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

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

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

Adv Sci (Weinh). 2024 Nov 25:e2408805. doi: 10.1002/advs.202408805. Online ahead of print.

Authors

Tao Wang^{1

2}, Jiyoung Ock¹, X Chelsea Chen¹, Fan Wang², Meijia Li¹, Matthew S Chambers¹, Gabriel M Veith¹, Lauren B Shepard³, Susan B Sinnott^{3

4

5

6}, Albina Borisevich⁷, Miaofang Chi⁷, Amit Bhattacharya⁸, Raphaële J Clément⁸, Alexei P Sokolov^{1

2}, Sheng Dai^{1

2}

Affiliations

¹ Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN, 37831, USA.
² Department of Chemistry, Institute for Advanced Materials and Manufacturing, University of Tennessee, Knoxville, TN, 37996, USA.
³ Department of Materials Science and Engineering, The Pennsylvania State University, University Park, PA, 16802, USA.
⁴ Department of Chemistry, The Pennsylvania State University, University Park, PA, 16802, USA.
⁵ Institute for Computational and Data Sciences, The Pennsylvania State University, University Park, PA, 16802, USA.
⁶ Materials Research Institute, The Pennsylvania State University, University Park, PA, 16802, USA.
⁷ Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee, 37831, USA.
⁸ Materials Department and Materials Research Laboratory, University of California, Santa Barbara, CA, 93106, USA.

PMID: 39586301
DOI: 10.1002/advs.202408805

Abstract

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).

Keywords: disordered structure; flux synthesis; molten salts; nanomaterials; solid composite electrolyte.

Abstract

Grants and funding