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A dielectric electrolyte composite with high lithium-ion conductivity for high-voltage solid-state lithium metal batteries

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Abstract

The ionic conductivity of composite solid-state electrolytes does not meet the application requirements of solid-state lithium (Li) metal batteries owing to the harsh space charge layer of different phases and low concentration of movable Li+. Herein, we propose a robust strategy for creating high-throughput Li+ transport pathways by coupling the ceramic dielectric and electrolyte to overcome the low ionic conductivity challenge of composite solid-state electrolytes. A highly conductive and dielectric composite solid-state electrolyte is constructed by compositing the poly(vinylidene difluoride) matrix and the BaTiO3–Li0.33La0.56TiO3–x nanowires with a side-by-side heterojunction structure (PVBL). The polarized dielectric BaTiO3 greatly promotes the dissociation of Li salt to produce more movable Li+, which locally and spontaneously transfers across the interface to coupled Li0.33La0.56TiO3–x for highly efficient transport. The BaTiO3–Li0.33La0.56TiO3–x effectively restrains the formation of the space charge layer with poly(vinylidene difluoride). These coupling effects contribute to a quite high ionic conductivity (8.2 × 10−4 S cm−1) and lithium transference number (0.57) of the PVBL at 25 °C. The PVBL also homogenizes the interfacial electric field with electrodes. The LiNi0.8Co0.1Mn0.1O2/PVBL/Li solid-state batteries stably cycle 1,500 times at a current density of 180 mA g1, and pouch batteries also exhibit an excellent electrochemical and safety performance.

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Fig. 1: Characterization of the side-by-side coupled BTO–LLTO nanowires and PVBL electrolyte.
Fig. 2: Physical and Li dendrite suppression properties of PVBL electrolyte.
Fig. 3: Characterization of the Li salt dissociation and ion transport in PVBL electrolyte.
Fig. 4: Ion transport mechanism analysis of the PVBL electrolyte.
Fig. 5: Properties of the NCM811/Li solid-state batteries using PVBL electrolyte.
Fig. 6: Characterization and simulation of the interfaces of PVBL electrolyte with cathode and Li metal anode.

Data availability

The data that support the findings of this study are available from the corresponding authors upon reasonable request or at https://zenodo.org/record/7597104.

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Acknowledgements

This work was supported by the National Key Research and Development Program of China (no. 2021YFF0500600, Y.-B.H.), National Natural Science Foundation of China (no. U2001220, Y.-B.H.; 22272175, G.Z.), Local Innovative Research Teams Project of Guangdong Pearl River Talents Program (no. 2017BT01N111, F.K.), Shenzhen All-Solid-State Lithium Battery Electrolyte Engineering Research Center (no. XMHT20200203006, Y.-B.H.) and Shenzhen Technical Plan Project (nos RCJC20200714114436091 and JCYJ20220818101003007, Y.-B.H.; JCYJ20220818101003008, F.K.). We acknowledge J. He at State Key Laboratory of Chemical Engineering at Zhejiang University for the nano-infrared measurement.

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Authors and Affiliations

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Contributions

Y.-B.H. and F.K. conceived the idea. Y.-B.H., G.Z. and F.K. supervised the project. Y.-B.H., P.S., G.Z., F.K., J.M. and M.L. designed the experiments. P.S. performed the experiments with help from S.G., Y.H., S.W., L.Z., L.C., K.Y., X.L., Y.L., X.A., D.Z., X.C. and Q.L. G.Z. performed the NMR experiment. All authors discussed the results in the manuscript. P.S., Y.-B.H., G.Z., M.L., W.L. and F.K. wrote and revised the initial paper, which was approved by all authors.

Corresponding authors

Correspondence to Guiming Zhong, Yan-Bing He or Feiyu Kang.

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Nature Nanotechnology thanks Frederick Nti and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 AFM and corresponding Young’s modulus test of various electrolytes.

a, b PVDF. c, d PVB. e, f, PVL. g, h PVBL.

Extended Data Fig. 2 Raman spectra of PVDF and PVB electrolytes at 25 oC.

a, PVDF. b, PVB.

Extended Data Fig. 3 6Li NMR spectra of pristine and 6Li cycled PVDF and PVB electrolytes.

a, b Pristine PVDF and PVB. c, d 6Li cycled PVDF and PVB.

Extended Data Fig. 4 Atomic model of BTO-LLTO heterogeneous structures and four possible Li diffusion paths.

a–d, Top view (a, b) and left view (c, d) of two possible BTO (1 1 0)-LLTO (1 1 0) structures. e-h, Top view (e, f) and left view (g, h) of corresponding optimized BTO (1 1 0)-LLTO (1 1 0) structures and four possible Li diffusion paths (path1-1, path2-1, path1-2 and path 2-2).

Extended Data Fig. 5 Ion transport mechanism of the BTO-LLTO heterogeneous structures.

a, b Left view of two possible BTO (1 1 0)-LLTO (1 1 0) structures. c-f, Top view of two Li diffusion paths (path 2-1 and path 2-2) (c, e) at the interface of BTO (1 1 0)-LLTO (1 1 0) heterogeneous structures and corresponding energy change (d, f). g, h, Top view of the Li diffusion path from the interface to the bulk phase of the LLTO lattice (g) and corresponding energy change (h).

Extended Data Fig. 6 Electrochemical performance of NCM811/Li solid-state batteries using BTO-LLTO coupled structure and BTO/LLTO nanowire mixture.

a, Rate performance of NCM811/Li batteries. b, c, Cycling stability of NCM811/Li batteries at 0.5 C (b) and 1 C (c) at 25 oC.

Supplementary information

Supplementary Information

Supplementary Notes 1–4, Figs. 1–35, Tables 1–4 and refs. 1–13.

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Shi, P., Ma, J., Liu, M. et al. A dielectric electrolyte composite with high lithium-ion conductivity for high-voltage solid-state lithium metal batteries. Nat. Nanotechnol. (2023). https://doi.org/10.1038/s41565-023-01341-2

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