Green Car Congress  
Home Topics Archives About Contact  RSS Headlines

« Six mobility start-ups move into the Volkswagen Incubator in the Transparent Factory; focus on Big Data | Main | Toyota CSRC launches new research tracks on autonomous & connected vehicle technologies; 11 projects with 8 institutions »

Print this post

ORNL team finds way to deliver on promise of VO2(B) Li-ion cathode

2 August 2017

Researchers at Oak Ridge National Laboratory (ORNL) have discovered a way to achieve the promise of bronze-phase vanadium dioxide [VO2(B)] as an electrode material for Li-ion batteries. In a paper in the ACS journal Nano Letters, the team reports that epitaxial VO2(B) films can accomplish the theoretical limit for capacity with persistent charging−discharging cyclability owing to the high structural stability and unique open pathways for Li-ion conduction.

Using atomic-scale characterization via scanning transmission electron microscopy and density functional theory calculations, the researchers determined that that the unique open pathways in VO2(B) provide the most stable sites for Li adsorption and diffusion. The work ultimately demonstrates that VO2(B) is a highly promising energy storage material and has no intrinsic hindrance in achieving superior cyclability with a very high power and capacity in a Li-ion conductor.

VO2(B) has been long regarded as a promising electrode material for LIBs after being first proposed in 1994 … owing to low cost, nontoxicity, and abundant sources. In addition, the theoretical capacity and energy density of VO2(B) (323 mAh/g at a redox voltage of 2.6 V, 0.84 Wh/g) are higher than those of state-of-the-art LIB electrodes, such as LiCoO2 (274 mAh/g at 4 V, 1.1 Wh/g), LiFePO4 (165 mAh/g at 3.5 V, 0.58 Wh/g), Nb2O5 (200 mAh/g at 1.2−2.4 V, 0.24−0.48 Wh/ g), and V2O5 (294 mAh/g at 2.7 V, 0.79 Wh/g). In particular, VO2(B) stands out because of its unique open framework with channels formed from edge-sharing VO6 octahedra. Thus, VO2(B) has been expected to exhibit both high capacity and rapid Li ion diffusion.

However, there has been no successful experimental confirmation of such intriguing properties despite many attempts with various VO2(B) nanostructures, including quantum-dots coated nano-structures, nanobelts, nanoscrolls, and mesocrystals. So far, the low capacity and rapid irreversible capacity loss have been observed in VO2(B) electrodes, hampering their further development. Furthermore, since VO2(B) is a metastable phase and easily forms a mixed phase with other VO2 polymorphs and/or other vanadium oxides with oxidation states other than V4+, it is still unclear whether such poor performance is intrinsic to VO2(B) or attributed to extrinsic factors, such as binder-induced losses, structural defects, dislocations, amorphous phases, and mixed orientations.

Here, we report the high capacity and excellent cycling performance with binder-free highly conductive VO2(B) films as LIB electrodes.

—Lee et al.

Batteries_promising_electrode_mats_ORNL
Researchers predicted where lithium ions (green spheres) would pack and move in an open framework of epitaxially strained vanadium dioxide, depicted here by a stick model (oxygen-connecting bonds are red and vanadium-connecting bonds, turquoise). Guided by theory and computation, they designed, synthesized and tested the material—proving it indeed had excellent storage capacity, ion conduction and structural stability. Image by Panchapakesan Ganesh, Oak Ridge National Laboratory/Dept. of Energy. Click to enlarge.

ORNL’s Ho Nyung Lee and his team used an advanced synthesis technique using pulsed laser epitaxy (PLE) to fabricate thin-film crystals and demonstrated that they remained stable even after numerous electrochemical charge/discharge cycles.

Lee
Electrochemical performance of VO2(B) electrodes. (a) Galvanostatic discharge (Li intercalation)−charge (Li deintercalation) profile of an epitaxial VO2(B) film in a voltage range of 1.5−3.2 V. At various current densities, a plateau related to the Li reduction into VO2(B) appears near 2.6 eV. (b) Capacity as a function of the discharging rate. The capacity of the epitaxial VO2(B) films (solid symbols) is close to the theoretical value (323 mAh/g). The capacity values of pure V2O5, nanobelt VO2(B), nanoscroll VO2(B), mesocrystal VO2(B), carbon, or graphene quantum-dots coated VO2(B) are included for comparison. (c) Cyclic capacity test up to 200 cycles reveals a Coulombic efficiency close to 100%. Credit: ACS, Lee et al. Click to enlarge.

The research provides a design strategy for more efficient, long-lived, miniaturized ionic conductors.

—Panchapakesan Ganesh of ORNL, who predicted vanadium dioxide’s theoretical capacity and lithium ion pathways

Resources

  • Shinbuhm Lee, Xiao-Guang Sun, Andrew A. Lubimtsev, Xiang Gao, Panchapakesan Ganesh, Thomas Z. Ward, Gyula Eres, Matthew F. Chisholm, Sheng Dai, and Ho Nyung Lee (2017) “Persistent Electrochemical Performance in Epitaxial VO2(B)” Nano Letters 17 (4), 2229-2233 doi: 10.1021/acs.nanolett.6b04831

  • Howard T Evans and John M Hughes (1990) “Crystal Chemistry of the natural vanadium bronzesAmerican Mineralogist, Vol. 75, pages 508-521

August 2, 2017 in Batteries | Permalink | Comments (2)

Comments

Do somebody here can tell me when there will be a good cheap ev for sale at 15 000$ with 500 miles range. Till then im driving my 2014 accent that do 47 mpg on a combination of 80% highway, 20% city.

gorr: I can't what you ask for, but here in Colorado you can get a new Leaf for $18000 after rebates.

Verify your Comment

Previewing your Comment

This is only a preview. Your comment has not yet been posted.

Working...
Your comment could not be posted. Error type:
Your comment has been posted. Post another comment

The letters and numbers you entered did not match the image. Please try again.

As a final step before posting your comment, enter the letters and numbers you see in the image below. This prevents automated programs from posting comments.

Having trouble reading this image? View an alternate.

Working...

Post a comment

Green Car Congress © 2017 BioAge Group, LLC. All Rights Reserved. | Home | BioAge Group