Electrospun nano-vanadium pentoxide cathode

doi:10.1016/j.elecom.2008.11.051

Electrochemistry Communications

Volume 11, Issue 3, March 2009, Pages 522-525

https://doi.org/10.1016/j.elecom.2008.11.051 Get rights and content

Abstract

Nanocrystallites of vanadium pentoxide were synthesized by the hydrothermal treatment of electrospun composite nanofibers. Each crystallite of dimension ⩽100 nm was found to be a single crystal of δ-phase H_xV₄O₁₀ · nH₂O. The crystallinity and morphology was maintained on heating to 500 °C when V₂O₅ was formed. The electrochemical capacity of the nano-V₂O₅ in a lithium cell was found to be above 350 mAh/g. The columbic efficiency is close to 100% when small amounts of lithium bis(oxalato)borate is added to the LiPF₆ electrolyte.

Introduction

A recent report [1] emphasized the need for much higher capacity cathode materials; this can be accomplished by using transition metals that have the capability to react with more than one lithium per redox ion. The report also emphasized the need for a better understanding of nano-sized materials. There has been much interest in such materials as the electrodes for lithium batteries [2], and their successful formation represents a challenge to the synthetic chemist [3], [4], [5]. A variety of methods have been used including precipitation from solution. Hydrothermal and solvothermal methods have proved highly successful in the formation of open or layered structures suitable for lithium intercalation [6], [7], [8]. Vanadium oxides have been of particular interest because of the availability of the two-electron V⁵⁺–V³⁺ couple and because of the variety of possible structures that are formed, leading to the possibility of tailoring the structure for cathode use. A range of nano-sized vanadium oxides have recently been synthesized, including nanorods [9], nanotubes [10], and vanadium oxide nanobelts [11].

We have shown [12] that nano-sized Mn₃O₄ formed from electrospun polymeric fibers showed promising anodic behavior, comparable to the pioneering work on the CoO anode [13]. Here, we report the extension of that work to the formation of nano-sized vanadium pentoxide, which has one of the highest theoretical capacities, 510 Ah/kg, of any transition metal oxide by a two-electron redox process. We used the electrospinning method to form the precursor that is hydrothermally treated to form nano-sized crystals of the double sheet δ-phase of vanadium oxide. This in turn was converted to the single sheet V₂O₅ by a thermal treatment.

Section snippets

Experimental

Poly-methylmethacralate (PMMA) of molecular weight 350,000, chloroform (CHCl₃), N, N dimethylformamide (DMF) and vanadium (V) oxytriisopropoxide (VOTIP) from Sigma–Aldrich were used as received. A solution of 0.8 g/ml VOTIP and 0.08 g/ml PMMA in a 1:1 DMF/CHCl₃ solvent was placed in a thin pipette. A positive potential of 20 kV was applied between this polymer solution and an aluminum foil collector; the pipette and current collector were placed 20 cm apart. Fibers were formed on the aluminum

Results and discussion

The electrospun fibers of PMMA and vanadium oxide have a diameter between 200 and 500 nm as shown in Fig. 1 (top inset). After hydrothermal treatment, the fibrous morphology is maintained, but they now have a belt-shape of 40–70 nm wide, 10–20 nm thick and several micrometers long. From the powder X-ray diffraction, Fig. 1 (middle), which shows only 00l reflections, it is clear that this compound is layered with an interlayer spacing of 11.40 Å. This spacing and the missing 002 reflection is

Conclusions

Unlike the nano δ-phase, nano-fibrous vanadium pentoxide was found to give a high capacity of 350 mAh/g, approaching a two-electron reduction of the vanadium. This capacity was maintained above 240 mAh/g for 25 cycles, even though the structure changed to a disordered rock-salt structure just as with bulk material. The addition of 5% LiBOB into the LiPF₆ electrolyte brought the coulombic efficiency to 100% because of the formation of an improved electrode/electrolyte interface.

Acknowledgments

Financial support from the National Science Foundation through Grant DMR-0705657, and from the US Dept. of Energy through the BATT program at Lawrence Berkeley National Laboratory is gratefully acknowledged. The authors would like to thank Prof. Wayne E. Jones Jr. at the Department of Chemistry at Binghamton and Dr. Hong Dong at the Department of Textiles and Apparel, Cornell University for valuable discussion and suggestions.

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Electrospun nano-vanadium pentoxide cathode

Abstract

Introduction

Section snippets

Experimental

Results and discussion

Conclusions

Acknowledgments

Solid State Ionics

Mater. Chem. Phys.

J. Power Sources

Mat. Res. Bull.

Mater. Res. Bull.

Mater. Res. Bull.

Electrochem. Commun.

Solid State Ionics

Dalton Transactions

Electrochemical and Solid-State Letters

Nature Nanotechnology