The effects of aluminum concentration on the microstructural and electrochemical properties of lithium lanthanum zirconium oxide

Moy, Alexandra C.; Häuschen, Grit; Fattakhova-Rohlfing, Dina; Wolfenstine, Jeffrey B.; Finsterbusch, Martin; Sakamoto, Jeff

doi:10.1039/d2ta03676b

The effects of aluminum concentration on the microstructural and electrochemical properties of lithium lanthanum zirconium oxide

Journal Article · Wed Sep 28 00:00:00 EDT 2022 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/d2ta03676b· OSTI ID:2423973

^[1]; ^[2]; ^[2]; Wolfenstine, Jeffrey B. ^[3]; ^[2]; ^[1]

University of Michigan, Ann Arbor, MI (United States)
Forschungszentrum Jülich GmbH (Germany)
Solid Ionic Consulting, Seattle, WA (United States)

Cubic lithium lanthanum zirconium oxide (Li_7-xAl_xLa₃Zr₂O₁₂, LLZO) garnet has gained attention as a promising next-generation electrolyte for lithium batteries due to its high ionic conductivity and chemical stability with lithium metal. The high conductivity can be achieved through doping over a range of aluminum concentrations. In this study, we hot-pressed samples to achieve <2% nominal porosity with aluminum concentrations from x = 0.25–0.55 mol to understand the effect of aluminum on microstructure and electrochemistry. It was observed that beyond the aluminum solubility limit (x = ~0.40), resistive secondary phases formed at the grain boundaries. As a result, the percent grain boundary resistance increased from 17.6 to 41.2% for x = 0.25 and x = 0.55, respectively. Both the grain boundary and bulk activation energies remained relatively constant as the aluminum concentrations increased (~0.44 eV and ~0.39 eV, respectively). It was, therefore, surmised that the mobility term of the Nernst–Einstein equation was roughly independent of aluminum concentration and the major variable controlling bulk conductivity was the number of lithium charge carriers. As a result, as the aluminum concentration increased from x = 0.25 to x = 0.55 the bulk conductivity decreased from 0.56 to 0.15 mS cm^-1. Following these trends of increasing grain boundary resistance and decreasing bulk conductivity with increasing aluminum concentration, x = 0.25 had the highest total conductivity (0.46 mS cm^-1). We demonstrated that aluminum concentration has a significant effect on the microstructure and electrochemical properties of LLZO. In conclusion, we believe this work could help understand how to link processing, microstructure, and electrochemical properties to guide the manufacturing of LLZO for use in solid-state batteries.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: German Federal Ministry of Education and Research (BMBF); USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2423973

Alternate ID(s):: OSTI ID: 1890004

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 41 Vol. 10; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (64)

Suppressing Li Dendrite Formation in Li ₂ S-P ₂ S ₅ Solid Electrolyte by LiI Incorporation Han, Fudong; Yue, Jie; Zhu, Xiangyang Advanced Energy Materials, Vol. 8, Issue 18 https://doi.org/10.1002/aenm.201703644	journal	March 2018
Commercialization of Lithium Battery Technologies for Electric Vehicles Zeng, Xiaoqiao; Li, Matthew; Abd El‐Hady, Deia Advanced Energy Materials, Vol. 9, Issue 27 https://doi.org/10.1002/aenm.201900161	journal	June 2019
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
Resolving the Grain Boundary and Lattice Impedance of Hot-Pressed Li ₇ La ₃ Zr ₂ O ₁₂ Garnet Electrolytes Tenhaeff, Wyatt E.; Rangasamy, Ezhiyl; Wang, Yangyang ChemElectroChem, Vol. 1, Issue 2 https://doi.org/10.1002/celc.201300022	journal	July 2013
Sintering Additives for Garnet-Type Electrolytes Rosero-Navarro, Nataly C.; Tadanaga, Kiyoharu Solid Electrolytes for Advanced Applications https://doi.org/10.1007/978-3-030-31581-8_5	book	January 2019
Simple method to determine electronic and ionic components of the conductivity in mixed conductors a review Huggins, R. A. Ionics, Vol. 8, Issue 3-4 https://doi.org/10.1007/BF02376083	journal	May 2002
Electron microscopy characterization of hot-pressed Al substituted Li7La3Zr2O12 Wolfenstine, J.; Sakamoto, J.; Allen, J. L. Journal of Materials Science, Vol. 47, Issue 10 https://doi.org/10.1007/s10853-012-6300-y	journal	February 2012
Mechanical behavior of Li-ion-conducting crystalline oxide-based solid electrolytes: a brief review Wolfenstine, Jeff; Allen, Jan L.; Sakamoto, Jeff Ionics, Vol. 24, Issue 5 https://doi.org/10.1007/s11581-017-2314-4	journal	November 2017
Digestion processes and elemental analysis of oxide and sulfide solid electrolytes Malkowski, Thomas F.; Boeding, Ethan D.; Fattakhova-Rohlfing, Dina Ionics, Vol. 28, Issue 7 https://doi.org/10.1007/s11581-022-04536-0	journal	April 2022
Li ion conduction in Li2ZrO3, Li4ZrO4, and LiScO2 Hellstrom, E.; Vangool, W. Solid State Ionics, Vol. 2, Issue 1 https://doi.org/10.1016/0167-2738(81)90021-7	journal	February 1981
Coupled thermodynamic-phase diagram assessment of the rare earth oxide-aluminium oxide binary systems Wu, Ping; Pelton, Arthur D. Journal of Alloys and Compounds, Vol. 179, Issue 1-2 https://doi.org/10.1016/0925-8388(92)90227-Z	journal	February 1992
High lithium ion conductive Li₇La₃Zr₂O₁₂ by inclusion of both Al and Si Kumazaki, Shota; Iriyama, Yasutoshi; Kim, Ki-Hyun Electrochemistry Communications, Vol. 13, Issue 5, p. 509-512 https://doi.org/10.1016/j.elecom.2011.02.035	journal	May 2011
High lithium ion conduction in garnet-type Li6La3ZrTaO12 Li, Yutao; Wang, Chang-An; Xie, Hui Electrochemistry Communications, Vol. 13, Issue 12 https://doi.org/10.1016/j.elecom.2011.07.008	journal	December 2011
High conductive yttrium doped Li7La3Zr2O12 cubic lithium garnet Murugan, Ramaswamy; Ramakumar, S.; Janani, N. Electrochemistry Communications, Vol. 13, Issue 12 https://doi.org/10.1016/j.elecom.2011.08.014	journal	December 2011
Temperature dependent flux balance of the Li/Li7La3Zr2O12 interface Wang, Michael; Wolfenstine, Jeffrey B.; Sakamoto, Jeff Electrochimica Acta, Vol. 296 https://doi.org/10.1016/j.electacta.2018.11.034	journal	February 2019
Recent Advances in Energy Chemical Engineering of Next-Generation Lithium Batteries Zhang, Xue-Qiang; Zhao, Chen-Zi; Huang, Jia-Qi Engineering, Vol. 4, Issue 6 https://doi.org/10.1016/j.eng.2018.10.008	journal	December 2018
Study on the structural change and lithium ion conductivity for the perovskite-type LaAlO3–La0.50Li0.50TiO3 solid solution Yang, Kai-Yun; Fung, Kuan-Zong; Leu, Ing-Chi Journal of Alloys and Compounds, Vol. 438, Issue 1-2 https://doi.org/10.1016/j.jallcom.2006.07.116	journal	July 2007
Advancing Lithium Metal Batteries Liu, Bin; Zhang, Ji-Guang; Xu, Wu Joule, Vol. 2, Issue 5 https://doi.org/10.1016/j.joule.2018.03.008	journal	May 2018
High lithium ionic conductivity in the garnet-type oxide Li_7−XLa₃(Zr_2−X, Nb_X)O₁₂ (X=0–2) Ohta, Shingo; Kobayashi, Tetsuro; Asaoka, Takahiko Journal of Power Sources, Vol. 196, Issue 6, p. 3342-3345 https://doi.org/10.1016/j.jpowsour.2010.11.089	journal	March 2011
Al-doped Li₇La₃Zr₂O₁₂ synthesized by a polymerized complex method Jin, Ying; McGinn, Paul J. Journal of Power Sources, Vol. 196, Issue 20, p. 8683-8687 https://doi.org/10.1016/j.jpowsour.2011.05.065	journal	October 2011
Lithium metal electrode kinetics and ionic conductivity of the solid lithium ion conductors “Li7La3Zr2O12” and Li7−xLa3Zr2−xTaxO12 with garnet-type structure Buschmann, Henrik; Berendts, Stefan; Mogwitz, Boris Journal of Power Sources, Vol. 206 https://doi.org/10.1016/j.jpowsour.2012.01.094	journal	May 2012
Effect of substitution (Ta, Al, Ga) on the conductivity of Li₇La₃Zr₂O₁₂ Allen, J. L.; Wolfenstine, J.; Rangasamy, E. Journal of Power Sources, Vol. 206, p. 315-319 https://doi.org/10.1016/j.jpowsour.2012.01.131	journal	May 2012
Stabilization of cubic lithium-stuffed garnets of the type “Li7La3Zr2O12” by addition of gallium El Shinawi, Hany; Janek, Jürgen Journal of Power Sources, Vol. 225 https://doi.org/10.1016/j.jpowsour.2012.09.111	journal	March 2013
Time-of-flight secondary ion mass spectrometry study of lithium intercalation process in LiCoO2 thin film Dellen, C.; Gehrke, H. -G.; Möller, S. Journal of Power Sources, Vol. 321 https://doi.org/10.1016/j.jpowsour.2016.04.084	journal	July 2016
Synthesis and structure analysis of tetragonal Li₇La₃Zr₂O₁₂ with the garnet-related type structure Awaka, Junji; Kijima, Norihito; Hayakawa, Hiroshi Journal of Solid State Chemistry, Vol. 182, Issue 8, p. 2046-2052 https://doi.org/10.1016/j.jssc.2009.05.020	journal	August 2009
Synthesis and high Li-ion conductivity of Ga-stabilized cubic Li7La3Zr2O12 Wolfenstine, Jeff; Ratchford, Joshua; Rangasamy, Ezhiyl Materials Chemistry and Physics, Vol. 134, Issue 2-3 https://doi.org/10.1016/j.matchemphys.2012.03.054	journal	June 2012
Synthesis of garnet-type Li7−xLa3Zr2O12−1/2x and its stability in aqueous solutions Shimonishi, Yuta; Toda, Akiharu; Zhang, Tao Solid State Ionics, Vol. 183, Issue 1 https://doi.org/10.1016/j.ssi.2010.12.010	journal	February 2011
Sol–gel synthesis and lithium ion conductivity of Li7La3Zr2O12 with garnet-related type structure Kokal, I.; Somer, M.; Notten, P. H. L. Solid State Ionics, Vol. 185, Issue 1 https://doi.org/10.1016/j.ssi.2011.01.002	journal	March 2011
Effect of sintering temperature on structure and ionic conductivity of Li7−xLa3Zr2O12−0.5x (x=0.5~0.7) ceramics Huang, Mian; Liu, Ting; Deng, Yufeng Solid State Ionics, Vol. 204-205 https://doi.org/10.1016/j.ssi.2011.10.003	journal	December 2011
The role of Al and Li concentration on the formation of cubic garnet solid electrolyte of nominal composition Li₇La₃Zr₂O₁₂ Rangasamy, Ezhiyl; Wolfenstine, Jeff; Sakamoto, Jeffrey Solid State Ionics, Vol. 206, p. 28-32 https://doi.org/10.1016/j.ssi.2011.10.022	journal	January 2012
Interface behavior between garnet-type lithium-conducting solid electrolyte and lithium metal Sudo, R.; Nakata, Y.; Ishiguro, K. Solid State Ionics, Vol. 262 https://doi.org/10.1016/j.ssi.2013.09.024	journal	September 2014
Competing Effects in the Hydration Mechanism of a Garnet-Type Li₇La₃Zr₂O₁₂ Electrolyte Arinicheva, Yulia; Guo, Xin; Gerhards, Marie-Theres Chemistry of Materials, Vol. 34, Issue 4 https://doi.org/10.1021/acs.chemmater.1c02581	journal	February 2022
Structure and Stoichiometry in Supervalent Doped Li ₇ La ₃ Zr ₂ O ₁₂ Mukhopadhyay, Saikat; Thompson, Travis; Sakamoto, Jeff Chemistry of Materials, Vol. 27, Issue 10 https://doi.org/10.1021/acs.chemmater.5b00362	journal	May 2015
Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review Cheng, Xin-Bing; Zhang, Rui; Zhao, Chen-Zi Chemical Reviews, Vol. 117, Issue 15 https://doi.org/10.1021/acs.chemrev.7b00115	journal	July 2017
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
An Outlook on Lithium Ion Battery Technology Manthiram, Arumugam ACS Central Science, Vol. 3, Issue 10 https://doi.org/10.1021/acscentsci.7b00288	journal	September 2017
Electrochemical Window of the Li-Ion Solid Electrolyte Li ₇ La ₃ Zr ₂ O ₁₂ Thompson, Travis; Yu, Seungho; Williams, Logan ACS Energy Letters, Vol. 2, Issue 2 https://doi.org/10.1021/acsenergylett.6b00593	journal	January 2017
DFT Study of the Role of Al ³⁺ in the Fast Ion-Conductor Li _{7–3 x} Al ³⁺ _x La ₃ Zr ₂ O ₁₂ Garnet Rettenwander, Daniel; Blaha, Peter; Laskowski, Robert Chemistry of Materials, Vol. 26, Issue 8 https://doi.org/10.1021/cm5000999	journal	April 2014
Crystal Chemistry and Stability of “Li₇La₃Zr₂O₁₂ ” Garnet: A Fast Lithium-Ion Conductor Geiger, Charles A.; Alekseev, Evgeny; Lazic, Biljana Inorganic Chemistry, Vol. 50, Issue 3, p. 1089-1097 https://doi.org/10.1021/ic101914e	journal	February 2011
Synthesis and Crystal Chemistry of the Fast Li-Ion Conductor Li ₇ La ₃ Zr ₂ O ₁₂ Doped with Fe Rettenwander, Daniel; Geiger, Charles A.; Amthauer, Georg Inorganic Chemistry, Vol. 52, Issue 14 https://doi.org/10.1021/ic400589u	journal	July 2013
The Li-Ion Rechargeable Battery: A Perspective Goodenough, John B.; Park, Kyu-Sung Journal of the American Chemical Society, Vol. 135, Issue 4 https://doi.org/10.1021/ja3091438	journal	January 2013
Mechanosynthesis of Solid Electrolytes: Preparation, Characterization, and Li Ion Transport Properties of Garnet-Type Al-Doped Li ₇ La ₃ Zr ₂ O ₁₂ Crystallizing with Cubic Symmetry Düvel, Andre; Kuhn, Alexander; Robben, Lars The Journal of Physical Chemistry C, Vol. 116, Issue 29 https://doi.org/10.1021/jp301193r	journal	July 2012
Beyond Lithium Ion Batteries Luntz, Alan The Journal of Physical Chemistry Letters, Vol. 6, Issue 2 https://doi.org/10.1021/jz502665r	journal	January 2015
Issues and challenges facing rechargeable lithium batteries Tarascon, J.-M.; Armand, M. Nature, Vol. 414, Issue 6861, p. 359-367 https://doi.org/10.1038/35104644	journal	November 2001
Promise and reality of post-lithium-ion batteries with high energy densities Choi, Jang Wook; Aurbach, Doron Nature Reviews Materials, Vol. 1, Issue 4 https://doi.org/10.1038/natrevmats.2016.13	journal	March 2016
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
Status and challenges in enabling the lithium metal electrode for high-energy and low-cost rechargeable batteries Albertus, Paul; Babinec, Susan; Litzelman, Scott Nature Energy, Vol. 3, Issue 1 https://doi.org/10.1038/s41560-017-0047-2	journal	December 2017
High electronic conductivity as the origin of lithium dendrite formation within solid electrolytes Han, Fudong; Westover, Andrew S.; Yue, Jie Nature Energy, Vol. 4, Issue 3 https://doi.org/10.1038/s41560-018-0312-z	journal	January 2019
Critical stripping current leads to dendrite formation on plating in lithium anode solid electrolyte cells Kasemchainan, Jitti; Zekoll, Stefanie; Spencer Jolly, Dominic Nature Materials, Vol. 18, Issue 10 https://doi.org/10.1038/s41563-019-0438-9	journal	July 2019
Effect of microstructure and surface impurity segregation on the electrical and electrochemical properties of dense Al-substituted Li ₇ La ₃ Zr ₂ O ₁₂ Cheng, Lei; Park, Joong Sun; Hou, Huaming J. Mater. Chem. A, Vol. 2, Issue 1 https://doi.org/10.1039/C3TA13999A	journal	January 2014
The origin of high electrolyte–electrode interfacial resistances in lithium cells containing garnet type solid electrolytes Cheng, Lei; Crumlin, Ethan J.; Chen, Wei Phys. Chem. Chem. Phys., Vol. 16, Issue 34 https://doi.org/10.1039/C4CP02921F	journal	January 2014
Tetragonal vs. cubic phase stability in Al – free Ta doped Li ₇ La ₃ Zr ₂ O ₁₂ (LLZO) Thompson, Travis; Wolfenstine, Jeff; Allen, Jan L. J. Mater. Chem. A, Vol. 2, Issue 33 https://doi.org/10.1039/C4TA02099E	journal	January 2014
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
The role of the solid electrolyte interphase layer in preventing Li dendrite growth in solid-state batteries Wu, Bingbin; Wang, Shanyu; Lochala, Joshua Energy & Environmental Science, Vol. 11, Issue 7 https://doi.org/10.1039/C8EE00540K	journal	January 2018
A bird's-eye view of Li-stuffed garnet-type Li ₇ La ₃ Zr ₂ O ₁₂ ceramic electrolytes for advanced all-solid-state Li batteries Samson, Alfred Junio; Hofstetter, Kyle; Bag, Sourav Energy & Environmental Science, Vol. 12, Issue 10 https://doi.org/10.1039/C9EE01548E	journal	January 2019
Local Li-ion conductivity changes within Al stabilized Li ₇ La ₃ Zr ₂ O ₁₂ and their relationship to three-dimensional variations of the bulk composition Smetaczek, Stefan; Wachter-Welzl, Andreas; Wagner, Reinhard Journal of Materials Chemistry A, Vol. 7, Issue 12 https://doi.org/10.1039/C9TA00356H	journal	January 2019
Atomistic insight into the dopant impacts at the garnet Li₇La₃Zr₂O₁₂ solid electrolyte grain boundaries Gao, Bo; Jalem, Randy; Tateyama, Yoshitaka Journal of Materials Chemistry A, Vol. 10, Issue 18 https://doi.org/10.1039/D2TA00545J	journal	January 2022
Structure and dynamics of the fast lithium ion conductor “Li7La3Zr2O12” Buschmann, Henrik; Dölle, Janis; Berendts, Stefan Physical Chemistry Chemical Physics, Vol. 13, Issue 43 https://doi.org/10.1039/c1cp22108f	journal	January 2011
Low temperature stabilization of cubic (Li7−xAlx/3)La3Zr2O12: role of aluminum during formation Hubaud, Aude A.; Schroeder, David J.; Key, Baris Journal of Materials Chemistry A, Vol. 1, Issue 31 https://doi.org/10.1039/c3ta11338h	journal	January 2013
Cubic phases of garnet-type Li7La3Zr2O12: the role of hydration Larraz, G.; Orera, A.; Sanjuán, M. L. Journal of Materials Chemistry A, Vol. 1, Issue 37 https://doi.org/10.1039/c3ta11996c	journal	January 2013
Li ⁺ transport properties of W substituted Li ₇ La ₃ Zr ₂ O ₁₂ cubic lithium garnets Dhivya, L.; Janani, N.; Palanivel, B. AIP Advances, Vol. 3, Issue 8 https://doi.org/10.1063/1.4818971	journal	August 2013
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
Optimized time-of-flight secondary ion mass spectroscopy depth profiling with a dual beam technique Iltgen, K.; Bendel, C.; Benninghoven, A. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 15, Issue 3 https://doi.org/10.1116/1.580874	journal	May 1997
Evaluation of Scalable Synthesis Methods for Aluminum-Substituted Li7La3Zr2O12 Solid Electrolytes Mann, Markus; Küpers, Michael; Häuschen, Grit Materials, Vol. 14, Issue 22 https://doi.org/10.3390/ma14226809	journal	November 2021

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