Tortuosity Effects in Garnet-Type Li7La3Zr2O12 Solid Electrolytes

Dixit, Marm B.; Regala, Matthew; Shen, Fengyu; Xiao, Xianghui; Hatzell, Kelsey B.

doi:10.1021/acsami.8b16536

Tortuosity Effects in Garnet-Type Li₇La₃Zr₂O₁₂ Solid Electrolytes

Journal Article · Tue Dec 18 04:00:00 EST 2018 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.8b16536· OSTI ID:1495002

Dixit, Marm B. ^[1]; Regala, Matthew ^[1]; Shen, Fengyu ^[1]; Xiao, Xianghui ^[2]; ^[1]

Vanderbilt Univ., Nashville, TN (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

Intrinsic material microstructure features, such as pores or void spaces, grains, and defects can affect local lithium-ion concentration profiles and transport properties in solid ion conductors. The formation of lithium-deficient or -excess regions can accelerate degradation phenomena, such as dendrite formation, lithium plating, and electrode/electrolyte delamination. This paper evaluates the effects pores or void spaces have on the tortuosity of a garnet-type Li₇La₃Zr₂O₁₂ solid electrolyte. Synchrotron X-ray tomography is used to obtain three-dimensional reconstructions of different electrolytes sintered at temperatures between 1050 and 1150 °C. The magnitude of the electrolyte tortuosity and the tortuosity directional anisotropy is shown to increase with sintering temperature. Electrolytes with highly anisometric tortuosity have lower critical current densities. Here, the alignment or elimination of pores within an electrolyte or composite cathode may provide a means or achieving higher critical current densities and higher power densities in all solid-state batteries.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012704

OSTI ID:: 1495002

Alternate ID(s):: OSTI ID: 1494764

Report Number(s):: BNL--211263-2019-JAAM

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 2 Vol. 11; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (60)

Tortuosity Anisotropy in Lithium-Ion Battery Electrodes Ebner, Martin; Chung, Ding-Wen; García, R. Edwin Advanced Energy Materials, Vol. 4, Issue 5 https://doi.org/10.1002/aenm.201301278	journal	October 2013
Electrochemical Stability of Li ₁₀ GeP ₂ S ₁₂ and Li ₇ La ₃ Zr ₂ O ₁₂ Solid Electrolytes Han, Fudong; Zhu, Yizhou; He, Xingfeng Advanced Energy Materials, Vol. 6, Issue 8 https://doi.org/10.1002/aenm.201501590	journal	January 2016
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
Fast Lithium Ion Conduction in Garnet-Type Li₇La₃Zr₂O₁₂ Murugan, Ramaswamy; Thangadurai, Venkataraman; Weppner, Werner Angewandte Chemie International Edition, Vol. 46, Issue 41, p. 7778-7781 https://doi.org/10.1002/anie.200701144	journal	October 2007
Relevance of solid electrolytes for lithium-based batteries: A realistic view Lotsch, Bettina V.; Maier, Joachim Journal of Electroceramics, Vol. 38, Issue 2-4 https://doi.org/10.1007/s10832-017-0091-0	journal	June 2017
Synthesis of a new lithium ionic conductor, thio-LISICON–lithium germanium sulfide system Kanno, R. Solid State Ionics, Vol. 130, Issue 1-2 https://doi.org/10.1016/S0167-2738(00)00277-0	journal	May 2000
Critical review of the impact of tortuosity on diffusion Shen, Lihua; Chen, Zhangxin Chemical Engineering Science, Vol. 62, Issue 14 https://doi.org/10.1016/j.ces.2007.03.041	journal	July 2007
LiNbO3-coated LiCoO2 as cathode material for all solid-state lithium secondary batteries Ohta, Narumi; Takada, Kazunori; Sakaguchi, Isao Electrochemistry Communications, Vol. 9, Issue 7 https://doi.org/10.1016/j.elecom.2007.02.008	journal	July 2007
Sintering Mechanisms of High-Performance Garnet-type Solid Electrolyte Densified by Spark Plasma Sintering Yamada, Hirotoshi; Ito, Tomoko; Hongahally Basappa, Rajendra Electrochimica Acta, Vol. 222 https://doi.org/10.1016/j.electacta.2016.11.020	journal	December 2016
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
Thermodynamics and cell chemistry of room temperature sodium/sulfur cells with liquid and liquid/solid electrolyte Wenzel, Sebastian; Metelmann, Hauke; Raiß, Christine Journal of Power Sources, Vol. 243 https://doi.org/10.1016/j.jpowsour.2013.05.194	journal	December 2013
Computational study of lithium nucleation tendency in Li7La3Zr2O12 (LLZO) and rational design of interlayer materials to prevent lithium dendrites Tian, Hong-Kang; Xu, Bo; Qi, Yue Journal of Power Sources, Vol. 392 https://doi.org/10.1016/j.jpowsour.2018.04.098	journal	July 2018
Ion transport limitations in all-solid-state lithium battery electrodes containing a sulfide-based electrolyte Kaiser, N.; Spannenberger, S.; Schmitt, M. Journal of Power Sources, Vol. 396 https://doi.org/10.1016/j.jpowsour.2018.05.095	journal	August 2018
The influence of void space on ion transport in a composite cathode for all-solid-state batteries Hlushkou, Dzmitry; Reising, Arved E.; Kaiser, Nico Journal of Power Sources, Vol. 396 https://doi.org/10.1016/j.jpowsour.2018.06.041	journal	August 2018
Characterization of the morphology of primary silicon particles using synchrotron X-ray tomography Wang, J.; Guo, Z.; Xiong, S. M. Materials Characterization, Vol. 123 https://doi.org/10.1016/j.matchar.2016.12.004	journal	January 2017
TauFactor: An open-source application for calculating tortuosity factors from tomographic data Cooper, S. J.; Bertei, A.; Shearing, P. R. SoftwareX, Vol. 5 https://doi.org/10.1016/j.softx.2016.09.002	journal	January 2016
Interphase formation on lithium solid electrolytes—An in situ approach to study interfacial reactions by photoelectron spectroscopy Wenzel, Sebastian; Leichtweiss, Thomas; Krüger, Dominik Solid State Ionics, Vol. 278 https://doi.org/10.1016/j.ssi.2015.06.001	journal	October 2015
Designing Ionic Conductors: The Interplay between Structural Phenomena and Interfaces in Thiophosphate-Based Solid-State Batteries Culver, Sean P.; Koerver, Raimund; Krauskopf, Thorben Chemistry of Materials, Vol. 30, Issue 13 https://doi.org/10.1021/acs.chemmater.8b01293	journal	May 2018
Attainable Gravimetric and Volumetric Energy Density of Li–S and Li Ion Battery Cells with Solid Separator-Protected Li Metal Anodes McCloskey, Bryan D. The Journal of Physical Chemistry Letters, Vol. 6, Issue 22 https://doi.org/10.1021/acs.jpclett.5b01814	journal	October 2015
All-Solid-State Batteries with Thick Electrode Configurations Kato, Yuki; Shiotani, Shinya; Morita, Keisuke The Journal of Physical Chemistry Letters, Vol. 9, Issue 3 https://doi.org/10.1021/acs.jpclett.7b02880	journal	January 2018
In Situ STEM-EELS Observation of Nanoscale Interfacial Phenomena in All-Solid-State Batteries Wang, Ziying; Santhanagopalan, Dhamodaran; Zhang, Wei Nano Letters, Vol. 16, Issue 6 https://doi.org/10.1021/acs.nanolett.6b01119	journal	May 2016
Interrelationships among Grain Size, Surface Composition, Air Stability, and Interfacial Resistance of Al-Substituted Li ₇ La ₃ Zr ₂ O ₁₂ Solid Electrolytes Cheng, Lei; Wu, Cheng Hao; Jarry, Angelique ACS Applied Materials & Interfaces, Vol. 7, Issue 32 https://doi.org/10.1021/acsami.5b02528	journal	August 2015
Improving Ionic Conductivity and Lithium-Ion Transference Number in Lithium-Ion Battery Separators Zahn, Raphael; Lagadec, Marie Francine; Hess, Michael ACS Applied Materials & Interfaces, Vol. 8, Issue 48 https://doi.org/10.1021/acsami.6b12085	journal	November 2016
New Insights into the Compositional Dependence of Li-Ion Transport in Polymer–Ceramic Composite Electrolytes Zheng, Jin; Hu, Yan-Yan ACS Applied Materials & Interfaces, Vol. 10, Issue 4 https://doi.org/10.1021/acsami.7b17301	journal	January 2018
Quantitative Analysis of Microstructures and Reaction Interfaces on Composite Cathodes in All-Solid-State Batteries Using a Three-Dimensional Reconstruction Technique Choi, Sungjun; Jeon, Minjae; Ahn, Junsung ACS Applied Materials & Interfaces, Vol. 10, Issue 28 https://doi.org/10.1021/acsami.8b04204	journal	June 2018
Effect of Pore Connectivity on Li Dendrite Propagation within LLZO Electrolytes Observed with Synchrotron X-ray Tomography Shen, Fengyu; Dixit, Marm B.; Xiao, Xianghui ACS Energy Letters, Vol. 3, Issue 4 https://doi.org/10.1021/acsenergylett.8b00249	journal	March 2018
Effect of Surface Microstructure on Electrochemical Performance of Garnet Solid Electrolytes Cheng, Lei; Chen, Wei; Kunz, Martin ACS Applied Materials & Interfaces, Vol. 7, Issue 3 https://doi.org/10.1021/am508111r	journal	January 2015
Atomic-Scale Influence of Grain Boundaries on Li-Ion Conduction in Solid Electrolytes for All-Solid-State Batteries Dawson, James A.; Canepa, Pieremanuele; Famprikis, Theodosios Journal of the American Chemical Society, Vol. 140, Issue 1 https://doi.org/10.1021/jacs.7b10593	journal	December 2017
A solid future for battery development Janek, Jürgen; Zeier, Wolfgang G. Nature Energy, Vol. 1, Issue 9 https://doi.org/10.1038/nenergy.2016.141	journal	September 2016
Magnetically aligned graphite electrodes for high-rate performance Li-ion batteries Billaud, Juliette; Bouville, Florian; Magrini, Tommaso Nature Energy, Vol. 1, Issue 8 https://doi.org/10.1038/nenergy.2016.97	journal	July 2016
NIH Image to ImageJ: 25 years of image analysis Schneider, Caroline A.; Rasband, Wayne S.; Eliceiri, Kevin W. Nature Methods, Vol. 9, Issue 7 https://doi.org/10.1038/nmeth.2089	journal	June 2012
Reviving the lithium metal anode for high-energy batteries Lin, Dingchang; Liu, Yayuan; Cui, Yi Nature Nanotechnology, Vol. 12, Issue 3 https://doi.org/10.1038/nnano.2017.16	journal	March 2017
Accessing the bottleneck in all-solid state batteries, lithium-ion transport over the solid-electrolyte-electrode interface Yu, Chuang; Ganapathy, Swapna; Eck, Ernst R. H. van Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-01187-y	journal	October 2017
Direct observation of active material interactions in flowable electrodes using X-ray tomography Hatzell, Kelsey B.; Eller, Jens; Morelly, Samantha L. Faraday Discussions, Vol. 199 https://doi.org/10.1039/C6FD00243A	journal	January 2017
Low-temperature densification of Al-doped Li ₇ La ₃ Zr ₂ O ₁₂ : a reliable and controllable synthesis of fast-ion conducting garnets El-Shinawi, Hany; Paterson, Gary W.; MacLaren, Donald A. Journal of Materials Chemistry A, Vol. 5, Issue 1 https://doi.org/10.1039/C6TA06961D	journal	January 2017
Determining the uncertainty in microstructural parameters extracted from tomographic data Pietsch, P.; Ebner, M.; Marone, F. Sustainable Energy & Fuels, Vol. 2, Issue 3 https://doi.org/10.1039/C7SE00498B	journal	January 2018
Li-ion transport in a representative ceramic–polymer–plasticizer composite electrolyte: Li ₇ La ₃ Zr ₂ O ₁₂ –polyethylene oxide–tetraethylene glycol dimethyl ether Zheng, Jin; Dang, Heather; Feng, Xuyong Journal of Materials Chemistry A, Vol. 5, Issue 35 https://doi.org/10.1039/C7TA05832B	journal	January 2017
Controlling and correlating the effect of grain size with the mechanical and electrochemical properties of Li ₇ La ₃ Zr ₂ O ₁₂ solid-state electrolyte Sharafi, Asma; Haslam, Catherine G.; Kerns, Robert D. J. Mater. Chem. A, Vol. 5, Issue 40 https://doi.org/10.1039/C7TA06790A	journal	January 2017
Understanding inks for porous-electrode formation Hatzell, Kelsey B.; Dixit, Marm B.; Berlinger, Sarah A. J. Mater. Chem. A, Vol. 5, Issue 39 https://doi.org/10.1039/C7TA07255D	journal	January 2017
A new method for the model‐independent assessment of thickness in three‐dimensional images Hildebrand, T.; Rüegsegger, P. Journal of Microscopy, Vol. 185, Issue 1 https://doi.org/10.1046/j.1365-2818.1997.1340694.x	journal	January 1997
Validity of the Bruggeman relation for porous electrodes Chung, Ding-Wen; Ebner, Martin; Ely, David R. Modelling and Simulation in Materials Science and Engineering, Vol. 21, Issue 7 https://doi.org/10.1088/0965-0393/21/7/074009	journal	October 2013
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
Contradicting Geometrical Concepts in Pore Size Analysis Attained with Electron Microscopy and Mercury Intrusion Münch, Beat; Holzer, Lorenz Journal of the American Ceramic Society, Vol. 91, Issue 12 https://doi.org/10.1111/j.1551-2916.2008.02736.x	journal	December 2008
Microstructure and Li-Ion Conductivity of Hot-Pressed Cubic Li ₇ La ₃ Zr ₂ O ₁₂ David, Isabel N.; Thompson, Travis; Wolfenstine, Jeff Journal of the American Ceramic Society, Vol. 98, Issue 4 https://doi.org/10.1111/jace.13455	journal	January 2015
Lithium Ionic Conductor Thio-LISICON: The Li₂S-GeS₂-P₂S₅ System Kanno, Ryoji; Murayama, Masahiro Journal of The Electrochemical Society, Vol. 148, Issue 7, p. A742-A746 https://doi.org/10.1149/1.1379028	journal	January 2001
Compatibility of Lithium Ion Conductive Sulfide Glass with Carbon-Lithium Electrode Takada, Kazunori; Nakano, Satoshi; Inada, Taro Journal of The Electrochemical Society, Vol. 150, Issue 3 https://doi.org/10.1149/1.1545453	journal	January 2003
Dendrite Growth in Lithium/Polymer Systems Monroe, Charles; Newman, John Journal of The Electrochemical Society, Vol. 150, Issue 10 https://doi.org/10.1149/1.1606686	journal	January 2003
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
The A-C Conductivity of Polycrystalline LISICON, Li[sub 2+2x]Zn[sub 1−x]GeO[sub 4], and a Model for Intergranular Constriction Resistances Bruce, P. G. Journal of The Electrochemical Society, Vol. 130, Issue 3 https://doi.org/10.1149/1.2119778	journal	January 1983
Designing Polyolefin Separators to Minimize the Impact of Local Compressive Stresses on Lithium Ion Battery Performance Lagadec, Marie Francine; Zahn, Raphael; Wood, Vanessa Journal of The Electrochemical Society, Vol. 165, Issue 9 https://doi.org/10.1149/2.0041809jes	journal	January 2018
Tool for Tortuosity Estimation in Lithium Ion Battery Porous Electrodes Ebner, Martin; Wood, Vanessa Journal of The Electrochemical Society, Vol. 162, Issue 2 https://doi.org/10.1149/2.0111502jes	journal	December 2014
Bruggeman's Exponents for Effective Thermal Conductivity of Lithium-Ion Battery Electrodes Vadakkepatt, Ajay; Trembacki, Bradley; Mathur, Sanjay R. Journal of The Electrochemical Society, Vol. 163, Issue 2 https://doi.org/10.1149/2.0151602jes	journal	November 2015
Catalyst Layer Ink Interactions That Affect Coatability Dixit, Marm B.; Harkey, Brice A.; Shen, Fengyu Journal of The Electrochemical Society, Vol. 165, Issue 5 https://doi.org/10.1149/2.0191805jes	journal	January 2018
Tortuosity of Battery Electrodes: Validation of Impedance-Derived Values and Critical Comparison with 3D Tomography Landesfeind, Johannes; Ebner, Martin; Eldiven, Askin Journal of The Electrochemical Society, Vol. 165, Issue 3 https://doi.org/10.1149/2.0231803jes	journal	January 2018
Nonequilibrium Thermodynamics of Porous Electrodes Ferguson, Todd R.; Bazant, Martin Z. Journal of The Electrochemical Society, Vol. 159, Issue 12 https://doi.org/10.1149/2.048212jes	journal	January 2012
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
Communication—Technique for Visualization and Quantification of Lithium-Ion Battery Separator Microstructure Lagadec, Marie Francine; Ebner, Martin; Zahn, Raphael Journal of The Electrochemical Society, Vol. 163, Issue 6 https://doi.org/10.1149/2.0811606jes	journal	January 2016
Influence of the Binder on Lithium Ion Battery Electrode Tortuosity and Performance Landesfeind, Johannes; Eldiven, Askin; Gasteiger, Hubert A. Journal of The Electrochemical Society, Vol. 165, Issue 5 https://doi.org/10.1149/2.0971805jes	journal	January 2018
An Analytical Method to Determine Tortuosity in Rechargeable Battery Electrodes Vijayaraghavan, Bharath; Ely, David R.; Chiang, Yet-Ming Journal of The Electrochemical Society, Vol. 159, Issue 5 https://doi.org/10.1149/2.jes113224	journal	January 2012
All-Solid-State Batteries and their Remaining Challenges Kasemchainan, Jitti; Bruce, Peter G. Johnson Matthey Technology Review, Vol. 62, Issue 2 https://doi.org/10.1595/205651318X696747	journal	April 2018

Cited By (4)

Lithium migration pathways at the composite interface of LiBH ₄ and two-dimensional MoS ₂ enabling superior ionic conductivity at room temperature Liu, Zhixiang; Xiang, Mengyuan; Zhang, Yao Physical Chemistry Chemical Physics, Vol. 22, Issue 7 https://doi.org/10.1039/c9cp06090a	journal	January 2020
Visualizing percolation and ion transport in hybrid solid electrolytes for Li–metal batteries Zaman, Wahid; Hortance, Nicholas; Dixit, Marm B. Journal of Materials Chemistry A, Vol. 7, Issue 41 https://doi.org/10.1039/c9ta05118j	journal	January 2019
Oriented porous LLZO 3D structures obtained by freeze casting for battery applications Shen, Hao; Yi, Eongyu; Amores, Marco Journal of Materials Chemistry A, Vol. 7, Issue 36 https://doi.org/10.1039/c9ta06520b	journal	January 2019
Composite Electrode Ink Formulation for All Solid-State Batteries Shen, Fengyu; Dixit, Marm B.; Zaman, Wahid Journal of The Electrochemical Society, Vol. 166, Issue 14 https://doi.org/10.1149/2.0141914jes	journal	January 2019

Similar Records

Fabrication of high-density and translucent Al-containing garnet, Li_7–xLa₃Zr_2–xTa_xO₁₂ (LLZTO) solid-state electrolyte by pressure filtration and sintering

Journal Article · Wed Apr 28 00:00:00 EDT 2021 · Solid State Ionics · OSTI ID:1865161

3D Printed, Low Tortuosity Garnet Framework For Beyond 500 Wh/kg Batteries

Technical Report · Thu Nov 11 23:00:00 EST 2021 · OSTI ID:1830009

(Invited) All-Solid-State Batteries Using Li₇La₃Zr₂O₁₂ Garnet Electrolyte Framework

Journal Article · Sun Nov 22 23:00:00 EST 2020 · Meeting abstracts (Electrochemical Society. Online) · OSTI ID:1765581

Related Subjects

42 ENGINEERING
microstructure
solid electrolyte
tomography
tortuosity
transport