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Title: Structure evolution and thermal stability of high-energy density Li-ion battery cathode Li 2VO 2F

Abstract

Lithium-ion batteries (LIBs) provide high-energy-density electrochemical energy storage, which plays a central role in advancing technologies ranging from portable electronics to electric vehicles (EVs). However, a demand for lighter, more compact devices and for extended range EVs continues to fuel the need for higher energy density storage systems. Li 2VO 2F, which is synthesized in its lithiated state, allows two-electron transfer per formula during the electrochemical reaction providing a high theoretical capacity of 462 mAh/g. Herein, the synthesis and electrochemical performance of Li 2VO 2F are optimized. The thermal stability of Li 2VO 2F, which is related to the safety of a battery is studied by thermal gravimetric analysis. The structure and vanadium oxidation state evolution along Li cycling are studied by ex-situ X-ray diffraction and absorption techniques. It is shown that the rock-salt structure of pristine Li 2VO 2F is stable up to at least 250°C, and is preserved upon Li cycling, which proceeds by the solid-solution mechanism. However, not all Li can be removed from the structure upon charge to 4.5 V, limiting the experimentally obtained capacity.

Authors:
 [1];  [1];  [2];  [2];  [3];  [4];  [4];  [5];  [5];  [1];  [6]
  1. Binghamton Univ., NY (United States). NorthEast Center for Chemical Energy Storage (NECCES)
  2. Binghamton Univ., NY (United States). Dept. of Chemistry and Materials
  3. Binghamton Univ., NY (United States). NorthEast Center for Chemical Energy Storage (NECCES); Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  4. Binghamton Univ., NY (United States). NorthEast Center for Chemical Energy Storage (NECCES); Binghamton Univ., NY (United States). Dept. of Physics, Applied Physics and Astronomy
  5. Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
  6. Binghamton Univ., NY (United States). NorthEast Center for Chemical Energy Storage (NECCES); Binghamton Univ., NY (United States). Dept. of Chemistry and Materials
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)
OSTI Identifier:
1367893
Grant/Contract Number:
AC02-06CH11357; SC0012583; SC0012704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 164; Journal Issue: 7; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Cathode materials; Li-ion battries; Reaction mechanism; Thermal stability

Citation Formats

Wang, Xiaoya, Huang, Yiqing, Ji, Dongsheng, Omenya, Fredrick, Karki, Khim, Sallis, Shawn, Piper, Louis F. J., Wiaderek, Kamila M., Chapman, Karena W., Chernova, Natasha A., and Whittingham, M. Stanley. Structure evolution and thermal stability of high-energy density Li-ion battery cathode Li2VO2F. United States: N. p., 2017. Web. doi:10.1149/2.1071707jes.
Wang, Xiaoya, Huang, Yiqing, Ji, Dongsheng, Omenya, Fredrick, Karki, Khim, Sallis, Shawn, Piper, Louis F. J., Wiaderek, Kamila M., Chapman, Karena W., Chernova, Natasha A., & Whittingham, M. Stanley. Structure evolution and thermal stability of high-energy density Li-ion battery cathode Li2VO2F. United States. doi:10.1149/2.1071707jes.
Wang, Xiaoya, Huang, Yiqing, Ji, Dongsheng, Omenya, Fredrick, Karki, Khim, Sallis, Shawn, Piper, Louis F. J., Wiaderek, Kamila M., Chapman, Karena W., Chernova, Natasha A., and Whittingham, M. Stanley. Wed . "Structure evolution and thermal stability of high-energy density Li-ion battery cathode Li2VO2F". United States. doi:10.1149/2.1071707jes. https://www.osti.gov/servlets/purl/1367893.
@article{osti_1367893,
title = {Structure evolution and thermal stability of high-energy density Li-ion battery cathode Li2VO2F},
author = {Wang, Xiaoya and Huang, Yiqing and Ji, Dongsheng and Omenya, Fredrick and Karki, Khim and Sallis, Shawn and Piper, Louis F. J. and Wiaderek, Kamila M. and Chapman, Karena W. and Chernova, Natasha A. and Whittingham, M. Stanley},
abstractNote = {Lithium-ion batteries (LIBs) provide high-energy-density electrochemical energy storage, which plays a central role in advancing technologies ranging from portable electronics to electric vehicles (EVs). However, a demand for lighter, more compact devices and for extended range EVs continues to fuel the need for higher energy density storage systems. Li2VO2F, which is synthesized in its lithiated state, allows two-electron transfer per formula during the electrochemical reaction providing a high theoretical capacity of 462 mAh/g. Herein, the synthesis and electrochemical performance of Li2VO2F are optimized. The thermal stability of Li2VO2F, which is related to the safety of a battery is studied by thermal gravimetric analysis. The structure and vanadium oxidation state evolution along Li cycling are studied by ex-situ X-ray diffraction and absorption techniques. It is shown that the rock-salt structure of pristine Li2VO2F is stable up to at least 250°C, and is preserved upon Li cycling, which proceeds by the solid-solution mechanism. However, not all Li can be removed from the structure upon charge to 4.5 V, limiting the experimentally obtained capacity.},
doi = {10.1149/2.1071707jes},
journal = {Journal of the Electrochemical Society},
number = 7,
volume = 164,
place = {United States},
year = {Wed May 24 00:00:00 EDT 2017},
month = {Wed May 24 00:00:00 EDT 2017}
}

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Cited by: 2works
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  • Lithium- and manganese-rich oxides undergo structural transformation and/or atomic rearrangements during the delithiation/lithiation process and ultimately suffer from several issues such as first cycle irreversible capacity and voltage fade. In order to understand the mechanism of these issues, perception of a detailed crystal structure of pristine material is obviously demanding. In this study, combined powder neutron diffraction (ND) and temperature-dependent magnetic susceptibility techniques were employed to investigate the structure of a pristine lithium- and manganese-rich Li1.2Mn0.55Ni0.15Co0.10O2 cathode oxide. Rietveld refinement on the experimental ND pattern yields good fits by considering either Li2MO3 (M = Co, Mn, Ni) type monoclinic (C2/m space group) phase with 1% of Ni residing in the 4h lithium site or a composite structure consisting of 50% of Li2MnO3 type monoclinic (C2/m space group) and 50% LiMO2 (M = Co, Mn, Ni) type trigonal (Rmore » $$\bar{3}$$m space group) structure. In the composite structure, 3% Li/Ni site exchange in the trigonal phase is also proposed. Further, temperature-dependent dc magnetic susceptibility shows Curie–Weiss paramagnetic behavior at T ≥ 100 K, and no ordering/deviation of the field cooling (FC) curve in the temperature range 2–320 K indicates the random distribution of metal ions in the transition metal (TM) layer in the trigonal phase. Bifurcation of the zero-field cooling (ZFC) curve from the FC curve showing a magnetic ordering at TN 50 K reveals the presence of cation ordering in the TM layers arising from a distinct Li2MnO3-like phase. These results suggest that the lithium- and manganese-rich oxide with a composition Li1.2Mn0.55Ni0.15Co0.10O2 is more likely a composite of monoclinic and trigonal phases. The report also highlights the unique materials diagnostic capability of combined ND and magnetic susceptibility techniques to obtain detailed structural information of complex oxide systems.« less
  • Lithium transition metal fluorophosphates (Li{sub 2}MPO{sub 4}F, M: Co and Ni) have been investigated from atomistic simulation. In order to predict the characteristics of these materials as cathode materials for lithium ion batteries, structural property, defect chemistry, and Li{sup +} ion transportation property are characterized. The core–shell model with empirical force fields is employed to reproduce the unit-cell parameters of crystal structure, which are in good agreement with the experimental data. In addition, the formation energies of intrinsic defects (Frenkel and antisite) are determined by energetics calculation. From migration energy calculations, it is found that these flurophosphates have a 3Dmore » Li{sup +} ion diffusion network forecasting good Li{sup +} ion conducting performances. Accordingly, we expect that this study provides an atomic scale insight as cathode materials for lithium ion batteries. - Graphical abstract: Lithium transition metal fluorophosphates (Li{sub 2}CoPO{sub 4}F and Li{sub 2}NiPO{sub 4}F). Display Omitted - Highlights: • Lithium transition metal fluorophosphates (Li{sub 2}MPO{sub 4}F, M: Co and Ni) are investigated from classical atomistic simulation. • The unit-cell parameters from experimental studies are reproduced by the core–shell model. • Li{sup +} ion conducting Li{sub 2}MPO{sub 4}F has a 3D Li{sup +} ion diffusion network. • It is predicted that Li/Co or Li/Ni antisite defects are well-formed at a substantial concentration level.« less
  • One of the metastable phases of vanadium dioxide, VO{sub 2}(B) bundles of nanorods and microspheres have been synthesized through a simple hydrothermal method by dispersing V{sub 2}O{sub 5} in aqueous quinol. The obtained products were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and electrochemical discharge-charge test for lithium battery. It was found that the morphologies of the obtained VO{sub 2}(B) can be tuned by manipulating the relative amount of quinol. The electrochemical test found that the bundles of nanorods exhibit an initial discharge capacity of 171 mAh g{sup -1} and its almost stabilizedmore » capacity was reached to 108 mAh g{sup -1} after 47 cycles at a current density of 0.1 mA g{sup -1}. The formation mechanism of the VO{sub 2}(B) bundles of nanorods and microspheres was also discussed. - Highlights: Black-Right-Pointing-Pointer VO{sub 2}(B) bundles of nanorods and microspheres were prepared by hydrothermal route at 180 Degree-Sign C for 1 day. Black-Right-Pointing-Pointer In this method for the synthesis of VO{sub 2}(B), we are the first to use quinol as a reducing agent. Black-Right-Pointing-Pointer Morphologies of the obtained VO{sub 2}(B) can be tuned by manipulating the relative amount of quinol. Black-Right-Pointing-Pointer VO{sub 2}(B) exhibits an initial capacity of 171 mAh g{sup -1} and reached to 108 mAh g{sup -1} after 47 cycles. Black-Right-Pointing-Pointer The formation mechanism of the VO{sub 2}(B) bundles of nanorods and microspheres is also discussed.« less
  • The reaction of Re{sub 2}O{sub 7} with XeF{sub 6} in anhydrous HF provides a convenient route to high-purity ReO{sub 2}F{sub 3}. The fluoride acceptor and Lewis base properties of ReO{sub 2}F{sub 3} have been investigated leading to the formation of [M][ReO{sub 2}F{sub 4}] [M = Li, Na, Cs, N(CH{sub 3}){sub 4}], [K][Re{sub 2}O{sub 4}F{sub 7}], [K][Re{sub 2}O{sub 4}F{sub 7}]{center_dot}2ReO{sub 2}F{sub 3}, [Cs][Re{sub 3}O{sub 6}F{sub 10}], and ReO{sub 2}F{sub 3}(CH{sub 3}CN). The ReO{sub 2}F{sub 4}{sup {minus}}, Re{sub 2}O{sub 4}F{sub 7}{sup {minus}}, and Re{sub 3}O{sub 6}F{sub 10{sup {minus}} anions and the ReO{sub 2}F{sub 3}(CH{sub 3}CN) adduct have been characterized in the solidmore » state by Raman spectroscopy, and the structures [Li][ReO{sub 2}F{sub 4}], [K][Re{sub 2}O{sub 4}F{sub 7}], [K][Re{sub 2}O{sub 4}F{sub 7}]{center_dot}2ReO{sub 2}F{approximately}3}, [Cs][Re{sub 3}O{sub 6}F{sub 10}], and ReO{sub 3}F(CH{sub 3}CN){sub 2}{center_dot}CH{sub 3}CN have been determined by X-ray crystallography. The structure of ReO{sub 2}F{sub 4}{sup {minus}} consists of a cis-dioxo arrangement of Re-O double bonds in which the Re-F bonds trans to the oxygen atoms are significantly lengthened as a result of the trans influence of the oxygens. The Re{sub 2}O{sub 4}F{sub 7}{sup {minus}} and Re{sub 3}O{sub 6}F{sub 10}{sup {minus}} anions and polymeric ReO{sub 2}F{sub 3} are open chains containing fluorine-bridged ReO{sub 2}F{sub 4} units in which each pair of Re-O bonds are cis to each other and the fluorine bridges are trans to oxygens. The trans influence of the oxygens is manifested by elongated terminal Re-F bonds trans to Re-O bonds as in ReO{sub 2}F{sub 4}{sup {minus}} and by the occurrence of both fluorine bridges trans to Re-O bonds. Fluorine-19 NMR spectra show that ReO{sub 2}F{sub 4}{sup {minus}}, Re{sub 2}O{sub 4}F{sub 7}{sup {minus}}, and ReO{sub 2}F{sub 3}(CH{sub 3}CN) have cis-dioxo arrangements in CH{sub 3}CN solution. Density functional theory calculations at the local and nonlocal levels confirm that the cis-dioxo isomers of ReO{sub 2}F{sub 4}{sup {minus}} and ReO{sub 2}F{sub 3}(CH{sub 3}CN), where CH{sub 3}CN is bonded trans to an oxygen, are the energy-minimized structures. The adduct ReO{sub 3}F(CH{sub 3}CN){sub 2}{center_dot}CH{sub 3}CN was obtained by hydrolysis of ReO{sub 2}F{sub 3}(CH{sub 3}CN), and was shown by X-ray crystallography to have a facial arrangement of oxygen atoms on rhenium.« less
  • The VO/sub 2/F/sub 4//sup 3 -/ ion has a cis octahedral structure, as is shown by single crystal structure analysis of the title compound. The unit cell of (NH/sub 4/)/sub 3/ VO/sub 2/F/sub 4/ (space group Immm or I222, a = 912.6(2), b = 1881.8(4), c = 626.4(1) pm, Z = 6) contains two symmetrically independent anions. One is rotationally disordered. Oxo and fluoro ligands cannot be distinguished. But the second one has a distorted cis octahedral structure with the lengths 170.0(4), 186.1(4), and 202.3(4) pm for the V-O, V-F (axial), and V-F (equatorial)bonds. Infrared and Raman spectra as wellmore » as theoretical considerations support the crystallographic results. The phase transitions at 418 and 215 K were confirmed by variable temperature X-ray powder diffraction. Above 418 K the cubic cryolite type structure is adopted with a = 902.6(2) pm. Plausible mechanisms for the phase transitions are suggested.« less