Morphological and Electrochemical Characterization of Nanostructured Li4Ti5O12 Electrodes Using Multiple Imaging Mode Synchrotron X-ray Computed Tomography

Kashkooli, Ali Ghorbani; Foreman, Evan; Farhad, Siamak; Lee, Dong Un; Feng, Kun; Lui, Gregory; De Andrade, Vincent; Chen, Zhongwei

doi:10.1149/2.0101713jes

Morphological and Electrochemical Characterization of Nanostructured Li₄Ti₅O₁₂ Electrodes Using Multiple Imaging Mode Synchrotron X-ray Computed Tomography

Journal Article · Thu Sep 21 00:00:00 EDT 2017 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/2.0101713jes· OSTI ID:1402041

^[1]; Foreman, Evan ^[2]; Farhad, Siamak ^[2]; Lee, Dong Un ^[1]; ^[1]; Lui, Gregory ^[1]; De Andrade, Vincent ^[3]; Chen, Zhongwei ^[1]

Univ. of Waterloo, Waterloo, ON (Canada)
Univ. of Akron, Akron, OH (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)

In this study, synchrotron X-ray computed tomography has been utilized using two different imaging modes, absorption and Zernike phase contrast, to reconstruct the real three-dimensional (3D) morphology of nanostructured Li₄Ti₅O₁₂ (LTO) electrodes. The morphology of the high atomic number active material has been obtained using the absorption contrast mode, whereas the percolated solid network composed of active material and carbon-doped polymer binder domain (CBD) has been obtained using the Zernike phase contrast mode. The 3D absorption contrast image revealed that some LTO nano-particles tend to agglomerate and form secondary micro-sized particles with varying degrees of sphericity. The tortuosity of electrode’s pore and solid phases were found to have directional dependence, different from Bruggeman’s tortuosity commonly used in macro-homogeneous models. The electrode’s heterogeneous structure was investigated by developing a numerical model to simulate galvanostatic discharge process using the Zernike phase contrast mode. The inclusion of CBD in the Zernike phase contrast results in an integrated percolated network of active material and CBD that is highly suited for continuum modeling. As a result, the simulation results highlight the importance of using the real 3D geometry since the spatial distribution of physical and electrochemical properties have a strong non-uniformity due to microstructural heterogeneities.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: Natural Sciences and Engineering Research Council of Canada (NSERC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); University of Akron

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1402041

Journal Information:: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 12 Vol. 164; ISSN 0013-4651

Publisher:: The Electrochemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (44)

Porous-electrode theory with battery applications Newman, John; Tiedemann, William AIChE Journal, Vol. 21, Issue 1 https://doi.org/10.1002/aic.690210103	journal	January 1975
Berechnung verschiedener physikalischer Konstanten von heterogenen Substanzen. I. Dielektrizitätskonstanten und Leitfähigkeiten der Mischkörper aus isotropen Substanzen Bruggeman, D. A. G. Annalen der Physik, Vol. 416, Issue 7 https://doi.org/10.1002/andp.19354160705	journal	January 1935
Representative volume element model of lithium-ion battery electrodes based on X-ray nano-tomography Kashkooli, Ali Ghorbani; Amirfazli, Amir; Farhad, Siamak Journal of Applied Electrochemistry, Vol. 47, Issue 3 https://doi.org/10.1007/s10800-016-1037-y	journal	January 2017
The use of mathematical modeling in the design of lithium/polymer battery systems Doyle, Marc; Newman, John Electrochimica Acta, Vol. 40, Issue 13-14 https://doi.org/10.1016/0013-4686(95)00162-8	journal	October 1995
On the origin and application of the Bruggeman correlation for analysing transport phenomena in electrochemical systems Tjaden, Bernhard; Cooper, Samuel J.; Brett, Daniel JL Current Opinion in Chemical Engineering, Vol. 12 https://doi.org/10.1016/j.coche.2016.02.006	journal	May 2016
Direct in situ measurements of Li transport in Li-ion battery negative electrodes Harris, Stephen J.; Timmons, Adam; Baker, Daniel R. Chemical Physics Letters, Vol. 485, Issue 4-6 https://doi.org/10.1016/j.cplett.2009.12.033	journal	January 2010
Controllable formation and electrochemical properties of one-dimensional nanostructured spinel Li4Ti5O12 Li, Junrong; Tang, Zilong; Zhang, Zhongtai Electrochemistry Communications, Vol. 7, Issue 9 https://doi.org/10.1016/j.elecom.2005.06.012	journal	September 2005
Three-dimensional reconstruction of a composite cathode for lithium-ion cells Ender, Moses; Joos, Jochen; Carraro, Thomas Electrochemistry Communications, Vol. 13, Issue 2 https://doi.org/10.1016/j.elecom.2010.12.004	journal	February 2011
Extended lithium titanate cycling potential window with near zero capacity loss Ahn, Dongjoon; Xiao, Xingcheng Electrochemistry Communications, Vol. 13, Issue 8 https://doi.org/10.1016/j.elecom.2011.05.005	journal	August 2011
FIB/SEM-based calculation of tortuosity in a porous LiCoO2 cathode for a Li-ion battery Hutzenlaub, T.; Asthana, A.; Becker, J. Electrochemistry Communications, Vol. 27 https://doi.org/10.1016/j.elecom.2012.11.006	journal	February 2013
Simulation of diffusion-induced stress using reconstructed electrodes particle structures generated by micro/nano-CT Lim, Cheolwoong; Yan, Bo; Yin, Leilei Electrochimica Acta, Vol. 75 https://doi.org/10.1016/j.electacta.2012.04.120	journal	July 2012
Effects of Diffusive Charge Transfer and Salt Concentration Gradient in Electrolyte on Li-ion Battery Energy and Power Densities Zarrin, Hadis; Farhad, Siamak; Hamdullahpur, Feridun Electrochimica Acta, Vol. 125 https://doi.org/10.1016/j.electacta.2014.01.022	journal	April 2014
Analysis of Polarization in Realistic Li Ion Battery Electrode Microstructure Using Numerical Simulation Yan, Bo; Lim, Cheolwoong; Song, Zhibin Electrochimica Acta, Vol. 185 https://doi.org/10.1016/j.electacta.2015.10.086	journal	December 2015
Mechanical and Electrochemical Response of a LiCoO2 Cathode using Reconstructed Microstructures Mendoza, Hector; Roberts, Scott A.; Brunini, Victor E. Electrochimica Acta, Vol. 190 https://doi.org/10.1016/j.electacta.2015.12.224	journal	February 2016
Nano-particle size effect on the performance of Li4Ti5O12 spinel Kashkooli, Ali Ghorbani; Lui, Gregory; Farhad, Siamak Electrochimica Acta, Vol. 196 https://doi.org/10.1016/j.electacta.2016.02.153	journal	April 2016
Synchrotron X-ray nano computed tomography based simulation of stress evolution in LiMn2O4 electrodes Ghorbani Kashkooli, Ali; Foreman, Evan; Farhad, Siamak Electrochimica Acta, Vol. 247 https://doi.org/10.1016/j.electacta.2017.07.089	journal	September 2017
Quantifying tortuosity in porous Li-ion battery materials Thorat, Indrajeet V.; Stephenson, David E.; Zacharias, Nathan A. Journal of Power Sources, Vol. 188, Issue 2 https://doi.org/10.1016/j.jpowsour.2008.12.032	journal	March 2009
Porous cathode optimization for lithium cells: Ionic and electronic conductivity, capacity, and selection of materials Chen, Y. -H.; Wang, C. -W.; Zhang, X. Journal of Power Sources, Vol. 195, Issue 9 https://doi.org/10.1016/j.jpowsour.2009.11.044	journal	May 2010
Image based modelling of microstructural heterogeneity in LiFePO 4 electrodes for Li-ion batteries Cooper, S. J.; Eastwood, D. S.; Gelb, J. Journal of Power Sources, Vol. 247 https://doi.org/10.1016/j.jpowsour.2013.04.156	journal	February 2014
Multiple imaging mode X-ray computed tomography for distinguishing active and inactive phases in lithium-ion battery cathodes Komini Babu, Siddharth; Mohamed, Alexander I.; Whitacre, Jay F. Journal of Power Sources, Vol. 283 https://doi.org/10.1016/j.jpowsour.2015.02.086	journal	June 2015
Multiscale modeling of lithium-ion battery electrodes based on nano-scale X-ray computed tomography Kashkooli, Ali Ghorbani; Farhad, Siamak; Lee, Dong Un Journal of Power Sources, Vol. 307 https://doi.org/10.1016/j.jpowsour.2015.12.134	journal	March 2016
4D analysis of the microstructural evolution of Si-based electrodes during lithiation: Time-lapse X-ray imaging and digital volume correlation Paz-Garcia, J. M.; Taiwo, O. O.; Tudisco, E. Journal of Power Sources, Vol. 320 https://doi.org/10.1016/j.jpowsour.2016.04.076	journal	July 2016
Analysis of geometric and electrochemical characteristics of lithium cobalt oxide electrode with different packing densities Lim, Cheolwoong; Yan, Bo; Kang, Huixiao Journal of Power Sources, Vol. 328 https://doi.org/10.1016/j.jpowsour.2016.07.119	journal	October 2016
Three-dimensional finite element study on stress generation in synchrotron X-ray tomography reconstructed nickel-manganese-cobalt based half cell Wu, Linmin; Xiao, Xianghui; Wen, Youhai Journal of Power Sources, Vol. 336 https://doi.org/10.1016/j.jpowsour.2016.10.052	journal	December 2016
Nanostructured electrodes for high-power lithium ion batteries Mukherjee, Rahul; Krishnan, Rahul; Lu, Toh-Ming Nano Energy, Vol. 1, Issue 4 https://doi.org/10.1016/j.nanoen.2012.04.001	journal	July 2012
Implementing an in-situ carbon network in Si/reduced graphene oxide for high performance lithium-ion battery anodes Feng, Kun; Ahn, Wook; Lui, Gregory Nano Energy, Vol. 19 https://doi.org/10.1016/j.nanoen.2015.10.025	journal	January 2016
The application of phase contrast X-ray techniques for imaging Li-ion battery electrodes Eastwood, D. S.; Bradley, R. S.; Tariq, F. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 324 https://doi.org/10.1016/j.nimb.2013.08.066	journal	April 2014
General synthesis of carbon-coated nanostructure Li ₄ Ti ₅ O ₁₂ as a high rate electrode material for Li-ion intercalation Cheng, Liang; Yan, Jing; Zhu, Guan-Nan J. Mater. Chem., Vol. 20, Issue 3 https://doi.org/10.1039/B914604K	journal	January 2010
TomoPy: a framework for the analysis of synchrotron tomographic data Gürsoy, Dogˇa; De Carlo, Francesco; Xiao, Xianghui Journal of Synchrotron Radiation, Vol. 21, Issue 5 https://doi.org/10.1107/S1600577514013939	journal	August 2014
Nanoscale 3D imaging at the Advanced Photon Source De Andrade, Vincent; Deriy, Alex; Wojcik, Michael J. SPIE Newsroom https://doi.org/10.1117/2.1201604.006461	journal	May 2016
Discharge Model for the Lithium Iron-Phosphate Electrode Srinivasan, Venkat; Newman, John Journal of The Electrochemical Society, Vol. 151, Issue 10 https://doi.org/10.1149/1.1785012	journal	January 2004
Cycle Life Modeling of Lithium-Ion Batteries Ning, Gang; Popov, Branko N. Journal of The Electrochemical Society, Vol. 151, Issue 10 https://doi.org/10.1149/1.1787631	journal	January 2004
Comparison of Modeling Predictions with Experimental Data from Plastic Lithium Ion Cells Doyle, Marc Journal of The Electrochemical Society, Vol. 143, Issue 6 https://doi.org/10.1149/1.1836921	journal	January 1996
Optimization of Lithium Titanate Electrodes for High-Power Cells Christensen, John; Srinivasan, Venkat; Newman, John Journal of The Electrochemical Society, Vol. 153, Issue 3 https://doi.org/10.1149/1.2172535	journal	January 2006
Optimizing the Performance of Lithium Titanate Spinel Paired with Activated Carbon or Iron Phosphate Stewart, Sarah; Albertus, Paul; Srinivasan, Venkat Journal of The Electrochemical Society, Vol. 155, Issue 3 https://doi.org/10.1149/1.2830552	journal	January 2008
The Effect of Microstructure on the Galvanostatic Discharge of Graphite Anode Electrodes in LiCoO[sub 2]-Based Rocking-Chair Rechargeable Batteries Smith, Madeleine; García, R. Edwin; Horn, Quinn C. Journal of The Electrochemical Society, Vol. 156, Issue 11 https://doi.org/10.1149/1.3216000	journal	January 2009
Single-Particle Model for a Lithium-Ion Cell: Thermal Behavior Guo, Meng; Sikha, Godfrey; White, Ralph E. Journal of The Electrochemical Society, Vol. 158, Issue 2 https://doi.org/10.1149/1.3521314	journal	January 2011
Modeling 3D Microstructure and Ion Transport in Porous Li-Ion Battery Electrodes Stephenson, David E.; Walker, Bryce C.; Skelton, Cole B. Journal of The Electrochemical Society, Vol. 158, Issue 7 https://doi.org/10.1149/1.3579996	journal	January 2011
Enhanced Imaging of Lithium Ion Battery Electrode Materials Biton, Moshiel; Yufit, Vladimir; Tariq, Farid Journal of The Electrochemical Society, Vol. 164, Issue 1 https://doi.org/10.1149/2.0061701jes	journal	September 2016
Three Dimensional Simulation of Galvanostatic Discharge of LiCoO ₂ Cathode Based on X-ray Nano-CT Images Yan, Bo; Lim, Cheolwoong; Yin, Leilei Journal of The Electrochemical Society, Vol. 159, Issue 10 https://doi.org/10.1149/2.024210jes	journal	January 2012
The Development and Future of Lithium Ion Batteries Blomgren, George E. Journal of The Electrochemical Society, Vol. 164, Issue 1 https://doi.org/10.1149/2.0251701jes	journal	December 2016
Understanding Li-Ion Battery Anode Degradation and Pore Morphological Changes through Nano-Resolution X-ray Computed Tomography Frisco, Sarah; Kumar, Arjun; Whitacre, Jay F. Journal of The Electrochemical Society, Vol. 163, Issue 13 https://doi.org/10.1149/2.0681613jes	journal	January 2016
Local Tortuosity Inhomogeneities in a Lithium Battery Composite Electrode Kehrwald, Dirk; Shearing, Paul R.; Brandon, Nigel P. Journal of The Electrochemical Society, Vol. 158, Issue 12 https://doi.org/10.1149/2.079112jes	journal	January 2011
Particle Size Polydispersity in Li-Ion Batteries Chung, Ding-Wen; Shearing, Paul R.; Brandon, Nigel P. Journal of The Electrochemical Society, Vol. 161, Issue 3 https://doi.org/10.1149/2.097403jes	journal	December 2013

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Related Subjects

25 ENERGY STORAGE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Image based modeling
Lithium titanate oxide
Lithium-ion battery
Synchrotron X-ray computed tomography
Tortuosity