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Title: Unraveling the Complex Delithiation and Lithiation Mechanisms of the High Capacity Cathode Material V 6O 13

Abstract

V 6O 13 is a promising Li-ion battery cathode material for use in the high temperature oil field environment. The material exhibits a high capacity, and the voltage profile contains several plateaus associated with a series of complex structural transformations, which are not fully understood. The underlying mechanisms are central to understanding and improving the performance of V 6O 13-based rechargeable batteries. In this study, we present in situ X-ray diffraction data that highlight an asymmetric six-step discharge and five step charge process, due to a phase that is only formed on discharge. The LixV 6O 13 unit cell expands sequentially in c, b, and a directions during discharge and reversibly contracts back during charge. The process is associated with change of Li ion positions as well as charge ordering in LixV 6O 13. Density functional theory calculations give further insight into the electronic structures and preferred Li positions in the different structures formed upon cycling, particularly at high lithium contents, where no prior structural data are available. Lastly, the results shed light into the high specific capacity of V 6O 13 and are likely to aid in the development of this material for use as a cathode for secondarymore » lithium batteries.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [2];  [3];  [3];  [3]; ORCiD logo [1]
  1. Univ. of Cambridge, Cambridge (United Kingdom)
  2. Chinese Academy of Sciences, Qingdao (China)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Scientific User Facilities Division; European Commission, Community Research and Development Information Service (CORDIS), Seventh Framework Programme (FP7)
OSTI Identifier:
1374427
Grant/Contract Number:
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 13; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Meng, Wei, Pigliapochi, Roberta, Bayley, Paul M., Pecher, Oliver, Gaultois, Michael W., Seymour, Ieuan D., Liang, Han -Pu, Xu, Wenqian, Wiaderek, Kamila M., Chapman, Karena W., and Grey, Clare P. Unraveling the Complex Delithiation and Lithiation Mechanisms of the High Capacity Cathode Material V6O13. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.7b00428.
Meng, Wei, Pigliapochi, Roberta, Bayley, Paul M., Pecher, Oliver, Gaultois, Michael W., Seymour, Ieuan D., Liang, Han -Pu, Xu, Wenqian, Wiaderek, Kamila M., Chapman, Karena W., & Grey, Clare P. Unraveling the Complex Delithiation and Lithiation Mechanisms of the High Capacity Cathode Material V6O13. United States. doi:10.1021/acs.chemmater.7b00428.
Meng, Wei, Pigliapochi, Roberta, Bayley, Paul M., Pecher, Oliver, Gaultois, Michael W., Seymour, Ieuan D., Liang, Han -Pu, Xu, Wenqian, Wiaderek, Kamila M., Chapman, Karena W., and Grey, Clare P. Mon . "Unraveling the Complex Delithiation and Lithiation Mechanisms of the High Capacity Cathode Material V6O13". United States. doi:10.1021/acs.chemmater.7b00428.
@article{osti_1374427,
title = {Unraveling the Complex Delithiation and Lithiation Mechanisms of the High Capacity Cathode Material V6O13},
author = {Meng, Wei and Pigliapochi, Roberta and Bayley, Paul M. and Pecher, Oliver and Gaultois, Michael W. and Seymour, Ieuan D. and Liang, Han -Pu and Xu, Wenqian and Wiaderek, Kamila M. and Chapman, Karena W. and Grey, Clare P.},
abstractNote = {V6O13 is a promising Li-ion battery cathode material for use in the high temperature oil field environment. The material exhibits a high capacity, and the voltage profile contains several plateaus associated with a series of complex structural transformations, which are not fully understood. The underlying mechanisms are central to understanding and improving the performance of V6O13-based rechargeable batteries. In this study, we present in situ X-ray diffraction data that highlight an asymmetric six-step discharge and five step charge process, due to a phase that is only formed on discharge. The LixV6O13 unit cell expands sequentially in c, b, and a directions during discharge and reversibly contracts back during charge. The process is associated with change of Li ion positions as well as charge ordering in LixV6O13. Density functional theory calculations give further insight into the electronic structures and preferred Li positions in the different structures formed upon cycling, particularly at high lithium contents, where no prior structural data are available. Lastly, the results shed light into the high specific capacity of V6O13 and are likely to aid in the development of this material for use as a cathode for secondary lithium batteries.},
doi = {10.1021/acs.chemmater.7b00428},
journal = {Chemistry of Materials},
number = 13,
volume = 29,
place = {United States},
year = {Mon Jun 05 00:00:00 EDT 2017},
month = {Mon Jun 05 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
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  • The delithiation mechanisms occurring within the olivine-type class of cathode materials for Li-ion batteries have received considerable attention owing to the good capacity retention at high rates for LiFePO4. A comprehensive mechanistic study of the (de)lithiation reactions that occur when the substituted olivine-type cathode materials LiFexCo1-xPO4 (x = 0, 0.05, 0.125, 0.25, 0.5, 0.75, 0.875, 0.95 and 1) are electrochemically cycled is reported here, using in situ X-ray diffraction (XRD) data. On the first charge, two intermediate phases are observed and identified: Li1-x(Fe3+)x(Co2+)1- xPO4 for 0 < x < 1 (i.e. after oxidation of Fe2+ => Fe3+) and Li2/3FexCo1-xPO4 formore » 0 ≤ x ≤ 0.5 (i.e. the Co-majority materials). For the Fe-rich materials, we study how nonequilibrium, single-phase mechanisms that occur discretely in single particles, as observed for LiFePO4 at high rates, is affected by Co substitution. In the Co-majority materials, a two-phase mechanism with a coherent interface is observed, as was seen in LiCoPO4, and we discuss how it is manifested in the XRD patterns. We then compare the nonequilibrium, single-phase mechanism with the bulk single-phase and the coherent interface two-phase mechanisms. Despite the apparent differences between these mechanisms, we discuss how they are related and interconverted as a function of Fe/Co substitution and the potential implications for the electrochemistry of this system.« less
  • Highlights: • Nanostructured Na{sub 1.08}V{sub 6}O{sub 15} was synthesized through additive-free sol-gel process. • Prepared Na{sub 1.08}V{sub 6}O{sub 15} demonstrated high capacity and sufficient cycling stability. • The reaction temperature was optimized to allow scalable Na{sub 1.08}V{sub 6}O{sub 15} fabrication. - Abstract: Developing high-capacity cathode material with feasibility and scalability is still challenging for lithium-ion batteries (LIBs). In this study, a high-capacity ternary sodium vanadate compound, nanostructured NaV{sub 6}O{sub 15}, was template-free synthesized through sol-gel process with high producing efficiency. The as-prepared sample was systematically post-treated at different temperature and the post-annealing temperature was found to determine the cycling stabilitymore » and capacity of NaV{sub 6}O{sub 15}. The well-crystallized one exhibited good electrochemical performance with a high specific capacity of 302 mAh g{sup −1} when cycled at current density of 0.03 mA g{sup −1}. Its relatively long-term cycling stability was characterized by the cell performance under the current density of 1 A g{sup −1}, delivering a reversible capacity of 118 mAh g{sup −1} after 300 cycles with 79% capacity retention and nearly 100% coulombic efficiency: all demonstrating its significant promise of proposed strategy for large-scale synthesis of NaV{sub 6}O{sub 15} as cathode with high-capacity and high energy density for LIBs.« less