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Title: Multi-Stage Structural Transformations in Zero-Strain Lithium Titanate Unveiled by in Situ X-ray Absorption Fingerprints

Abstract

Zero-strain electrodes, such as spinel lithium titanate (Li4/3Ti5/3O4), are appealing for application in batteries due to their negligible volume change and extraordinary stability upon repeated charge/discharge cycles. On the other hand, this same property makes it challenging to probe their structural changes during the electrochemical reaction. Herein, we report in situ studies of lithiation-driven structural transformations in Li4/3Ti5/3O4 via a combination of X-ray absorption spectroscopy and ab initio calculations. Based on excellent agreement between computational and experimental spectra of Ti K-edge, we identified key spectral features as fingerprints for quantitative assessment of structural evolution at different length scales. Results from this study indicate that, despite the small variation in the crystal lattice during lithiation, pronounced structural transformations occur in Li4/3Ti5/3O4, both locally and globally, giving rise to a multi-stage kinetic process involving mixed quasi-solid solution/macroscopic two-phase transformations over a wide range of Li concentrations. This work highlights the unique capability of combining in situ core-level spectroscopy and first-principles calculations for probing Li-ion intercalation in zero-strain electrodes, which is crucial to designing high-performance electrode materials for long-life batteries.

Authors:
 [1];  [2];  [3];  [4];  [1];  [5];  [6];  [6]; ORCiD logo [7];  [8]; ORCiD logo [9]; ORCiD logo [9];  [2]; ORCiD logo [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States). Sustainable Energy Technologies Dept.
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
  3. Stony Brook Univ., NY (United States). Dept. of Chemistry
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). Energy and Photon Sciences Directorate
  5. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II
  6. Brookhaven National Lab. (BNL), Upton, NY (United States). Condensed Matter Physics and Materials Science Dept.
  7. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.; Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering
  8. Stony Brook Univ., NY (United States). Dept. of Chemistry. Dept. of Materials Science and Chemical Engineering
  9. Stony Brook Univ., NY (United States). Dept. of Chemistry. Dept. of Materials Science and Chemical Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States). Energy and Photon Sciences Directorate
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2mt); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); BNL Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1439804
Alternate Identifier(s):
OSTI ID: 1489025
Report Number(s):
BNL-114533-2017-JAAM
Journal ID: ISSN 0002-7863
Grant/Contract Number:  
SC0012704; SC0012673; FG02-03ER15476; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 46; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zhang, Wei, Topsakal, Mehmet, Cama, Christina, Pelliccione, Christopher J., Zhao, Hu, Ehrlich, Steven, Wu, Lijun, Zhu, Yimei, Frenkel, Anatoly I., Takeuchi, Kenneth J., Takeuchi, Esther S., Marschilok, Amy C., Lu, Deyu, and Wang, Feng. Multi-Stage Structural Transformations in Zero-Strain Lithium Titanate Unveiled by in Situ X-ray Absorption Fingerprints. United States: N. p., 2017. Web. https://doi.org/10.1021/jacs.7b07628.
Zhang, Wei, Topsakal, Mehmet, Cama, Christina, Pelliccione, Christopher J., Zhao, Hu, Ehrlich, Steven, Wu, Lijun, Zhu, Yimei, Frenkel, Anatoly I., Takeuchi, Kenneth J., Takeuchi, Esther S., Marschilok, Amy C., Lu, Deyu, & Wang, Feng. Multi-Stage Structural Transformations in Zero-Strain Lithium Titanate Unveiled by in Situ X-ray Absorption Fingerprints. United States. https://doi.org/10.1021/jacs.7b07628
Zhang, Wei, Topsakal, Mehmet, Cama, Christina, Pelliccione, Christopher J., Zhao, Hu, Ehrlich, Steven, Wu, Lijun, Zhu, Yimei, Frenkel, Anatoly I., Takeuchi, Kenneth J., Takeuchi, Esther S., Marschilok, Amy C., Lu, Deyu, and Wang, Feng. Fri . "Multi-Stage Structural Transformations in Zero-Strain Lithium Titanate Unveiled by in Situ X-ray Absorption Fingerprints". United States. https://doi.org/10.1021/jacs.7b07628. https://www.osti.gov/servlets/purl/1439804.
@article{osti_1439804,
title = {Multi-Stage Structural Transformations in Zero-Strain Lithium Titanate Unveiled by in Situ X-ray Absorption Fingerprints},
author = {Zhang, Wei and Topsakal, Mehmet and Cama, Christina and Pelliccione, Christopher J. and Zhao, Hu and Ehrlich, Steven and Wu, Lijun and Zhu, Yimei and Frenkel, Anatoly I. and Takeuchi, Kenneth J. and Takeuchi, Esther S. and Marschilok, Amy C. and Lu, Deyu and Wang, Feng},
abstractNote = {Zero-strain electrodes, such as spinel lithium titanate (Li4/3Ti5/3O4), are appealing for application in batteries due to their negligible volume change and extraordinary stability upon repeated charge/discharge cycles. On the other hand, this same property makes it challenging to probe their structural changes during the electrochemical reaction. Herein, we report in situ studies of lithiation-driven structural transformations in Li4/3Ti5/3O4 via a combination of X-ray absorption spectroscopy and ab initio calculations. Based on excellent agreement between computational and experimental spectra of Ti K-edge, we identified key spectral features as fingerprints for quantitative assessment of structural evolution at different length scales. Results from this study indicate that, despite the small variation in the crystal lattice during lithiation, pronounced structural transformations occur in Li4/3Ti5/3O4, both locally and globally, giving rise to a multi-stage kinetic process involving mixed quasi-solid solution/macroscopic two-phase transformations over a wide range of Li concentrations. This work highlights the unique capability of combining in situ core-level spectroscopy and first-principles calculations for probing Li-ion intercalation in zero-strain electrodes, which is crucial to designing high-performance electrode materials for long-life batteries.},
doi = {10.1021/jacs.7b07628},
journal = {Journal of the American Chemical Society},
number = 46,
volume = 139,
place = {United States},
year = {2017},
month = {10}
}

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Works referenced in this record:

History, Evolution, and Future Status of Energy Storage
journal, May 2012


Electrical Energy Storage for the Grid: A Battery of Choices
journal, November 2011


Structure and electrochemistry of the spinel oxides LiTi2O4 and Li43Ti53O4
journal, May 1989


Zero-Strain Insertion Material of Li[Li[sub 1∕3]Ti[sub 5∕3]]O[sub 4] for Rechargeable Lithium Cells
journal, January 1995

  • Ohzuku, Tsutomu
  • Journal of The Electrochemical Society, Vol. 142, Issue 5
  • DOI: 10.1149/1.2048592

Spinel Anodes for Lithium-Ion Batteries
journal, January 1994

  • Ferg, E.; Gummow, R. J.; de Kock, A.
  • Journal of The Electrochemical Society, Vol. 141, Issue 11, p. L147-L150
  • DOI: 10.1149/1.2059324

Recent development and application of Li4Ti5O12 as anode material of lithium ion battery
journal, September 2010

  • Yi, Ting-Feng; Jiang, Li-Juan; Shu, J.
  • Journal of Physics and Chemistry of Solids, Vol. 71, Issue 9, p. 1236-1242
  • DOI: 10.1016/j.jpcs.2010.05.001

Safe and fast-charging Li-ion battery with long shelf life for power applications
journal, April 2011


Two-phase separation in a lithiated spinel Li4Ti5O12 crystal as confirmed by electron energy-loss spectroscopy
journal, July 2014


Lithium Storage in Li4Ti5O12 Spinel: The Full Static Picture from Electron Microscopy
journal, May 2012


Lithium Migration in Li 4 Ti 5 O 12 Studied Using in Situ Neutron Powder Diffraction
journal, March 2014

  • Pang, Wei Kong; Peterson, Vanessa K.; Sharma, Neeraj
  • Chemistry of Materials, Vol. 26, Issue 7
  • DOI: 10.1021/cm5002779

Evidence of Two-Phase Formation upon Lithium Insertion into the Li[sub 1.33]Ti[sub 1.67]O[sub 4] Spinel
journal, January 1999

  • Scharner, S.
  • Journal of The Electrochemical Society, Vol. 146, Issue 3
  • DOI: 10.1149/1.1391692

A Kinetic Two-Phase and Equilibrium Solid Solution in Spinel Li4+xTi5O12
journal, December 2006

  • Wagemaker, M.; Simon, D. R.; Kelder, E. M.
  • Advanced Materials, Vol. 18, Issue 23
  • DOI: 10.1002/adma.200601636

Small Change—Great Effect: Steep Increase of Li Ion Dynamics in Li 4 Ti 5 O 12 at the Early Stages of Chemical Li Insertion
journal, February 2015

  • Schmidt, Walter; Bottke, Patrick; Sternad, Michael
  • Chemistry of Materials, Vol. 27, Issue 5
  • DOI: 10.1021/cm504564k

Li-Ion Diffusion in the Equilibrium Nanomorphology of Spinel Li 4+ x Ti 5 O 12
journal, January 2009

  • Wagemaker, Marnix; van Eck, Ernst R. H.; Kentgens, Arno P. M.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 1
  • DOI: 10.1021/jp8073706

Microscopic Li self-diffusion parameters in the lithiated anode material Li4+xTi5O12 (0 ≤x≤ 3) measured by 7Li solid state NMR
journal, January 2007

  • Wilkening, Martin; Iwaniak, Wojciech; Heine, Jessica
  • Physical Chemistry Chemical Physics, Vol. 9, Issue 47
  • DOI: 10.1039/b713311a

Study of local structure and Li dynamics in () using 6Li and 7Li NMR spectroscopy
journal, April 2012


The Fine Line between a Two-Phase and Solid-Solution Phase Transformation and Highly Mobile Phase Interfaces in Spinel Li 4+ x Ti 5 O 12
journal, December 2016

  • Ganapathy, Swapna; Vasileiadis, Alexandros; Heringa, Jouke R.
  • Advanced Energy Materials, Vol. 7, Issue 9
  • DOI: 10.1002/aenm.201601781

Sustainability and in situ monitoring in battery development
journal, December 2016

  • Grey, C. P.; Tarascon, J. M.
  • Nature Materials, Vol. 16, Issue 1
  • DOI: 10.1038/nmat4777

The electrochemical and local structural analysis of the mesoporous Li4Ti5O12 anode
journal, December 2014


An NMR Investigation of Lithium Occupancy of Different Sites in the Oxide Superconductor LiTi2O4 and Related Compounds
journal, July 2000

  • Kartha, J. P.; Tunstall, D. P.; Irvine, John T. S.
  • Journal of Solid State Chemistry, Vol. 152, Issue 2
  • DOI: 10.1006/jssc.2000.8696

Coordination chemistry of Ti(IV) in silicate glasses and melts: I. XAFS study of titanium coordination in oxide model compounds
journal, August 1996


Electron Population Analysis by Full-Potential X-Ray Absorption Simulations
journal, March 1999


Determination of Ti coordination from pre-edge peaks in Ti K -edge XANES
journal, December 2007


Electronic structure of the spinel Li4Ti5O12 studied by ab initio calculations and X-ray absorption spectroscopy
journal, February 2004


Excess lithium storage and charge compensation in nanoscale Li 4+ x Ti 5 O 12
journal, September 2013


Electrochemical properties of nano-sized Li4Ti5O12 powders synthesized by a sol–gel process and characterized by X-ray absorption spectroscopy
journal, August 2005


In situ neutron diffraction study of Li insertion in Li4Ti5O12
journal, June 2010


Electrochemical behavior and stability of Li4Ti5O12 in a broad voltage window
journal, November 2008


IFEFFIT  : interactive XAFS analysis and FEFF fitting
journal, March 2001


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


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

Heyd-Scuseria-Ernzerhof hybrid functional for calculating the lattice dynamics of semiconductors
journal, September 2009


Screened hybrid density functionals applied to solids
journal, April 2006

  • Paier, J.; Marsman, M.; Hummer, K.
  • The Journal of Chemical Physics, Vol. 124, Issue 15
  • DOI: 10.1063/1.2187006

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


Ab initiomolecular dynamics for liquid metals
journal, January 1993


Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994


Ab initio study of the electronic states induced by oxygen vacancies in rutile and anatase TiO 2
journal, December 2008


First-principles analysis on role of spinel (111) phase boundaries in Li 4+3x Ti 5 O 12 Li-ion battery anodes
journal, January 2016

  • Tanaka, Yoshinori; Ikeda, Minoru; Sumita, Masato
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 33
  • DOI: 10.1039/C6CP04131K

Linear response approach to the calculation of the effective interaction parameters in the LDA + U method
journal, January 2005


Facet-dependent trapping and dynamics of excess electrons at anatase TiO2 surfaces and aqueous interfaces
journal, June 2016

  • Selcuk, Sencer; Selloni, Annabella
  • Nature Materials, Vol. 15, Issue 10
  • DOI: 10.1038/nmat4672

Efficient implementation of core-excitation Bethe–Salpeter equation calculations
journal, December 2015


Bethe-Salpeter equation calculations of core excitation spectra
journal, March 2011


QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009

  • Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
  • Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
  • DOI: 10.1088/0953-8984/21/39/395502

Theoretical optical and x-ray spectra of liquid and solid H 2 O
journal, January 2012


An Electrochemical Cell for Operando Study of Lithium Batteries Using Synchrotron Radiation
journal, January 2010

  • Leriche, J. B.; Hamelet, S.; Shu, J.
  • Journal of The Electrochemical Society, Vol. 157, Issue 5
  • DOI: 10.1149/1.3355977

Electronic Structure of the Electrochemically Delithiated Li[sub 1−x]FePO[sub 4] Electrodes Investigated by P K-edge X-Ray Absorption Spectroscopy
journal, January 2006

  • Yoon, Won-Sub; Chung, Kyung Yoon; McBreen, James
  • Electrochemical and Solid-State Letters, Vol. 9, Issue 9
  • DOI: 10.1149/1.2216619

MCR-ALS GUI 2.0: New features and applications
journal, January 2015


Vanadium K-Edge X-ray Absorption Spectroscopy as a Probe of the Heterogeneous Lithiation of V 2 O 5 : First-Principles Modeling and Principal Component Analysis
journal, October 2016

  • Horrocks, Gregory A.; Braham, Erick J.; Liang, Yufeng
  • The Journal of Physical Chemistry C, Vol. 120, Issue 42
  • DOI: 10.1021/acs.jpcc.6b06499

Lithium diffusion in the spinel phase Li 4 Ti 5 O 12 and in the rocksalt phase Li 7 Ti 5 O 12 of lithium titanate from first principles
journal, May 2014


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

Tailoring Native Defects and Zinc Impurities in Li 4 Ti 5 O 12 : Insights from First-Principles Study
journal, February 2015


Atomistic Structure and Ab Initio Electrochemical Properties of Li 4 Ti 5 O 12 Defect Spinel for Li Ion Batteries
journal, December 2013

  • Tsai, Ping-chun; Hsu, Wen-Dung; Lin, Shih-kang
  • Journal of The Electrochemical Society, Vol. 161, Issue 3
  • DOI: 10.1149/2.095403jes

Ab initio Studies on Li 4+ x Ti 5 O 12 Compounds as Anode Materials for Lithium-Ion Batteries
journal, October 2008


Elucidating the Phase Transformation of Li 4 Ti 5 O 12 Lithiation at the Nanoscale
journal, March 2016


Phase stability and nondilute Li diffusion in spinel Li 1 + x Ti 2 O 4
journal, March 2010


Pressure-induced disappearance of the local rhombohedral distortion in BaTiO 3
journal, May 2006


Ti 1s pre-edge features in rutile: a Bethe-Salpeter calculation
journal, May 2004


Atomic signatures of local environment from core-level spectroscopy in β Ga 2 O 3
journal, August 2016


Quasiparticle lifetime broadening in resonant x-ray scattering of NH 4 NO 3
journal, July 2016


Accurate X-Ray Spectral Predictions: An Advanced Self-Consistent-Field Approach Inspired by Many-Body Perturbation Theory
journal, March 2017


On the hydration and hydrolysis of carbon dioxide
journal, October 2011


Neutron diffraction study of Li 4 Ti 5 O 12 at low temperatures
journal, October 2014


Formation of the pre-edge structure and dramatic polarization dependence of Ti K NEXAFS in PbTiO3 crystals
journal, March 1995


Capturing metastable structures during high-rate cycling of LiFePO4 nanoparticle electrodes
journal, June 2014


Novel lithium insertion material of LiCo1/3Ni1/3Mn1/3O2 for advanced lithium-ion batteries
journal, June 2003


Kinetics of non-equilibrium lithium incorporation in LiFePO4
journal, July 2011

  • Malik, Rahul; Zhou, Fei; Ceder, G.
  • Nature Materials, Vol. 10, Issue 8
  • DOI: 10.1038/nmat3065

Understanding the Zero-Strain Lithium Insertion Scheme of Li[Li 1/3 Ti 5/3 ]O 4 : Structural Changes at Atomic Scale Clarified by Raman Spectroscopy
journal, January 2014

  • Mukai, Kazuhiko; Kato, Yuichi; Nakano, Hideyuki
  • The Journal of Physical Chemistry C, Vol. 118, Issue 6
  • DOI: 10.1021/jp412196v

    Works referencing / citing this record:

    Toward Optimal Performance and In-Depth Understanding of Spinel Li 4 Ti 5 O 12 Electrodes through Phase Field Modeling
    journal, February 2018

    • Vasileiadis, Alexandros; de Klerk, Niek J. J.; Smith, Raymond B.
    • Advanced Functional Materials, Vol. 28, Issue 16
    • DOI: 10.1002/adfm.201705992

    Electron-Hole Theory of the Effect of Quantum Nuclei on the X-Ray Absorption Spectra of Liquid Water
    journal, September 2018


    Atomic-scale structural and chemical evolution of Li3V2(PO4)3 cathode cycled at high voltage window
    journal, May 2019


    Identifying the Origin and Contribution of Surface Storage in TiO 2 (B) Nanotube Electrode by In Situ Dynamic Valence State Monitoring
    journal, July 2018

    • Tang, Yuxin; Zhang, Yanyan; Malyi, Oleksandr I.
    • Advanced Materials, Vol. 30, Issue 33
    • DOI: 10.1002/adma.201802200

    Crystal structure, solid phase diffusion path and coefficient of Zr-doped Li 4 Ti 5 O 12
    journal, September 2019