Flux Synthesis of A-site Disordered Perovskite La0.5M0.5TiO3 (M$=$Li, Na, K) Nanorods Tailored for Solid Composite Electrolytes

Wang, Tao; Ock, Jiyoung; Chen, X. Chelsea; Wang, Fan; Li, Meijia; Chambers, Matthew S.; Veith, Gabriel M.; Shepard, Lauren B.; Sinnott, Susan B.; Borisevich, Albina; Chi, Miaofang; Bhattacharya, Amit; Clément, Raphaële J.; Sokolov, Alexei P.; Dai, Sheng

doi:10.1002/advs.202408805

Flux Synthesis of A-site Disordered Perovskite La_0.5M_0.5TiO₃ (M$$=$$Li, Na, K) Nanorods Tailored for Solid Composite Electrolytes

Journal Article · Sun Nov 24 23:00:00 EST 2024 · Advanced Science

DOI:https://doi.org/10.1002/advs.202408805· OSTI ID:2538432

^[1]; ^[2]; ^[2]; Wang, Fan ^[3]; Li, Meijia ^[2]; ^[2]; ^[2]; ^[4]; ^[4]; ^[5]; ^[5]; Bhattacharya, Amit ^[6]; Clément, Raphaële J. ^[6]; ^[1]; ^[1]

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Univ. of Tennessee, Knoxville, TN (United States)
Pennsylvania State Univ., University Park, PA (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Univ. of California, Santa Barbara, CA (United States)

Inorganic fillers play an important role in improving the ionic conductivity of solid composite electrolytes (SCEs) for Li-ion batteries. Among inorganic fillers, perovskite-type lithium lanthanum titanate (LLTO) stands out for its high bulk Li⁺ conductivity on the order of 10^-3 S cm^-1 at room temperature. According to a literature survey, the optimal LLTO filler should possess the following characteristics: i) a single-crystal structure to minimize grain boundaries; ii) a small particle size to increase the filler/polymer interface area; iii) a 1D morphology for efficient interface channels; and iv) cubic symmetry to facilitate rapid bulk Li⁺ diffusion within the filler. However, the synthesis of single crystal, 1D LLTO nanomaterials with cubic symmetry is challenging. Herein, a flux strategy is developed to synthesize La_0.5M_0.5TiO₃ (LMTO, M$$=$$Li, Na, and K) single-crystal nanorods with an A-site-disordered, cubic perovskite phase. The flux media promotes the oriented growth of nanorods, prevents nanorods from sintering, and provides multiple alkali metal ion doping at M sites to stabilize the cubic phase. SCEs compositing the Li⁺-conducting LMTO nanorods as fillers and poly[vinylene carbonate-co-lithium sulfonyl(trifluoromethane sulfonyl)imide methacrylate] matrix exhibit more than twice the conductivity of the neat polymer electrolyte (30.6 vs 14.0 µS cm^-1 at 303 K).

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2538432

Journal Information:: Advanced Science, Journal Name: Advanced Science Journal Issue: 3 Vol. 12; ISSN 2198-3844

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (52)

Promises, Challenges, and Recent Progress of Inorganic Solid-State Electrolytes for All-Solid-State Lithium Batteries Gao, Zhonghui; Sun, Huabin; Fu, Lin Advanced Materials, Vol. 30, Issue 17 https://doi.org/10.1002/adma.201705702	journal	February 2018
High‐Entropy Oxides: Fundamental Aspects and Electrochemical Properties Sarkar, Abhishek; Wang, Qingsong; Schiele, Alexander Advanced Materials, Vol. 31, Issue 26 https://doi.org/10.1002/adma.201806236	journal	March 2019
ICET – A Python Library for Constructing and Sampling Alloy Cluster Expansions Ångqvist, Mattias; Muñoz, William A.; Rahm, J. Magnus Advanced Theory and Simulations, Vol. 2, Issue 7 https://doi.org/10.1002/adts.201900015	journal	May 2019
Direct Recycling of Spent NCM Cathodes through Ionothermal Lithiation Wang, Tao; Luo, Huimin; Bai, Yaocai Advanced Energy Materials, Vol. 10, Issue 30 https://doi.org/10.1002/aenm.202001204	journal	June 2020
Preparing Two‐Dimensional Ordered Li_0.33La_0.557TiO₃ Crystal in Interlayer Channel of Thin Laminar Inorganic Solid‐State Electrolyte towards Ultrafast Li⁺ Transfer Lv, Ruixin; Kou, Weijie; Guo, Shiyuan Angewandte Chemie International Edition, Vol. 61, Issue 7 https://doi.org/10.1002/anie.202114220	journal	December 2021
A Stable Solid Polymer Electrolyte for Lithium Metal Battery with Electronically Conductive Fillers Guo, Xuelin; Ju, Zhengyu; Qian, Xitang Angewandte Chemie International Edition, Vol. 62, Issue 7 https://doi.org/10.1002/anie.202217538	journal	January 2023
Approaching high performancePVDF‐HFPbased solid composite electrolytes withLLTOnanorods for solid‐state lithium‐ion batteries Li, Jialun; Zhu, Lin; Zhang, Junwen International Journal of Energy Research, Vol. 45, Issue 5 https://doi.org/10.1002/er.6347	journal	January 2021
Composition Modulation and Structure Design of Inorganic‐in‐Polymer Composite Solid Electrolytes for Advanced Lithium Batteries Liu, Yuan; Xu, Bingqing; Zhang, Wenyu Small, Vol. 16, Issue 15 https://doi.org/10.1002/smll.201902813	journal	October 2019
A high-entropy perovskite titanate lithium-ion battery anode Yan, Jinhua; Wang, Dan; Zhang, Xiaoyan Journal of Materials Science, Vol. 55, Issue 16 https://doi.org/10.1007/s10853-020-04482-0	journal	March 2020
Sol–gel carbons from ionothermal syntheses Fellinger, Tim-Patrick Journal of Sol-Gel Science and Technology, Vol. 81, Issue 1 https://doi.org/10.1007/s10971-016-4115-z	journal	June 2016
The effect of sintering on the grain boundary conductivity of lithium lanthanum titanates Ban, C. Solid State Ionics, Vol. 140, Issue 3-4 https://doi.org/10.1016/S0167-2738(01)00821-9	journal	April 2001
In search of the cubic phase of the Li+ ion-conducting perovskite La2/3−xLi3xTiO3: structure and properties of quenched and in situ heated samples Bohnke, O. Solid State Ionics, Vol. 149, Issue 3-4 https://doi.org/10.1016/S0167-2738(02)00142-X	journal	August 2002
Electrical behaviour of La1.33−xM3xTi2O6 perovskites (M=Li, Na and K) Ruiz, A. I.; López, M. L.; Veiga, M. L. International Journal of Inorganic Materials, Vol. 1, Issue 3-4 https://doi.org/10.1016/S1466-6049(99)00029-X	journal	September 1999
Template-free fabrication of pure single-crystalline BaTiO3 nano-wires by molten salt synthesis technique Li, Bao-rang; Shang, Wei; Hu, Zhong-liang Ceramics International, Vol. 40, Issue 1 https://doi.org/10.1016/j.ceramint.2013.05.105	journal	January 2014
A novel solid PEO/LLTO-nanowires polymer composite electrolyte for solid-state lithium-ion battery Zhu, Lin; Zhu, Penghui; Fang, Qunxiang Electrochimica Acta, Vol. 292 https://doi.org/10.1016/j.electacta.2018.10.005	journal	December 2018
Mechanisms and properties of ion-transport in inorganic solid electrolytes Zhang, Bingkai; Tan, Rui; Yang, Luyi Energy Storage Materials, Vol. 10 https://doi.org/10.1016/j.ensm.2017.08.015	journal	January 2018
Recent advances in organic-inorganic composite solid electrolytes for all-solid-state lithium batteries Cheng, Zhiwei; Liu, Tong; Zhao, Bin Energy Storage Materials, Vol. 34 https://doi.org/10.1016/j.ensm.2020.09.016	journal	January 2021
Strategies to Boost Ionic Conductivity and Interface Compatibility of Inorganic - Organic Solid Composite Electrolytes Zhu, Xiaoqi; Wang, Kai; Xu, Yanan Energy Storage Materials, Vol. 36 https://doi.org/10.1016/j.ensm.2021.01.002	journal	April 2021
Recent progress in molten salt synthesis of low-dimensional perovskite oxide nanostructures, structural characterization, properties, and functional applications: A review Xue, Piaojie; Wu, Heng; Lu, Yao Journal of Materials Science & Technology, Vol. 34, Issue 6 https://doi.org/10.1016/j.jmst.2017.10.005	journal	June 2018
Polymer-ceramic composite electrolytes for all-solid-state lithium batteries: Ionic conductivity and chemical interaction enhanced by oxygen vacancy in ceramic nanofibers Yang, Hui; Abdullah, Muhammad; Bright, Joeseph Journal of Power Sources, Vol. 495 https://doi.org/10.1016/j.jpowsour.2021.229796	journal	May 2021
Direct recycling of spent nickel-rich cathodes in reciprocal ternary molten salts Wang, Tao; Luo, Huimin; Bai, Yaocai Journal of Power Sources, Vol. 593 https://doi.org/10.1016/j.jpowsour.2023.233798	journal	February 2024
Realizing fourfold enhancement in conductivity of perovskite Li0.33La0.557TiO3 electrolyte membrane via a Sr and Ta co-doping strategy Li, Ruixia; Liao, Kaiming; Zhou, Wei Journal of Membrane Science, Vol. 582 https://doi.org/10.1016/j.memsci.2019.03.074	journal	July 2019
A composite solid electrolyte with a framework of vertically aligned perovskite for all-solid-state Li-metal batteries Liu, Ke; Wu, Maochun; Wei, Lei Journal of Membrane Science, Vol. 610 https://doi.org/10.1016/j.memsci.2020.118265	journal	September 2020
Effect of the LLTO nanoparticles on the conducting properties of PEO-based solid electrolyte Milian Pila, Carlos Ricardo; Cappe, Eduardo Pérez; Mohallem, Nelcy Della Santina Solid State Sciences, Vol. 88 https://doi.org/10.1016/j.solidstatesciences.2018.10.014	journal	February 2019
Li mobility in Li0.5−xNaxLa0.5TiO3 perovskites (0≤x≤0.5)Influence of structural and compositional parameters Jimenez, R.; Rivera, A.; Varez, A. Solid State Ionics, Vol. 180, Issue 26-27 https://doi.org/10.1016/j.ssi.2009.08.002	journal	October 2009
Characterization of Sr-doped lithium lanthanum titanate with improved transport properties Zhang, Saisai; Zhao, Hailei; Guo, Jingrong Solid State Ionics, Vol. 336 https://doi.org/10.1016/j.ssi.2019.03.015	journal	August 2019
Innovative Design for the Enhancement of Lithium Lanthanum Titanate Electrolytes de Oliveira, Rafael B.; Andreeta, Marcello R. B.; de Souza, Dulcina M. P. F. Crystal Growth & Design, Vol. 19, Issue 9 https://doi.org/10.1021/acs.cgd.9b00825	journal	July 2019
Metastability in Li–La–Ti–O Perovskite Materials and Its Impact on Ionic Conductivity Jonderian, Antranik; Ting, Michelle; McCalla, Eric Chemistry of Materials, Vol. 33, Issue 12 https://doi.org/10.1021/acs.chemmater.1c01490	journal	June 2021
Memory Effect on the Synthesis of Perovskite-Type Li-Ion Conductor Li_xLa_2/3–x/3TiO₃ (LLTO) Chambers, Matthew S.; Chen, Jiadong; Sacci, Robert L. Chemistry of Materials, Vol. 36, Issue 3 https://doi.org/10.1021/acs.chemmater.3c01928	journal	January 2024
Percolating Interfacial Layers Enhance Conductivity in Polymer–Composite Electrolytes Ock, Ji-young; Bhattacharya, Amit; Wang, Tao Macromolecules, Vol. 57, Issue 15 https://doi.org/10.1021/acs.macromol.4c00615	journal	July 2024
Lithium Lanthanum Titanate Single Crystals: Dependence of Lithium-Ion Conductivity on Crystal Domain Orientation Kobayashi, Shunsuke; Yokoe, Daisaku; Fujiwara, Yasuyuki Nano Letters, Vol. 22, Issue 13 https://doi.org/10.1021/acs.nanolett.2c01655	journal	June 2022
Ionic Conductivity Enhancement of Polymer Electrolytes with Ceramic Nanowire Fillers Liu, Wei; Liu, Nian; Sun, Jie Nano Letters, Vol. 15, Issue 4, p. 2740-2745 https://doi.org/10.1021/acs.nanolett.5b00600	journal	March 2015
Inhibition of Crystallization of Poly(ethylene oxide) by Ionic Liquid: Insight into Plasticizing Mechanism and Application for Solid-State Sodium Ion Batteries Chen, Guanghai; Bai, Ying; Gao, Yongsheng ACS Applied Materials & Interfaces, Vol. 11, Issue 46 https://doi.org/10.1021/acsami.9b16294	journal	October 2019
Stable Solid Electrolyte Interphase Layer Formed by Electrochemical Pretreatment of Gel Polymer Coating on Li Metal Anode for Lithium–Oxygen Batteries Lim, Hyung-Seok; Kwak, Won-Jin; Chae, Sujong ACS Energy Letters, Vol. 6, Issue 9 https://doi.org/10.1021/acsenergylett.1c01144	journal	August 2021
Lithium Lanthanum Titanates: A Review Stramare, S.; Thangadurai, V.; Weppner, W. Chemistry of Materials, Vol. 15, Issue 21 https://doi.org/10.1021/cm0300516	journal	October 2003
Morphology-Controlled Synthesis of Barium Titanate Nanostructures Huang, Kuan-Chih; Huang, Tung-Ching; Hsieh, Wen-Feng Inorganic Chemistry, Vol. 48, Issue 19 https://doi.org/10.1021/ic900854x	journal	September 2009
Nanocomposite polymer electrolytes for lithium batteries Croce, F.; Appetecchi, G. B.; Persi, L. Nature, Vol. 394, Issue 6692 https://doi.org/10.1038/28818	journal	July 1998
Enhancing ionic conductivity in composite polymer electrolytes with well-aligned ceramic nanowires Liu, Wei; Lee, Seok Woo; Lin, Dingchang Nature Energy, Vol. 2, Issue 5 https://doi.org/10.1038/nenergy.2017.35	journal	April 2017
Rational design of a topological polymeric solid electrolyte for high-performance all-solid-state alkali metal batteries Su, Yun; Rong, Xiaohui; Gao, Ang Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-31792-5	journal	July 2022
Fundamentals of inorganic solid-state electrolytes for batteries Famprikis, Theodosios; Canepa, Pieremanuele; Dawson, James A. Nature Materials, Vol. 18, Issue 12 https://doi.org/10.1038/s41563-019-0431-3	journal	August 2019
Cation-disordered rocksalt-type high-entropy cathodes for Li-ion batteries Lun, Zhengyan; Ouyang, Bin; Kwon, Deok-Hwang Nature Materials, Vol. 20, Issue 2 https://doi.org/10.1038/s41563-020-00816-0	journal	October 2020
Topochemical molten salt synthesis for functional perovskite compounds Li, Lihong; Deng, Jinxia; Chen, Jun Chemical Science, Vol. 7, Issue 2 https://doi.org/10.1039/C5SC03521J	journal	January 2016
Room temperature lithium superionic conductivity in high entropy oxides Bérardan, D.; Franger, S.; Meena, A. K. Journal of Materials Chemistry A, Vol. 4, Issue 24 https://doi.org/10.1039/C6TA03249D	journal	January 2016
Preparation of silica aerogel using ionic liquids as solvents Dai, Sheng; Ju, Y. H.; Gao, H. J. Chemical Communications, Issue 3 https://doi.org/10.1039/a907147d	journal	January 2000
Tetragonal superstructure and thermal history of Li0.3La0.567TiO3 (LLTO) solid electrolyte by neutron diffraction Catti, Michele; Sommariva, Marco; Ibberson, Richard M. Journal of Materials Chemistry, Vol. 17, Issue 13 https://doi.org/10.1039/b614345h	journal	January 2007
Electrolytes for solid-state lithium rechargeable batteries: recent advances and perspectives Quartarone, Eliana; Mustarelli, Piercarlo Chemical Society Reviews, Vol. 40, Issue 5 https://doi.org/10.1039/c0cs00081g	journal	January 2011
Influence of tetragonal/cubic phase composition on the total ionic conductivity of Li3xLa2/3−xTiO3 Wu, Qi Yun; Zheng, De Yi; Mao, Run Yu AIP Advances, Vol. 13, Issue 10 https://doi.org/10.1063/5.0161316	journal	October 2023
Microscopic dynamics of lithium diffusion in single crystal of the solid-state electrolyte La 2 / 3 − x Li 3 x TiO 3 ( x = 0.13 ) studied by quasielastic neutron scattering Matsuura, Masato; Fujiwara, Yasuyuki; Moriwake, Hiroki Physical Review B, Vol. 104, Issue 9 https://doi.org/10.1103/PhysRevB.104.094305	journal	September 2021
Li self-diffusion in garnet-type Li 7 La 3 Zr 2 O 12 as probed directly by diffusion-induced Li 7 spin-lattice relaxation NMR spectroscopy Kuhn, A.; Narayanan, S.; Spencer, L. Physical Review B, Vol. 83, Issue 9 https://doi.org/10.1103/PhysRevB.83.094302	journal	March 2011
Size–strain line-broadening analysis of the ceria round-robin sample Balzar, D.; Audebrand, N.; Daymond, M. R. Journal of Applied Crystallography, Vol. 37, Issue 6 https://doi.org/10.1107/S0021889804022551	journal	November 2004
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Shannon, R. D. Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767 https://doi.org/10.1107/S0567739476001551	journal	September 1976
Cycling of block copolymer composites with lithium-conducting ceramic nanoparticles Patel, Vivaan; Dato, Michael A.; Chakraborty, Saheli Frontiers in Chemistry, Vol. 11 https://doi.org/10.3389/fchem.2023.1199677	journal	June 2023

Similar Records

Critical role of polymer-ceramic ion exchange for high conductivity composite electrolytes

Journal Article · Wed Jun 25 00:00:00 EDT 2025 · Solid State Ionics · OSTI ID:2584496

Polymer-ceramic composite electrolytes for all-solid-state lithium batteries: Ionic conductivity and chemical interaction enhanced by oxygen vacancy in ceramic nanofibers

Journal Article · Thu Mar 25 00:00:00 EDT 2021 · Journal of Power Sources · OSTI ID:1787473

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
disordered structure
flux synthesis
molten salts
nanomaterials
solid composite electrolyte

Flux Synthesis of A-site Disordered Perovskite La0.5M0.5TiO3 (M$$=$$Li, Na, K) Nanorods Tailored for Solid Composite Electrolytes

Citation Formats

References (52)

Similar Records

Related Subjects

Flux Synthesis of A-site Disordered Perovskite La_0.5M_0.5TiO₃ (M$$=$$Li, Na, K) Nanorods Tailored for Solid Composite Electrolytes