Lithium Nafion-Modified Li6.05Ga0.25La3Zr2O11.8F0.2 Trilayer Hybrid Solid Electrolyte for High-Voltage Cathodes in All-Solid-State Lithium-Metal Batteries

Kumlachew Zelalem Walle; Yi-Shiuan Wu; She-Huang Wu; Jeng-Kuei Chang; Rajan Jose; Chun-Chen Yang

doi:10.1021/acsami.2c00753

Lithium Nafion-Modified Li_6.05Ga_0.25La₃Zr₂O_11.8F_0.2 Trilayer Hybrid Solid Electrolyte for High-Voltage Cathodes in All-Solid-State Lithium-Metal Batteries

ACS Appl Mater Interfaces. 2022 Apr 6;14(13):15259-15274. doi: 10.1021/acsami.2c00753. Epub 2022 Mar 28.

Authors

Kumlachew Zelalem Walle^{1

2}, Yi-Shiuan Wu¹, She-Huang Wu³, Jeng-Kuei Chang⁴, Rajan Jose⁵, Chun-Chen Yang^{1

2

6}

Affiliations

¹ Battery Research Center of Green Energy, Ming Chi University of Technology, New Taipei City 24301, Taiwan, R.O.C.
² Department of Chemical Engineering, Ming Chi University of Technology, New Taipei City 24301, Taiwan, R.O.C.
³ Graduate Institute of Science and Technology, National Taiwan University of Science and Technology, 43, Sec. 4, Keelung Road, Taipei 106, Taiwan, R.O.C.
⁴ Department of Materials Science and Engineering, National Chiao Tung University, Hsinchu, 30010, Taiwan, R.O.C.
⁵ Nanostructured Renewable Energy Materials Laboratory, Faculty of Industrial Sciences and Technology, University Malaysia Pahang, 26300 Kuantan, Malaysia.
⁶ Department of Chemical and Materials Engineering, and Green Technology Research Center, Chang Gung University, Taoyuan City 333, Taiwan, R.O.C.

PMID: 35344344
DOI: 10.1021/acsami.2c00753

Abstract

All-solid-state batteries containing ceramic-polymer solid electrolytes are possible alternatives to lithium-metal batteries containing liquid electrolytes in terms of their safety, energy storage, and stability at elevated temperatures. In this study we prepared a garnet-type Li_6.05Ga_0.25La₃Zr₂O_11.8F_0.2 (LGLZOF) solid electrolyte modified with lithium Nafion (LiNf) and incorporated it into poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrixes. We used a solution-casting method to obtain bilayer (Bi-HSE) and trilayer (Tri-HSE) hybrid solid electrolytes. A layer of functionalized multiwalled carbon nanotubes (f-MWCNTs) coated with LiNf (LiNf@f-MWCNT) in the Tri-HSE led to good compatibility with the polymer slurry and adhered well to the Li anode, thereby improving the interfacial contact at the electrode-solid electrolyte interface and suppressing dendrite growth. The Tri-HSE membrane displayed high ionic conductivity (5.6 × 10^-4 S cm^-1 at 30 °C), a superior Li⁺ transference number (0.87), and a wide electrochemical window (0-5.0 V vs Li/Li⁺). In addition, Li symmetrical cells incorporating this hybrid electrolyte possessed excellent interfacial stability over 600 h at 0.1 mA cm^-2 and a high critical current density (1.5 mA cm^-2). Solid-state lithium batteries having the structure LiNf@LiNi_0.8Co_0.1Mn_0.1O₂/Tri-HSE/Li delivered excellent room-temperature stable cycling performance at 0.5C, with a capacity retention of 85.1% after 450 cycles.

Keywords: Li6.05Ga0.25La3Zr2O11.8F0.2 (LGLZOF); Li7La3Zr2O12 (LLZO); all-solid-state lithium-metal batteries (ASSLMBs); hybrid solid electrolytes (HSEs); poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP).