the half-reaction occurring during the intercalation, wasmore » found to be independent of the intercalation ratio of lithium cations, y. The chemical diffusion coefficient, {tilde D}{sub Li}, and the conductivity, {sigma}{sub Li}, obtained were deduced from impedance data by considering the geometric surface area. Both are roughly constant for all the y-range: {tilde D}{sub Li} = 3.8 {times} 10{sup {minus}10} cm{sup 2}/s and {sigma}{sub Li} = 9.3 {times} 10{sup {minus}7} {Omega}{sup {minus}1} cm{sup {minus}1} for C{sub 17.7}(VOF{sub 3})F; {tilde D}{sub Li} = 4.5 {times} 10{sup {minus}10} cm{sup 2}/s and {sigma}{sub Li} = 2.7 {times} 10{sup {minus}7} {Omega}{sup {minus}1} cm{sup {minus}1} for C{sub 20.4}(VOF{sub 3})F.« less