Y-doped Li 8 ZrO 6 : A Li-Ion Battery Cathode Material with High Capacity
Abstract
We study—experimentally and theoretically—the energetics, structural changes, and charge flows during the charging and discharging processes for a new high-capacity cathode material, Li8ZrO6 (LZO), which we study both pure and yttrium-doped. We quantum mechanically calculated the stable delithiated configurations, the delithiation energy, the charge flow during delithiation, and the stability of the delithiated materials. We find that Li atoms are easier to extract from tetrahedral sites than octahedral ones. We calculate a large average voltage of 4.04 eV vs Li/Li+ for delithiation of the first Li atom in a primitive cell, which is confirmed by galvanostatic charge/discharge cycling data. Energy calculations indicate that topotactic delithiation is kinetically favored over decomposition into Li, ZrO2, and O2 during the charging process, although the thermodynamic energy of the topotactic reaction is less favorable. When one or two lithium atoms are extracted from a primitive cell of LZO, its volume and structure change little, whereas extraction of the third lithium greatly distorts the layered structure. The Li6ZrO6 and Li5ZrO6 delithiation products can be thermodynamically metastable to release of O2. Experimentally, materials with sufficiently small particle size for efficient delithiation and relithiation were achieved within an yttrium-doped LZO/carbon composite cathode that exhibited an initial dischargemore »
- Authors:
-
- Department of Chemistry, Chemical Theory Center, and Supercomputing Institute and ‡Department of Chemistry, University of Minnesota, 207 Pleasant Street S.E., Minneapolis, Minnesota 55455-0431, United States
- Publication Date:
- Research Org.:
- Univ. of Minnesota, Minneapolis, MN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1212268
- Alternate Identifier(s):
- OSTI ID: 1455137
- Grant/Contract Number:
- SC0008662
- Resource Type:
- Published Article
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Name: Journal of the American Chemical Society Journal Volume: 137 Journal Issue: 34; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE
Citation Formats
Huang, Shuping, Wilson, Benjamin E., Wang, Bo, Fang, Yuan, Buffington, Keegan, Stein, Andreas, and Truhlar, Donald G. Y-doped Li 8 ZrO 6 : A Li-Ion Battery Cathode Material with High Capacity. United States: N. p., 2015.
Web. doi:10.1021/jacs.5b04690.
Huang, Shuping, Wilson, Benjamin E., Wang, Bo, Fang, Yuan, Buffington, Keegan, Stein, Andreas, & Truhlar, Donald G. Y-doped Li 8 ZrO 6 : A Li-Ion Battery Cathode Material with High Capacity. United States. https://doi.org/10.1021/jacs.5b04690
Huang, Shuping, Wilson, Benjamin E., Wang, Bo, Fang, Yuan, Buffington, Keegan, Stein, Andreas, and Truhlar, Donald G. Thu .
"Y-doped Li 8 ZrO 6 : A Li-Ion Battery Cathode Material with High Capacity". United States. https://doi.org/10.1021/jacs.5b04690.
@article{osti_1212268,
title = {Y-doped Li 8 ZrO 6 : A Li-Ion Battery Cathode Material with High Capacity},
author = {Huang, Shuping and Wilson, Benjamin E. and Wang, Bo and Fang, Yuan and Buffington, Keegan and Stein, Andreas and Truhlar, Donald G.},
abstractNote = {We study—experimentally and theoretically—the energetics, structural changes, and charge flows during the charging and discharging processes for a new high-capacity cathode material, Li8ZrO6 (LZO), which we study both pure and yttrium-doped. We quantum mechanically calculated the stable delithiated configurations, the delithiation energy, the charge flow during delithiation, and the stability of the delithiated materials. We find that Li atoms are easier to extract from tetrahedral sites than octahedral ones. We calculate a large average voltage of 4.04 eV vs Li/Li+ for delithiation of the first Li atom in a primitive cell, which is confirmed by galvanostatic charge/discharge cycling data. Energy calculations indicate that topotactic delithiation is kinetically favored over decomposition into Li, ZrO2, and O2 during the charging process, although the thermodynamic energy of the topotactic reaction is less favorable. When one or two lithium atoms are extracted from a primitive cell of LZO, its volume and structure change little, whereas extraction of the third lithium greatly distorts the layered structure. The Li6ZrO6 and Li5ZrO6 delithiation products can be thermodynamically metastable to release of O2. Experimentally, materials with sufficiently small particle size for efficient delithiation and relithiation were achieved within an yttrium-doped LZO/carbon composite cathode that exhibited an initial discharge capacity of at least 200 mAh/g over the first 10 cycles, with 142 mAh/g maintained after 60 cycles. Computations predict that during the charging process, the oxygen ion near the Li vacancy is oxidized for both pure LZO and yttrium-doped LZO, which leads to a small-polaron hole.},
doi = {10.1021/jacs.5b04690},
journal = {Journal of the American Chemical Society},
number = 34,
volume = 137,
place = {United States},
year = {Thu Aug 20 00:00:00 EDT 2015},
month = {Thu Aug 20 00:00:00 EDT 2015}
}
https://doi.org/10.1021/jacs.5b04690
Web of Science
Works referenced in this record:
Lithium diffusion mechanisms in layered intercalation compounds
journal, July 2001
- Van der Ven, A.; Ceder, G.
- Journal of Power Sources, Vol. 97-98
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
High-Pressure Investigation of Li 2 MnSiO 4 and Li 2 CoSiO 4 Electrode Materials for Lithium-Ion Batteries
journal, May 2012
- Santamaría-Pérez, D.; Amador, U.; Tortajada, J.
- Inorganic Chemistry, Vol. 51, Issue 10
Quest for a universal density functional: the accuracy of density functionals across a broad spectrum of databases in chemistry and physics
journal, March 2014
- Peverati, Roberto; Truhlar, Donald G.
- Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 372, Issue 2011
Challenges for Rechargeable Li Batteries
journal, February 2010
- Goodenough, John B.; Kim, Youngsik
- Chemistry of Materials, Vol. 22, Issue 3, p. 587-603
�ber Lithium- und Natriumuranate(V) und �ber strukturelle Beziehungen zwischen den Verbindungstypen Li7AO6 und Li8AO6
journal, February 1964
- Scholder, R.; Gl�ser, H.
- Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 327, Issue 1-2
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Three-Step Calcination Synthesis of High-Purity Li 8 ZrO 6 with CO 2 Absorption Properties
journal, April 2011
- Yin, Xian-Sheng; Zhang, Qin-Hui; Yu, Jian-Guo
- Inorganic Chemistry, Vol. 50, Issue 7
Nondilute diffusion from first principles: Li diffusion in
journal, September 2008
- Van der Ven, Anton; Thomas, John C.; Xu, Qingchuan
- Physical Review B, Vol. 78, Issue 10
Spectroscopic and Photoluminescence Studies of a Wide Band Gap Insulating Material: Powdered and Colloidal ZrO 2 Sols
journal, September 1998
- Emeline, Alexei; Kataeva, Galina V.; Litke, Alexander S.
- Langmuir, Vol. 14, Issue 18
X-ray-photoelectron-spectroscopy evidence for peroxide in 1:2:3 copper oxides containing disordered or excess oxygen
journal, September 1988
- Dai, Y.; Manthiram, A.; Campion, A.
- Physical Review B, Vol. 38, Issue 7
Phase transformations and volume changes in spinel LixMn2O4
journal, November 2000
- Van der Ven, A.
- Solid State Ionics, Vol. 135, Issue 1-4
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Enhanced Li Adsorption and Diffusion on MoS2 Zigzag Nanoribbons by Edge Effects: A Computational Study
journal, August 2012
- Li, Yafei; Wu, Dihua; Zhou, Zhen
- The Journal of Physical Chemistry Letters, Vol. 3, Issue 16, p. 2221-2227
Thermodynamic stability of the lithium zirconates and lithium yttrate
journal, June 1994
- Zou, Yun; Petric, Anthony
- Journal of Physics and Chemistry of Solids, Vol. 55, Issue 6
Structural and electronic properties of Li8ZrO6 and its CO2 capture capabilities: an ab initio thermodynamic approach
journal, January 2013
- Duan, Yuhua
- Physical Chemistry Chemical Physics, Vol. 15, Issue 24
On the Energetic Stability and Electrochemistry of Li 2 MnSiO 4 Polymorphs
journal, September 2008
- Arroyo-deDompablo, M. E.; Dominko, R.; Gallardo-Amores, J. M.
- Chemistry of Materials, Vol. 20, Issue 17
Band-gap energy estimation from diffuse reflectance measurements on sol–gel and commercial TiO2: a comparative study
journal, September 2011
- López, Rosendo; Gómez, Ricardo
- Journal of Sol-Gel Science and Technology, Vol. 61, Issue 1
First principles computational materials design for energy storage materials in lithium ion batteries
journal, January 2009
- Meng, Ying Shirley; Arroyo-de Dompablo, M. Elena
- Energy & Environmental Science, Vol. 2, Issue 6
First-principles calculations of the electronic structure and spectra of strongly correlated systems: the LDA + U method
journal, January 1997
- Anisimov, Vladimir I.; Aryasetiawan, F.; Lichtenstein, A. I.
- Journal of Physics: Condensed Matter, Vol. 9, Issue 4, p. 767-808
Ordered Mesoporous Polymers and Homologous Carbon Frameworks: Amphiphilic Surfactant Templating and Direct Transformation
journal, November 2005
- Meng, Yan; Gu, Dong; Zhang, Fuqiang
- Angewandte Chemie International Edition, Vol. 44, Issue 43, p. 7053-7059
PHON: A program to calculate phonons using the small displacement method
journal, December 2009
- Alfè, Dario
- Computer Physics Communications, Vol. 180, Issue 12
Synthesis of yttria-stabilized zirconia nanoparticles by decomposition of metal nitrates coated on carbon powder
journal, September 1996
- Jiang, Shusheng; Stangle, Gregory C.; Amarakoon, Vasantha R. W.
- Journal of Materials Research, Vol. 11, Issue 9
Electronic structural and electrochemical properties of lithium zirconates and their capabilities of CO2 capture: A first-principles density-functional theory and phonon dynamics approach
journal, January 2011
- Duan, Yuhua
- Journal of Renewable and Sustainable Energy, Vol. 3, Issue 1
Optical Properties and Electronic Structure of Amorphous Germanium
journal, January 1966
- Tauc, J.; Grigorovici, R.; Vancu, A.
- physica status solidi (b), Vol. 15, Issue 2
Des conducteurs ioniques pseudo-bidimensionnels: Li8MO6 (M = Zr, Sn), Li7LO6 (L = Nb, Ta) et Li6In2O6
journal, May 1979
- Delmas, C.; Maazaz, A.; Guillen, F.
- Materials Research Bulletin, Vol. 14, Issue 5
First-principles investigation of phase stability in
journal, August 1998
- Van der Ven, A.; Aydinol, M. K.; Ceder, G.
- Physical Review B, Vol. 58, Issue 6
Hole localization in Al doped silica: A DFT+U description
journal, October 2006
- Nolan, Michael; Watson, Graeme W.
- The Journal of Chemical Physics, Vol. 125, Issue 14
The electronic structure of alkali doped alkaline earth metal oxides: Li doping of MgO studied with DFT-GGA and GGA+U
journal, July 2005
- Nolan, Michael; Watson, Graeme W.
- Surface Science, Vol. 586, Issue 1-3
Germanium–tin alloy nanocrystals for high-performance lithium ion batteries
journal, January 2013
- Cho, Yong Jae; Kim, Chang Hyun; Im, Hyung Soon
- Physical Chemistry Chemical Physics, Vol. 15, Issue 28
DFT+U Study of Polaronic Conduction in Li 2 O 2 and Li 2 CO 3 : Implications for Li–Air Batteries
journal, March 2013
- Garcia-Lastra, J. M.; Myrdal, J. S. G.; Christensen, R.
- The Journal of Physical Chemistry C, Vol. 117, Issue 11
Opportunities and challenges for first-principles materials design and applications to Li battery materials
journal, September 2010
- Ceder, Gerbrand
- MRS Bulletin, Vol. 35, Issue 9
Recharging lithium battery research with first-principles methods
journal, March 2011
- Ceder, G.; Hautier, G.; Jain, A.
- MRS Bulletin, Vol. 36, Issue 3
Multiconstituent Synthesis of LiFePO 4 /C Composites with Hierarchical Porosity as Cathode Materials for Lithium Ion Batteries
journal, July 2011
- Vu, Anh; Stein, Andreas
- Chemistry of Materials, Vol. 23, Issue 13
New Insights into the Structural and Dynamical Features of Lithium Hexaoxometalates Li 7 MO 6 (M = Nb, Ta, Sb, Bi)
journal, February 2004
- Mühle, Claus; Dinnebier, Robert E.; van Wüllen, Leo
- Inorganic Chemistry, Vol. 43, Issue 3
Thermal stability improvement on pore and phase structure of sol-gel derived zirconia
journal, June 1995
- Gopalan, R.; Chang, C. -H.; Lin, Y. S.
- Journal of Materials Science, Vol. 30, Issue 12
Exchange–Correlation Functional with Good Accuracy for Both Structural and Energetic Properties while Depending Only on the Density and Its Gradient
journal, June 2012
- Peverati, Roberto; Truhlar, Donald G.
- Journal of Chemical Theory and Computation, Vol. 8, Issue 7
Enhanced Li+ ion transport in LiNi0.5Mn1.5O4 through control of site disorder
journal, January 2012
- Zheng, Jianming; Xiao, Jie; Yu, Xiqian
- Physical Chemistry Chemical Physics, Vol. 14, Issue 39
Ion transport and phase transition in Li 7−x La 3 (Zr 2−x M x )O 12 (M = Ta 5+ , Nb 5+ , x = 0, 0.25)
journal, January 2012
- Adams, Stefan; Rao, Rayavarapu Prasada
- J. Mater. Chem., Vol. 22, Issue 4
Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965
- Kohn, W.; Sham, L. J.
- Physical Review, Vol. 140, Issue 4A, p. A1133-A1138
Performance of the M11-L density functional for bandgaps and lattice constants of unary and binary semiconductors
journal, April 2012
- Peverati, Roberto; Truhlar, Donald G.
- The Journal of Chemical Physics, Vol. 136, Issue 13
Phase diagrams of lithium transition metal oxides: investigations from first principles
journal, September 1999
- Ceder, Gerbrand; Van der Ven, Anton
- Electrochimica Acta, Vol. 45, Issue 1-2, p. 131-150
Defect ordering in aliovalently doped cubic zirconia from first principles
journal, June 2001
- Bogicevic, A.; Wolverton, C.; Crosbie, G. M.
- Physical Review B, Vol. 64, Issue 1
Surface structures and crystal morphologies of LiFePO4: relevance to electrochemical behaviour
journal, January 2008
- Fisher, Craig A. J.; Islam, M. Saiful
- Journal of Materials Chemistry, Vol. 18, Issue 11
A Facile Mechanism for Recharging Li2O2 in Li–O2 Batteries
journal, August 2013
- Kang, ShinYoung; Mo, Yifei; Ong, Shyue Ping
- Chemistry of Materials, Vol. 25, Issue 16, p. 3328-3336
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Rotationally invariant ab initio evaluation of Coulomb and exchange parameters for DFT+U calculations
journal, July 2008
- Mosey, Nicholas J.; Liao, Peilin; Carter, Emily A.
- The Journal of Chemical Physics, Vol. 129, Issue 1
Metallic VS 2 Monolayer: A Promising 2D Anode Material for Lithium Ion Batteries
journal, November 2013
- Jing, Yu; Zhou, Zhen; Cabrera, Carlos R.
- The Journal of Physical Chemistry C, Vol. 117, Issue 48
Phase stability and nondilute Li diffusion in spinel
journal, March 2010
- Bhattacharya, Jishnu; Van der Ven, Anton
- Physical Review B, Vol. 81, Issue 10
Screened-exchange density functionals with broad accuracy for chemistry and solid-state physics
journal, January 2012
- Peverati, Roberto; Truhlar, Donald G.
- Physical Chemistry Chemical Physics, Vol. 14, Issue 47
Influence of the exchange screening parameter on the performance of screened hybrid functionals
journal, December 2006
- Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F.
- The Journal of Chemical Physics, Vol. 125, Issue 22
Low hole polaron migration barrier in lithium peroxide
journal, February 2012
- Ong, Shyue Ping; Mo, Yifei; Ceder, Gerbrand
- Physical Review B, Vol. 85, Issue 8
First-Principles Investigation of Phase Stability in the O2-LiCoO 2 System
journal, July 2003
- Carlier, D.; Van der Ven, A.; Delmas, C.
- Chemistry of Materials, Vol. 15, Issue 13
Control of TiO 2 Grain Size and Positioning in Three-Dimensionally Ordered Macroporous TiO 2 /C Composite Anodes for Lithium Ion Batteries
journal, December 2013
- Petkovich, Nicholas D.; Rudisill, Stephen G.; Wilson, Benjamin E.
- Inorganic Chemistry, Vol. 53, Issue 2
A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions
journal, November 2006
- Zhao, Yan; Truhlar, Donald G.
- The Journal of Chemical Physics, Vol. 125, Issue 19, Article No. 194101
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Challenges in the development of advanced Li-ion batteries: a review
journal, January 2011
- Etacheri, Vinodkumar; Marom, Rotem; Elazari, Ran
- Energy & Environmental Science, Vol. 4, Issue 9
Ab initio study of lithium transition metal fluorophosphate cathodes for rechargeable batteries
journal, January 2011
- Yu, Jianguo; Rosso, Kevin M.; Zhang, Ji-Guang
- Journal of Materials Chemistry, Vol. 21, Issue 32
Toward reliable density functional methods without adjustable parameters: The PBE0 model
journal, April 1999
- Adamo, Carlo; Barone, Vincenzo
- The Journal of Chemical Physics, Vol. 110, Issue 13
Li−Fe−P−O 2 Phase Diagram from First Principles Calculations
journal, February 2008
- Ong, Shyue Ping; Wang, Lei; Kang, Byoungwoo
- Chemistry of Materials, Vol. 20, Issue 5
Charge Model 5: An Extension of Hirshfeld Population Analysis for the Accurate Description of Molecular Interactions in Gaseous and Condensed Phases
journal, February 2012
- Marenich, Aleksandr V.; Jerome, Steven V.; Cramer, Christopher J.
- Journal of Chemical Theory and Computation, Vol. 8, Issue 2, p. 527-541
Crystal Structure, Energetics, And Electrochemistry of Li 2 FeSiO 4 Polymorphs from First Principles Calculations
journal, December 2011
- Saracibar, A.; Van der Ven, A.; Arroyo-de Dompablo, M. E.
- Chemistry of Materials, Vol. 24, Issue 3
Li 2 MnSiO 4 Lithium Battery Material: Atomic-Scale Study of Defects, Lithium Mobility, and Trivalent Dopants
journal, November 2009
- Kuganathan, N.; Islam, M. S.
- Chemistry of Materials, Vol. 21, Issue 21
Surface states on NiO (100) and the origin of the contrast reversal in atomically resolved scanning tunneling microscope images
journal, August 1997
- Dudarev, S. L.; Liechtenstein, A. I.; Castell, M. R.
- Physical Review B, Vol. 56, Issue 8
La1−xCaxCoO3 perovskite-type oxides: Identification of the surface oxygen species by XPS
journal, November 2006
- Merino, Nora A.; Barbero, Bibiana P.; Eloy, Pierre
- Applied Surface Science, Vol. 253, Issue 3
Nanostructured materials for advanced energy conversion and storage devices
journal, May 2005
- Aricò, Antonino Salvatore; Bruce, Peter; Scrosati, Bruno
- Nature Materials, Vol. 4, Issue 5, p. 366-377
Calculation of semiconductor band gaps with the M06-L density functional
journal, February 2009
- Zhao, Yan; Truhlar, Donald G.
- The Journal of Chemical Physics, Vol. 130, Issue 7, Article No. 074103
Insights into Changes in Voltage and Structure of Li 2 FeSiO 4 Polymorphs for Lithium-Ion Batteries
journal, May 2012
- Eames, C.; Armstrong, A. R.; Bruce, P. G.
- Chemistry of Materials, Vol. 24, Issue 11
Are MXenes Promising Anode Materials for Li Ion Batteries? Computational Studies on Electronic Properties and Li Storage Capability of Ti 3 C 2 and Ti 3 C 2 X 2 (X = F, OH) Monolayer
journal, September 2012
- Tang, Qing; Zhou, Zhen; Shen, Panwen
- Journal of the American Chemical Society, Vol. 134, Issue 40
Nanostructured electrode materials for electrochemical energy storage and conversion
journal, January 2008
- Manthiram, A.; Vadivel Murugan, A.; Sarkar, A.
- Energy & Environmental Science, Vol. 1, Issue 6
Defect Physics, Delithiation Mechanism, and Electronic and Ionic Conduction in Layered Lithium Manganese Oxide Cathode Materials
journal, February 2015
- Hoang, Khang
- Physical Review Applied, Vol. 3, Issue 2
POWDER CELL – a program for the representation and manipulation of crystal structures and calculation of the resulting X-ray powder patterns
journal, June 1996
- Kraus, W.; Nolze, G.
- Journal of Applied Crystallography, Vol. 29, Issue 3, p. 301-303
First-principles investigations on delithiation of Li 4 NiTeO 6
journal, January 2014
- Bao, Jie; Wu, Dihua; Tang, Qing
- Physical Chemistry Chemical Physics, Vol. 16, Issue 30
Magnetism from states in alkaline earth monoxides: Trends with varying N impurity concentration
journal, October 2008
- Pardo, V.; Pickett, W. E.
- Physical Review B, Vol. 78, Issue 13
Multicomponent Silicate Cathode Materials for Rechargeable Li-Ion Batteries: An Ab Initio Study
journal, November 2012
- Longo, R. C.; Xiong, K.; Cho, K.
- Journal of The Electrochemical Society, Vol. 160, Issue 1
Porous Electrode Materials for Lithium-Ion Batteries - How to Prepare Them and What Makes Them Special
journal, August 2012
- Vu, Anh; Qian, Yuqiang; Stein, Andreas
- Advanced Energy Materials, Vol. 2, Issue 9