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Title: B4C as a stable non-carbon-based oxygen electrode material for lithium-oxygen batteries

Abstract

Lithium-oxygen (Li-O 2) batteries have extremely high theoretical specific capacities and energy densities when compared with Li-ion batteries. However, the instability of both electrolyte and carbon-based oxygen electrode related to the nucleophilic attack of reduced oxygen species during oxygen reduction reaction and the electrochemical oxidation during oxygen evolution reaction are recognized as the major challenges in this field. Here we report the application of boron carbide (B 4C) as the non-carbon based oxygen electrode material for aprotic Li-O 2 batteries. B 4C has high resistance to chemical attack, good conductivity, excellent catalytic activity and low density that are suitable for battery applications. The electrochemical activity and chemical stability of B4C are systematically investigated in aprotic electrolyte. Li-O 2 cells using B4C based air electrodes exhibit better cycling stability than those used TiC based air electrode in 1 M LiTf-Tetraglyme electrolyte. The degradation of B 4C based electrode is mainly due to be the loss of active sites on B 4C electrode during cycles as identified by the structure and composition characterizations. These results clearly demonstrate that B 4C is a very promising alternative oxygen electrode material for aprotic Li-O 2 batteries. It can also be used as a standard electrodemore » to investigate the stability of electrolytes.« less

Authors:
; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1344641
Report Number(s):
PNNL-SA-119212
Journal ID: ISSN 2211-2855; 48379; VT1201000
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Nano Energy; Journal Volume: 33; Journal Issue: C
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE; boron carbide; non-carbon electrode; oxygen electrode; lithium-oxygen battery; approtic electrode; Environmental Molecular Sciences Laboratory

Citation Formats

Song, Shidong, Xu, Wu, Cao, Ruiguo, Luo, Langli, Engelhard, Mark H., Bowden, Mark E., Liu, Bin, Estevez, Luis, Wang, Chong-Min, and Zhang, Ji-Guang. B4C as a stable non-carbon-based oxygen electrode material for lithium-oxygen batteries. United States: N. p., 2017. Web. doi:10.1016/j.nanoen.2017.01.042.
Song, Shidong, Xu, Wu, Cao, Ruiguo, Luo, Langli, Engelhard, Mark H., Bowden, Mark E., Liu, Bin, Estevez, Luis, Wang, Chong-Min, & Zhang, Ji-Guang. B4C as a stable non-carbon-based oxygen electrode material for lithium-oxygen batteries. United States. doi:10.1016/j.nanoen.2017.01.042.
Song, Shidong, Xu, Wu, Cao, Ruiguo, Luo, Langli, Engelhard, Mark H., Bowden, Mark E., Liu, Bin, Estevez, Luis, Wang, Chong-Min, and Zhang, Ji-Guang. Thu . "B4C as a stable non-carbon-based oxygen electrode material for lithium-oxygen batteries". United States. doi:10.1016/j.nanoen.2017.01.042.
@article{osti_1344641,
title = {B4C as a stable non-carbon-based oxygen electrode material for lithium-oxygen batteries},
author = {Song, Shidong and Xu, Wu and Cao, Ruiguo and Luo, Langli and Engelhard, Mark H. and Bowden, Mark E. and Liu, Bin and Estevez, Luis and Wang, Chong-Min and Zhang, Ji-Guang},
abstractNote = {Lithium-oxygen (Li-O2) batteries have extremely high theoretical specific capacities and energy densities when compared with Li-ion batteries. However, the instability of both electrolyte and carbon-based oxygen electrode related to the nucleophilic attack of reduced oxygen species during oxygen reduction reaction and the electrochemical oxidation during oxygen evolution reaction are recognized as the major challenges in this field. Here we report the application of boron carbide (B4C) as the non-carbon based oxygen electrode material for aprotic Li-O2 batteries. B4C has high resistance to chemical attack, good conductivity, excellent catalytic activity and low density that are suitable for battery applications. The electrochemical activity and chemical stability of B4C are systematically investigated in aprotic electrolyte. Li-O2 cells using B4C based air electrodes exhibit better cycling stability than those used TiC based air electrode in 1 M LiTf-Tetraglyme electrolyte. The degradation of B4C based electrode is mainly due to be the loss of active sites on B4C electrode during cycles as identified by the structure and composition characterizations. These results clearly demonstrate that B4C is a very promising alternative oxygen electrode material for aprotic Li-O2 batteries. It can also be used as a standard electrode to investigate the stability of electrolytes.},
doi = {10.1016/j.nanoen.2017.01.042},
journal = {Nano Energy},
number = C,
volume = 33,
place = {United States},
year = {Thu Jan 19 00:00:00 EST 2017},
month = {Thu Jan 19 00:00:00 EST 2017}
}
  • Although lithium-oxygen (Li-O2) batteries have great potential to be used as one of the next generation energy storage systems due to their ultrahigh theoretical specific energy, there are still many significant barriers before their practical applications. These barriers include electrolyte and electrode instability, poor ORR/OER efficiency and cycling capability, etc. Development of a highly efficient catalyst will not only enhance ORR/OER efficiency, it may also improve the stability of electrolyte because the reduced charge voltage. Here we report the synthesis of nano-sheet-assembled ZnCo2O4 spheres/single walled carbon nanotubes (ZCO/SWCNTs) composites as high performance air electrode materials for Li-O2 batteries. The ZCOmore » catalyzed SWCNTs electrodes delivered high discharge capacities, decreased the onset of oxygen evolution reaction by 0.9 V during charge processes, and led to more stable cycling stability. These results indicate that ZCO/SWCNTs composite can be used as highly efficient air electrode for oxygen reduction and evolution reactions. The highly enhanced catalytic activity by uniformly dispersed ZnCo2O4 catalyst on nanostructured electrodes is expected to inspire« less
  • The gas-diffusion-electrode used in a Li-air cell has been studied in a unique homemade electrochemical cell. Three major obstacles for the development of a feasible Li-air system were discussed with a focus on the development of a functional gas-diffusion-electrode in non-aqueous electrolytes and the way of avoiding the passivation of gas-diffusion-electrodes caused by the deposition of the reduction products. It is the first time that the importance of establishing the 3-phase electrochemical interface in non-aqueous electrolyte is demonstrated by creating air-diffusion paths and an air saturated portion for an air cathode. A model mechanism of electrode passivation by the reactionmore » products was also proposed. Lithium oxides formed during O{sub 2} reduction tend to block small pores, preventing them from further utilization in the electrochemical reaction. On the other hand, lithium oxides would accumulate inside the large pores during the reduction until the density of oxides becomes high enough to choke-off the mass transfer. Carbon materials with a high surface area associated with larger pores should be selected to make the gas-diffusion-electrode for Li-air battery. For the first time, a near linear relationship between the capacity of GDE in a non-aqueous electrolyte and the average pore diameter was demonstrated, which could be used to estimate the capacity of the GDE quantitatively.« less
  • Low negative electrode potential and high reactivity makes lithium (Li) ideal candidate for obtaining highest possible energy density among other materials. Here, we show a novel route with which the overall electrode potential could significantly be enhanced through selection of cluster size. In using first principles density functional theory and continuum dielectric model, we studied free energy and redox potential as well as investigated relative stability of Li n (n ≤ 8) clusters in both gas phase and solution. We found that Li 3 has the lowest negative redox potential (thereby highest overall electrode potential) suggesting that cluster based approachmore » could provide a novel way of engineering the next generation battery technology. The microscopic origin of Li 3 cluster’s superior performance is related to two major factors: gas phase ionization and difference between solvation free energy for neutral and positive ion. Taken together, our study provides insight into the engineering of redox potential in battery and could stimulate further work in this direction.« less
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