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Vol. 18 (2026)

BaTiO3 Nanoparticle-Induced Interfacial Electric Field Optimization in Chloride Solid Electrolytes for 4.8 V All-Solid-State Lithium Batteries

https://doi.org/10.1007/s40820-025-01901-2
Qingmei Xiao
Guangdong Provincial Key Laboratory of New Energy Materials Service Safety, College of Materials Science and Engineering, Shenzhen University, Shenzhen 518060, People’s Republic of China
Shiming Huang
Guangdong Provincial Key Laboratory of New Energy Materials Service Safety, College of Materials Science and Engineering, Shenzhen University, Shenzhen 518060, People’s Republic of China
Donghao Liang
Guangdong Provincial Key Laboratory of New Energy Materials Service Safety, College of Materials Science and Engineering, Shenzhen University, Shenzhen 518060, People’s Republic of China
Cheng Liu
Guangdong Provincial Key Laboratory of New Energy Materials Service Safety, College of Materials Science and Engineering, Shenzhen University, Shenzhen 518060, People’s Republic of China
Ruonan Zhang
Guangdong Provincial Key Laboratory of New Energy Materials Service Safety, College of Materials Science and Engineering, Shenzhen University, Shenzhen 518060, People’s Republic of China
Wenjin Li
Guangdong Provincial Key Laboratory of New Energy Materials Service Safety, College of Materials Science and Engineering, Shenzhen University, Shenzhen 518060, People’s Republic of China
Guangliang Gary Liu
Guangdong Provincial Key Laboratory of New Energy Materials Service Safety, College of Materials Science and Engineering, Shenzhen University, Shenzhen 518060, People’s Republic of China

Corresponding Author: Guangliang Gary Liu

ggliu@szu.edu.cn

Nano-Micro Letters, Vol. 18 (2026), Article Number: 52

Abstract

Chloride-based solid electrolytes are considered promising candidates for next-generation high-energy–density all-solid-state batteries (ASSBs). However, their relatively low oxidative decomposition threshold (~ 4.2 V vs. Li+/Li) constrains their use in ultrahigh-voltage systems (e.g., 4.8 V). In this work, ferroelectric BaTiO3 (BTO) nanoparticles with optimized thickness of ~ 50–100 nm were successfully coated onto Li2.5Y0.5Zr0.5Cl6 (LYZC@5BTO) electrolytes using a time-efficient ball-milling process. The nanoparticle-induced interfacial ionic conduction enhancement mechanism contributed to the preservation of LYZC’s high ionic conductivity, which remained at 1.06 mS cm−1 for LYZC@5BTO. Furthermore, this surface electric field engineering strategy effectively mitigates the voltage-induced self-decomposition of chloride-based solid electrolytes, suppresses parasitic interfacial reactions with single-crystal NCM811 (SCNCM811), and inhibits the irreversible phase transition of SCNCM811. Consequently, the cycling stability of LYZC under high-voltage conditions (4.8 V vs. Li⁺/Li) is significantly improved. Specifically, ASSB cells employing LYZC@5BTO exhibited a superior discharge capacity of 95.4 mAh g−1 over 200 cycles at 1 C, way outperforming cell using pristine LYZC that only shows a capacity of 55.4 mAh g−1. Furthermore, time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy analysis revealed that Metal-O-Cl by-products from cumulative interfacial side reactions accounted for 6% of the surface species initially, rising to 26% after 200 cycles in pristine LYZC. In contrast, LYZC@5BTO limited this increase to only 14%, confirming the effectiveness of BTO in stabilizing the interfacial chemistry. This electric field modulation strategy offers a promising route toward the commercialization of high-voltage solid-state electrolytes and energy-dense ASSBs.


Highlights:
1 Time efficient ball milling achieves uniform BaTiO3 ( coating without sacrificing ionic conductivity (1.06 mS cm−1).
2 Ferroelectric BTO coating suppresses Li2.5Y0.5Zr0.5Cl6 (LYZC decomposition at 4.8 V via electric field modulation, enabling 76% capacity retention after 150 cycles.
3 BTO effectively minimizes the formation of interfacial ZrCl3O /YCl2O byproducts and mitigates the irreversible phase transition of single crystal NCM811 (SCNCM811), thereby improving the compatibility between LYZC and SCNCM811.

Keywords

All-solid-state batteries Chloride electrolyte Ferroelectric BaTiO3 High-voltage stability Surface modification
Xiao, Qingmei, Shiming Huang, Donghao Liang, Cheng Liu, Ruonan Zhang, Wenjin Li, and Guangliang Gary Liu. 2025. “BaTiO3 Nanoparticle-Induced Interfacial Electric Field Optimization in Chloride Solid Electrolytes for 4.8 V All-Solid-State Lithium Batteries”. Nano-Micro Letters 18 (September):52. https://doi.org/10.1007/s40820-025-01901-2.
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