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Title: Design principles for high transition metal capacity in disordered rocksalt Li-ion cathodes

Abstract

Design rules for high capacity disordered rocksalt Li-ion cathodes applied to the Li–Mn–V–O–F system.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1];  [2]; ORCiD logo [3]; ORCiD logo [4];  [5];  [6];  [7];  [8];  [9]; ORCiD logo [6];  [3];  [10]
  1. Department of Materials Science and Engineering, MIT, Cambridge, USA
  2. Materials Science Division, LBNL, Berkeley, USA, Department of Materials Science and Engineering
  3. Department of Materials Science and Engineering, UC Berkeley, Berkeley, USA
  4. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, USA
  5. Materials Science Division, LBNL, Berkeley, USA
  6. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, USA
  7. Department of Chemical and Biomolecular Engineering, UC Berkeley, Berkeley, USA
  8. Department of Chemistry, UC Berkeley, Berkeley, USA
  9. Department of Chemical and Biomolecular Engineering, UC Berkeley, Berkeley, USA, Energy Storage and Distributed Resources Division
  10. Department of Materials Science and Engineering, MIT, Cambridge, USA, Materials Science Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1441056
Alternate Identifier(s):
OSTI ID: 1471056; OSTI ID: 1477348
Grant/Contract Number:  
AC02-05CH11231; AC02-06CH11357
Resource Type:
Published Article
Journal Name:
Energy & Environmental Science
Additional Journal Information:
Journal Name: Energy & Environmental Science Journal Volume: 11 Journal Issue: 8; Journal ID: ISSN 1754-5692
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Kitchaev, Daniil A., Lun, Zhengyan, Richards, William D., Ji, Huiwen, Clément, Raphaële J., Balasubramanian, Mahalingam, Kwon, Deok-Hwang, Dai, Kehua, Papp, Joseph K., Lei, Teng, McCloskey, Bryan D., Yang, Wanli, Lee, Jinhyuk, and Ceder, Gerbrand. Design principles for high transition metal capacity in disordered rocksalt Li-ion cathodes. United Kingdom: N. p., 2018. Web. doi:10.1039/C8EE00816G.
Kitchaev, Daniil A., Lun, Zhengyan, Richards, William D., Ji, Huiwen, Clément, Raphaële J., Balasubramanian, Mahalingam, Kwon, Deok-Hwang, Dai, Kehua, Papp, Joseph K., Lei, Teng, McCloskey, Bryan D., Yang, Wanli, Lee, Jinhyuk, & Ceder, Gerbrand. Design principles for high transition metal capacity in disordered rocksalt Li-ion cathodes. United Kingdom. doi:10.1039/C8EE00816G.
Kitchaev, Daniil A., Lun, Zhengyan, Richards, William D., Ji, Huiwen, Clément, Raphaële J., Balasubramanian, Mahalingam, Kwon, Deok-Hwang, Dai, Kehua, Papp, Joseph K., Lei, Teng, McCloskey, Bryan D., Yang, Wanli, Lee, Jinhyuk, and Ceder, Gerbrand. Mon . "Design principles for high transition metal capacity in disordered rocksalt Li-ion cathodes". United Kingdom. doi:10.1039/C8EE00816G.
@article{osti_1441056,
title = {Design principles for high transition metal capacity in disordered rocksalt Li-ion cathodes},
author = {Kitchaev, Daniil A. and Lun, Zhengyan and Richards, William D. and Ji, Huiwen and Clément, Raphaële J. and Balasubramanian, Mahalingam and Kwon, Deok-Hwang and Dai, Kehua and Papp, Joseph K. and Lei, Teng and McCloskey, Bryan D. and Yang, Wanli and Lee, Jinhyuk and Ceder, Gerbrand},
abstractNote = {Design rules for high capacity disordered rocksalt Li-ion cathodes applied to the Li–Mn–V–O–F system.},
doi = {10.1039/C8EE00816G},
journal = {Energy & Environmental Science},
number = 8,
volume = 11,
place = {United Kingdom},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C8EE00816G

Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Thermodynamic stability and synthesis of mixed Mn2+/V4+ disordered rocksalt oxyfluorides. a. Computed phase diagram of the MnO/Li2VO3/LiF alloy space. The temperature–marked contours denote the extent of the binodal, starting from the MnO and Li2VO3 endpoints, at the given temperature. The color–coded overlay plots the theoretical gravimetric capacitymore » of compositions across the phase diagram based on Li and transition metal redox content. The percolation threshold marks compositions exceeding the 10% Li-excess requirement.2 The inset illustrates the region of the phase diagram we focus on, with the stoichiometric, transition metal-rich, and Li-rich compositions to synthesize. b. XRD profiles and refined lattice parameters of the synthesized disordered rocksalt compounds.« less

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Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005


Characterization of Different Precursors and Activated Vanadium Phosphate Catalysis by 31P NMR Spin Echo Mapping
journal, July 1994

  • Sananes, M. T.; Tuel, A.; Hutchings, G. J.
  • Journal of Catalysis, Vol. 148, Issue 1
  • DOI: 10.1006/jcat.1994.1221

Lithium Batteries and Cathode Materials
journal, October 2004

  • Whittingham, M. Stanley
  • Chemical Reviews, Vol. 104, Issue 10, p. 4271-4302
  • DOI: 10.1021/cr020731c

Characterization of Disordered Li (1+ x ) Ti 2 x Fe (1–3 x ) O 2 as Positive Electrode Materials in Li-Ion Batteries Using Percolation Theory
journal, November 2015


Hybrid functionals based on a screened Coulomb potential
journal, May 2003

  • Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
  • The Journal of Chemical Physics, Vol. 118, Issue 18
  • DOI: 10.1063/1.1564060

Soft X-Ray Irradiation Effects of Li2O2, Li2CO3 and Li2O Revealed by Absorption Spectroscopy
journal, November 2012


Effect of High Voltage on the Structure and Electrochemistry of LiNi 0.5 Mn 0.5 O 2 :  A Joint Experimental and Theoretical Study
journal, October 2006

  • Bréger, Julien; Meng, Ying S.; Hinuma, Yoyo
  • Chemistry of Materials, Vol. 18, Issue 20
  • DOI: 10.1021/cm060886r

Spectroscopic fingerprints of valence and spin states in manganese oxides and fluorides
journal, May 2013


Reversible Mn2+/Mn4+ double redox in lithium-excess cathode materials
journal, April 2018


Recent Achievements on Inorganic Electrode Materials for Lithium-Ion Batteries
journal, February 2015

  • Croguennec, Laurence; Palacin, M. Rosa
  • Journal of the American Chemical Society, Vol. 137, Issue 9
  • DOI: 10.1021/ja507828x

Reversible Three-Electron Redox Reaction of Mo 3+ /Mo 6+ for Rechargeable Lithium Batteries
journal, March 2017


Lithium-Excess Cation-Disordered Rocksalt-Type Oxide with Nanoscale Phase Segregation: Li 1.25 Nb 0.25 V 0.5 O 2
journal, July 2017


Performance and design considerations for lithium excess layered oxide positive electrode materials for lithium ion batteries
journal, January 2016

  • Hy, Sunny; Liu, Haodong; Zhang, Minghao
  • Energy & Environmental Science, Vol. 9, Issue 6
  • DOI: 10.1039/C5EE03573B

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Electron-energy-loss near-edge structures in the oxygen K -edge spectra of transition-metal oxides
journal, May 1993


K -edge absorption spectra of selected vanadium compounds
journal, November 1984


Unlocking the Potential of Cation-Disordered Oxides for Rechargeable Lithium Batteries
journal, January 2014


Twin Problems of Interfacial Carbonate Formation in Nonaqueous Li–O 2 Batteries
journal, March 2012

  • McCloskey, B. D.; Speidel, A.; Scheffler, R.
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 8
  • DOI: 10.1021/jz300243r

Frequency-stepped acquisition in nuclear magnetic resonance spectroscopy under magic angle spinning
journal, March 2013

  • Pell, Andrew J.; Clément, Raphaële J.; Grey, Clare P.
  • The Journal of Chemical Physics, Vol. 138, Issue 11
  • DOI: 10.1063/1.4795001

Lithiation-driven structural transition of VO 2 F into disordered rock-salt Li x VO 2 F
journal, January 2016

  • Chen, Ruiyong; Maawad, Emad; Knapp, Michael
  • RSC Advances, Vol. 6, Issue 69
  • DOI: 10.1039/C6RA14276A

71Ga and 69Ga nuclear magnetic resonance study of β-Ga2O3: resolution of four- and six-fold coordinated Ga sites in static conditions
journal, May 1995

  • Massiot, Dominique; Farnan, Ian; Gautier, Nathalie
  • Solid State Nuclear Magnetic Resonance, Vol. 4, Issue 4
  • DOI: 10.1016/0926-2040(95)00002-8

Energetics of MnO 2 polymorphs in density functional theory
journal, January 2016


Synthesis of “Li[sub 1.1](Ni[sub 0.425]Mn[sub 0.425]Co[sub 0.15])[sub 0.9]O[sub 1.8]F[sub 0.2]” Materials by Different Routes: Is There Fluorine Substitution for Oxygen?
journal, January 2009

  • Croguennec, L.; Bains, J.; Ménétrier, M.
  • Journal of The Electrochemical Society, Vol. 156, Issue 5
  • DOI: 10.1149/1.3080659

Disordered Lithium-Rich Oxyfluoride as a Stable Host for Enhanced Li + Intercalation Storage
journal, February 2015

  • Chen, Ruiyong; Ren, Shuhua; Knapp, Michael
  • Advanced Energy Materials, Vol. 5, Issue 9
  • DOI: 10.1002/aenm.201401814

Residual Lithium Carbonate Predominantly Accounts for First Cycle CO 2 and CO Outgassing of Li-Stoichiometric and Li-Rich Layered Transition-Metal Oxides
journal, November 2017

  • Renfrew, Sara E.; McCloskey, Bryan D.
  • Journal of the American Chemical Society, Vol. 139, Issue 49
  • DOI: 10.1021/jacs.7b08461

Electronic-Structure Origin of Cation Disorder in Transition-Metal Oxides
journal, October 2017


High-efficiency in situ resonant inelastic x-ray scattering (iRIXS) endstation at the Advanced Light Source
journal, March 2017

  • Qiao, Ruimin; Li, Qinghao; Zhuo, Zengqing
  • Review of Scientific Instruments, Vol. 88, Issue 3
  • DOI: 10.1063/1.4977592

High-capacity electrode materials for rechargeable lithium batteries: Li 3 NbO 4 -based system with cation-disordered rocksalt structure
journal, June 2015

  • Yabuuchi, Naoaki; Takeuchi, Mitsue; Nakayama, Masanobu
  • Proceedings of the National Academy of Sciences, Vol. 112, Issue 25
  • DOI: 10.1073/pnas.1504901112

Evaluating structure selection in the hydrothermal growth of FeS2 pyrite and marcasite
journal, December 2016

  • Kitchaev, Daniil A.; Ceder, Gerbrand
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms13799

Oxygen 1 s x-ray-absorption edges of transition-metal oxides
journal, September 1989


A new class of high capacity cation-disordered oxides for rechargeable lithium batteries: Li–Ni–Ti–Mo oxides
journal, January 2015

  • Lee, Jinhyuk; Seo, Dong-Hwa; Balasubramanian, Mahalingam
  • Energy & Environmental Science, Vol. 8, Issue 11
  • DOI: 10.1039/C5EE02329G

Acquisition of ultra-wideline NMR spectra from quadrupolar nuclei by frequency stepped WURST–QCPMG
journal, January 2009


Determination of Mn valence states in mixed-valent manganates by XANES spectroscopy
journal, May 2012

  • Manceau, A.; Marcus, M. A.; Grangeon, S.
  • American Mineralogist, Vol. 97, Issue 5-6
  • DOI: 10.2138/am.2012.3903

Lithium-Rich Rock-Salt-Type Vanadate as Energy Storage Cathode: Li 2– x VO 3
journal, December 2011

  • Pralong, Valerie; Gopal, Venkatesh; Caignaert, Vincent
  • Chemistry of Materials, Vol. 24, Issue 1
  • DOI: 10.1021/cm203281q

Designing New Lithium-Excess Cathode Materials from Percolation Theory: Nanohighways in Li x Ni 2–4 x /3 Sb x /3 O 2
journal, December 2014

  • Twu, Nancy; Li, Xin; Urban, Alexander
  • Nano Letters, Vol. 15, Issue 1
  • DOI: 10.1021/nl5040754

Efficient first-principles prediction of solid stability: Towards chemical accuracy
journal, March 2018


ω-LixV2O5 — a new electrode material for rechargeable lithium batteries
journal, March 1991


Compressive sensing as a paradigm for building physics models
journal, January 2013


Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials
journal, October 2017


Reversible Li storage for nanosize cation/anion-disordered rocksalt-type oxyfluorides: LiMoO 2 – x LiF (0 ≤ x ≤ 2) binary system
journal, November 2017


High-Performance Low-Temperature Li + Intercalation in Disordered Rock-Salt Li-Cr-V Oxyfluorides
journal, April 2016


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


On the Efficacy of Electrocatalysis in Nonaqueous Li–O 2 Batteries
journal, November 2011

  • McCloskey, Bryan D.; Scheffler, Rouven; Speidel, Angela
  • Journal of the American Chemical Society, Vol. 133, Issue 45
  • DOI: 10.1021/ja207229n

Nanocrystalline metals prepared by high-energy ball milling
journal, September 1990

  • Fecht, H. J.; Hellstern, E.; Fu, Z.
  • Metallurgical Transactions A, Vol. 21, Issue 9
  • DOI: 10.1007/BF02646980

Fluorination of Lithium-Excess Transition Metal Oxide Cathode Materials
journal, October 2017

  • Richards, William D.; Dacek, Stephen T.; Kitchaev, Daniil A.
  • Advanced Energy Materials, Vol. 8, Issue 5
  • DOI: 10.1002/aenm.201701533

Formation enthalpies by mixing GGA and GGA + U calculations
journal, July 2011


Design of Li 1+2x Zn 1−x PS 4 , a new lithium ion conductor
journal, January 2016

  • Richards, William D.; Wang, Yan; Miara, Lincoln J.
  • Energy & Environmental Science, Vol. 9, Issue 10
  • DOI: 10.1039/C6EE02094A

Understanding the Effect of Cation Disorder on the Voltage Profile of Lithium Transition-Metal Oxides
journal, July 2016


NMR evidence of LiF coating rather than fluorine substitution in Li(Ni0.425Mn0.425Co0.15)O2
journal, December 2008


The Configurational Space of Rocksalt-Type Oxides for High-Capacity Lithium Battery Electrodes
journal, May 2014

  • Urban, Alexander; Lee, Jinhyuk; Ceder, Gerbrand
  • Advanced Energy Materials, Vol. 4, Issue 13
  • DOI: 10.1002/aenm.201400478

Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries
journal, December 2016

  • Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms13814

Oxidation energies of transition metal oxides within the GGA + U framework
journal, May 2006


Key electronic states in lithium battery materials probed by soft X-ray spectroscopy
journal, October 2013

  • Yang, Wanli; Liu, Xiaosong; Qiao, Ruimin
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 190
  • DOI: 10.1016/j.elspec.2013.03.008

Solvents’ Critical Role in Nonaqueous Lithium–Oxygen Battery Electrochemistry
journal, May 2011

  • McCloskey, B. D.; Bethune, D. S.; Shelby, R. M.
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 10, p. 1161-1166
  • DOI: 10.1021/jz200352v

Python Materials Genomics (pymatgen): A robust, open-source python library for materials analysis
journal, February 2013


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