Origin of high Li⁺ conduction in doped Li₇La₃Zr₂O₁₂ garnets

Chen, Yan; Rangasamy, Ezhiylmurugan; Liang, Chengdu; An, Ke

doi:10.1021/acs.chemmater.5b02521

Title: Origin of high Li⁺ conduction in doped Li₇La₃Zr₂O₁₂ garnets

Journal Article · Thu Aug 06 00:00:00 EDT 2015 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.5b02521· OSTI ID:1213330

Chen, Yan ^[1]; Rangasamy, Ezhiylmurugan ^[1]; Liang, Chengdu ^[1]; An, Ke ^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Substitution of a native ion in the crystals with a foreign ion that differs in valence (aliovalent doping) has been widely attempted to upgrade solid-state ionic conductors for various charge carriers including O²⁻, H⁺, Li⁺, Na⁺, etc. The doping helps promote the high-conductive framework and dredge the tunnel for fast ion transport. The garnet-type Li₇La₃Zr₂O₁₂ (LLZO) is a fast Li⁺ solid conductor, which received much attention as an electrolyte candidate for all-solid-state lithium ion batteries, showing great potential to offer high energy density and minimize battery safety concerns to meet extensive applications in large energy storage systems such as those for electric vehicles and aerospace. In the Li-stuffed garnet framework of LLZO, the 3D pathway formed by the incompletely occupied tetrahedral sites bridged by a single octahedron enables the superior Li⁺ conductivity. For optimal performance, many aliovalent-doping efforts have been made throughout metal elements (Al³⁺, Ta⁵⁺) and metalloid elements (Ga³⁺, Te⁶⁺) in the periodic table with various valences to stabilize the high-conductive phase and increase the Li vacancy concentration.

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Research Organization:: Oak Ridge National Laboratory (ORNL). Center for Nanophase Materials Sciences (CNMS); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1213330

Journal Information:: Chemistry of Materials, Vol. 27, Issue 16; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 70 works

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References (30)

Intermediate temperature solid oxide fuel cells Brett, Daniel J. L.; Atkinson, Alan; Brandon, Nigel P. Chemical Society Reviews, Vol. 37, Issue 8 https://doi.org/10.1039/b612060c	journal	January 2008
Novel Chemically Stable Ba ₃ Ca _1.18 Nb _{1.82– x} Y _x O _9−δ Proton Conductor: Improved Proton Conductivity through Tailored Cation Ordering Wang, Siwei; Chen, Yan; Fang, Shumin Chemistry of Materials, Vol. 26, Issue 6 https://doi.org/10.1021/cm403684b	journal	March 2014
Inorganic solid Li ion conductors: An overview Knauth, Philippe Solid State Ionics, Vol. 180, Issue 14-16, p. 911-916 https://doi.org/10.1016/j.ssi.2009.03.022	journal	June 2009
Ion transport in sodium ion conducting solid electrolytes Fergus, Jeffrey W. Solid State Ionics, Vol. 227 https://doi.org/10.1016/j.ssi.2012.09.019	journal	October 2012
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
A preliminary investigation of fracture toughness of Li7La3Zr2O12 and its comparison to other solid Li-ionconductors Wolfenstine, Jeff; Jo, Hyungyung; Cho, Yong-Hun Materials Letters, Vol. 96 https://doi.org/10.1016/j.matlet.2013.01.021	journal	April 2013
Characterization of the interface between LiCoO2 and Li7La3Zr2O12 in an all-solid-state rechargeable lithium battery Kim, Ki Hyun; Iriyama, Yasutoshi; Yamamoto, Kazuo Journal of Power Sources, Vol. 196, Issue 2 https://doi.org/10.1016/j.jpowsour.2010.07.073	journal	January 2011
Compatibility of Li[sub 7]La[sub 3]Zr[sub 2]O[sub 12] Solid Electrolyte to All-Solid-State Battery Using Li Metal Anode Kotobuki, Masashi; Munakata, Hirokazu; Kanamura, Kiyoshi Journal of The Electrochemical Society, Vol. 157, Issue 10 https://doi.org/10.1149/1.3474232	journal	January 2010
Lithium Distribution in Aluminum-Free Cubic Li ₇ La ₃ Zr ₂ O ₁₂ Xie, Hui; Alonso, Jose A.; Li, Yutao Chemistry of Materials, Vol. 23, Issue 16 https://doi.org/10.1021/cm201671k	journal	August 2011
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
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
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
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
Lithium ion transport properties of high conductive tellurium substituted Li7La3Zr2O12 cubic lithium garnets Deviannapoorani, C.; Dhivya, L.; Ramakumar, S. Journal of Power Sources, Vol. 240 https://doi.org/10.1016/j.jpowsour.2013.03.166	journal	October 2013
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
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
Mechanisms of Li $^{+}$ transport in garnet-type cubic Li $_{3 + x}$ La $_{3} M_{2}$ O $_{12}$ ( $M$ = Te, Nb, Zr) Xu, Ming; Park, Min Sik; Lee, Jae Myung Physical Review B, Vol. 85, Issue 5 https://doi.org/10.1103/PhysRevB.85.052301	journal	February 2012
First In Situ Lattice Strains Measurements Under Load at VULCAN An, Ke; Skorpenske, Harley D.; Stoica, Alexandru D. Metallurgical and Materials Transactions A, Vol. 42, Issue 1 https://doi.org/10.1007/s11661-010-0495-9	journal	October 2010
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
High lithium ion conductivity of Li7La3Zr2O12 synthesized by solid state reaction Lee, Jae-Myung; Kim, Taeyoung; Baek, Seung-Wook Solid State Ionics, Vol. 258 https://doi.org/10.1016/j.ssi.2014.01.043	journal	May 2014
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
Concerted Migration Mechanism in the Li Ion Dynamics of Garnet-Type Li ₇ La ₃ Zr ₂ O ₁₂ Jalem, Randy; Yamamoto, Yoshihiro; Shiiba, Hiromasa Chemistry of Materials, Vol. 25, Issue 3 https://doi.org/10.1021/cm303542x	journal	January 2013
Effects of Gallium Doping in Garnet-Type Li ₇ La ₃ Zr ₂ O ₁₂ Solid Electrolytes Jalem, Randy; Rushton, M. J. D.; Manalastas, William Chemistry of Materials, Vol. 27, Issue 8 https://doi.org/10.1021/cm5045122	journal	April 2015
Garnet-type solid-state fast Li ion conductors for Li batteries: critical review Thangadurai, Venkataraman; Narayanan, Sumaletha; Pinzaru, Dana Chemical Society Reviews, Vol. 43, Issue 13 https://doi.org/10.1039/c4cs00020j	journal	January 2014
Ionic distribution and conductivity in lithium garnet Li7La3Zr2O12 Li, Yutao; Han, Jian- Tao; Wang, Chang- An Journal of Power Sources, Vol. 209 https://doi.org/10.1016/j.jpowsour.2012.02.100	journal	July 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
Effect of calcining and Al doping on structure and conductivity of Li 7 La 3 Zr 2 O 12 Chen, Ru-Jun; Huang, Mian; Huang, Wen-Ze Solid State Ionics, Vol. 265 https://doi.org/10.1016/j.ssi.2014.07.004	journal	November 2014
Low temperature synthesis of highly ion conductive Li7La3Zr2O12–Li3BO3 composites Tadanaga, Kiyoharu; Takano, Ryohei; Ichinose, Takahiro Electrochemistry Communications, Vol. 33 https://doi.org/10.1016/j.elecom.2013.04.004	journal	August 2013
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
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

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