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Title: Uniform second Li ion intercalation in solid state ϵ-LiVOPO4

Authors:
 [1];  [2];  [3];  [4];  [5];  [1];  [5];  [6];  [3];  [3];  [7];  [7];  [4];  [3];  [5]; ORCiD logo [8]
  1. Department of Physics, Applied Physics and Astronomy, Binghamton University, Binghamton, New York 13902, USA
  2. Materials Science and Engineering, Binghamton University, Binghamton, New York 13902, USA
  3. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, USA
  4. Department of NanoEngineering, University of California San Diego, 9500 Gilman Drive 0448, La Jolla, California 92093, USA
  5. NECCES, Binghamton University, Binghamton, New York 13902, USA
  6. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA
  7. Diamond Light Source Ltd., Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE, United Kingdom
  8. Department of Physics, Applied Physics and Astronomy, Binghamton University, Binghamton, New York 13902, USA, Materials Science and Engineering, Binghamton University, Binghamton, New York 13902, USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1282420
Grant/Contract Number:
AC02-05CH11231; SC0012583
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Applied Physics Letters
Additional Journal Information:
Journal Volume: 109; Journal Issue: 5; Related Information: CHORUS Timestamp: 2018-03-09 11:44:25; Journal ID: ISSN 0003-6951
Publisher:
American Institute of Physics
Country of Publication:
United States
Language:
English

Citation Formats

Wangoh, Linda W., Sallis, Shawn, Wiaderek, Kamila M., Lin, Yuh-Chieh, Wen, Bohua, Quackenbush, Nicholas F., Chernova, Natasha A., Guo, Jinghua, Ma, Lu, Wu, Tianpin, Lee, Tien-Lin, Schlueter, Christoph, Ong, Shyue Ping, Chapman, Karena W., Whittingham, M. Stanley, and Piper, Louis F. J. Uniform second Li ion intercalation in solid state ϵ-LiVOPO4. United States: N. p., 2016. Web. doi:10.1063/1.4960452.
Wangoh, Linda W., Sallis, Shawn, Wiaderek, Kamila M., Lin, Yuh-Chieh, Wen, Bohua, Quackenbush, Nicholas F., Chernova, Natasha A., Guo, Jinghua, Ma, Lu, Wu, Tianpin, Lee, Tien-Lin, Schlueter, Christoph, Ong, Shyue Ping, Chapman, Karena W., Whittingham, M. Stanley, & Piper, Louis F. J. Uniform second Li ion intercalation in solid state ϵ-LiVOPO4. United States. doi:10.1063/1.4960452.
Wangoh, Linda W., Sallis, Shawn, Wiaderek, Kamila M., Lin, Yuh-Chieh, Wen, Bohua, Quackenbush, Nicholas F., Chernova, Natasha A., Guo, Jinghua, Ma, Lu, Wu, Tianpin, Lee, Tien-Lin, Schlueter, Christoph, Ong, Shyue Ping, Chapman, Karena W., Whittingham, M. Stanley, and Piper, Louis F. J. Thu . "Uniform second Li ion intercalation in solid state ϵ-LiVOPO4". United States. doi:10.1063/1.4960452.
@article{osti_1282420,
title = {Uniform second Li ion intercalation in solid state ϵ-LiVOPO4},
author = {Wangoh, Linda W. and Sallis, Shawn and Wiaderek, Kamila M. and Lin, Yuh-Chieh and Wen, Bohua and Quackenbush, Nicholas F. and Chernova, Natasha A. and Guo, Jinghua and Ma, Lu and Wu, Tianpin and Lee, Tien-Lin and Schlueter, Christoph and Ong, Shyue Ping and Chapman, Karena W. and Whittingham, M. Stanley and Piper, Louis F. J.},
abstractNote = {},
doi = {10.1063/1.4960452},
journal = {Applied Physics Letters},
number = 5,
volume = 109,
place = {United States},
year = {Thu Aug 04 00:00:00 EDT 2016},
month = {Thu Aug 04 00:00:00 EDT 2016}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1063/1.4960452

Citation Metrics:
Cited by: 2works
Citation information provided by
Web of Science

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  • Full, reversible intercalation of two Li+ has not yet been achieved in promising VOPO4 electrodes. A pronounced Li+ gradient has been reported in the low voltage window (i.e. second lithium reaction) that is thought to originate from disrupted kinetics in the high voltage regime (i.e first lithium reaction). Here we employ a combination of hard and soft x–ray photoelectron and absorption spectroscopy techniques to depth profile solid state synthesized LiVOPO4 cycled within the low voltage window only. Analysis of the vanadium environment revealed no evidence of a Li+ gradient, which combined with almost full theoretical capacity confirms that disrupted kineticsmore » in the high voltage window are responsible for hindering full two lithium insertion. Furthermore, we argue that the uniform Li+ intercalation is a prerequisite for the formation of intermediate phases Li1:50VOPO4 and Li1:75VOPO4. The evolution from LiVOPO4 to Li2VOPO4 via the intermediate phases is confirmed by direct comparison between O K–edge absorption spectroscopy and density functional theory.« less
  • Full, reversible intercalation of two Li{sup +} has not yet been achieved in promising VOPO{sub 4} electrodes. A pronounced Li{sup +} gradient has been reported in the low voltage window (i.e., second lithium reaction) that is thought to originate from disrupted kinetics in the high voltage regime (i.e., first lithium reaction). Here, we employ a combination of hard and soft x–ray photoelectron and absorption spectroscopy techniques to depth profile solid state synthesized LiVOPO{sub 4} cycled within the low voltage window only. Analysis of the vanadium environment revealed no evidence of a Li{sup +} gradient, which combined with almost full theoreticalmore » capacity confirms that disrupted kinetics in the high voltage window are responsible for hindering full two lithium insertion. Furthermore, we argue that the uniform Li{sup +} intercalation is a prerequisite for the formation of intermediate phases Li{sub 1.50}VOPO{sub 4} and Li{sub 1.75}VOPO{sub 4}. The evolution from LiVOPO{sub 4} to Li{sub 2}VOPO{sub 4} via the intermediate phases is confirmed by direct comparison between O K–edge absorption spectroscopy and density functional theory.« less
  • The electroanalytical behavior of thin Li{sub 1{minus}x}CoO{sub 2} electrodes is elucidated by the simultaneous application of three electroanalytical techniques: slow-scan-rate cyclic voltammetry (SSCV), potentiostatic intermittent titration technique, and electrochemical impedance spectroscopy. The data were treated within the framework of a simple model expressed by a Frumkin-type sorption isotherm. The experimental SSCV curves were well described by an equation combining such an isotherm with the Butler-Volmer equation for slow interfacial Li-ion transfer. The apparent attraction constant was {minus}4.2, which is characteristic of a quasi-equilibrium, first-order phase transition. Impedance spectra reflected a process with the following steps: Li{sup +} ion migration inmore » solution, Li{sup +} ion migration through surface films, strongly potential-dependent charge-transfer resistance, solid-state Li{sup +} diffusion, and accumulation of the intercalants into the host materials. An excellent fit was found between these spectra and an equivalent circuit, including a Voigt-type analog (Li{sup +} migration through multilayer surface films and charge transfer) in series with a finite-length Warburg-type element (Li{sup +} solid-state diffusion), and a capacitor (Li accumulation). In this paper, the authors compare the solid-state diffusion time constants and the differential intercalation capacities obtained by the three electroanalytical techniques.« less
  • In a solid-state Li ion battery, the solid-state electrolyte exits principally in regions of high externally applied potentials, and this varies rapidly at the interfaces with electrodes due to the formation of electrochemical double layers. Here, we investigate the implications of these for a model solid-state Li ion battery Li|Li 3OCl|C, where C is simply a metallic intercalation cathode. We use DFT to calculate the potential dependence of the formation energies of the Li + charge carriers in superionic Li 3OCl. We find that Li+ vacancies are the dominant species at the cathode while Li+ interstitials dominate at the anode.more » With typical Mg aliovalent doping of Li 3OCl, Li + vacancies dominate the bulk of the electrolyte as well, with freely mobile vacancies only ~ 10 -4 of the Mg doping density at room temperature. We study the repulsive interaction between Li+ vacancies and find that this is extremely short range, typically only one lattice constant due to local structural relaxation around the vacancy and this is significantly shorter than pure electrostatic screening. We model a Li 3OCl- cathode interface by treating the cathode as a nearly ideal metal using a polarizable continuum model with an ε r = 1000. There is a large interface segregation free energy of ~ - 1 eV per Li + vacancy. Combined with the short range for repulsive interactions of the vacancies, this means that very large vacancy concentrations will build up in a single layer of Li 3OCl at the cathode interface to form a compact double layer. The calculated potential drop across the interface is ~ 3 V for a nearly full concentration of vacancies at the surface. This suggests that nearly all the cathode potential drop in Li 3OCl occurs at the Helmholtz plane rather than in a diffuse space-charge region. We suggest that the conclusions found here will be general to other superionic conductors as well.« less