Mechanism Study on Garnet-type Li6.4La3Zr1.4Ta0.6O12 Regulating the Solid Electrolyte Interphases of Si/C Anodes

doi:10.15541/jim20220196

Abstract

Abstract:

The large volume change of silicon anode leads to rupture of the solid electrolyte interface (SEI) and the pulverization of Si electrode during charge-discharge process, which results in uncontrolled capacity loss. In this work, a strategy to regulate the SEI composition of Si/C anodes utilizing Li_6.4La₃Zr_1.4Ta_0.6O₁₂ (LLZTO) solid electrolyte was proposed. LLZTO layer is uniformly coated on the surface of polypropylene (PP) separator, which not only improves wettability of the electrolyte to the separator, thereby homogenizing the lithium-ion flux, but also increases the proportion of inorganic components in SEI and enhances the interfacial stability of Si/C anodes. As a result, Li batteries using the LLZTO coated PP separator exhibit better cycling stability and rate capability. Li-Si/C half cell exhibits a reversible capacity of 876 mAh·g^-1 with 81% capacity retention for more than 200 cycles at 0.3C (1C= 1.5 A·g^-1), and Si/C-LiFePO₄ (LFP) full cell delivers a capacity of 125 mAh·g^-1 with 91.8% capacity retention after 100 cycles at 0.3C (1C=170 mA·g^-1). This work reveals the mechanism of LLZTO solid electrolytes in regulating the SEI of Si/C anodes and sparks new ideas for developing high-performance silicon-based lithium batteries.

Key words: solid electrolyte interphase, composition regulation, garnet-type solid electrolyte, Si/C anode, lithium- ion battery

CLC Number:

TM912

SU Dongliang, CUI Jin, ZHAI Pengbo, GUO Xiangxin. Mechanism Study on Garnet-type Li_6.4La₃Zr_1.4Ta_0.6O₁₂ Regulating the Solid Electrolyte Interphases of Si/C Anodes[J]. Journal of Inorganic Materials, 2022, 37(7): 802-808.

Figures/Tables 16

Fig. 1 Schematic diagram of PP separator coated by LLZTO

Fig. 2 Structural characterization of PP-10 μm-LLZTO separator (a) XRD patterns of LLZTO powder, bare PP separator, PVDF and PP-10 μm-LLZTO separator; (b) Optical photos of PP-10 μm-LLZTO separator; (c) Photograph of LLZTO-PVDF slurry after stirring; (d) SEM image of LLZTO powder; (e) Cross-sectional SEM image of PP separator; (f) Top-view and (g) cross-sectional SEM images of PP-10 μm-LLZTO separator; Electrolyte contact angles of (h) PP and (i) PP-10 μm-LLZTO separators

Fig. S1 (a) SEM image and corresponding EDS elemental mapping of Si/C particles, (b) EDS spectrum of Si/C particles

Fig. 3 Electrochemical performance of Li-Si/C half cells (a) CV curves of the initial 5 cycles of half-cell using PP-10 μm-LLZTO separator; (b) Rate tests of half-cells using PP and PP-10 μm-LLZTO separators; (c) Charge-discharge curves of Li/Si half-cell using PP-10 μm-LLZTO separator; (d) Stability tests of Li/Si half-cells using PP and PP-10 μm-LLZTO separators with different thicknesses; (e) EIS spectra of half-cells with PP and PP-10 μm-LLZTO separators before cycling. Colorful figures are available on website

Fig. S2 Charge-discharge curves of Li-Si/C half-cell using PP separator

Fig. S3 Cross-sectional SEM images of PP-6 μm-LLZTO separator

Fig. S4 Cross-sectional SEM images of PP-12 μm-LLZTO separator

Fig. S5 Stability test of Li-Si/C half-cell using PP-PVDF separator

Fig. S6 (a) Top-view and (b) cross-sectional SEM images of the Si/C anode of the Li|PP-10 μm-LLZTO|Si/C half-cell after 10 cycles

Fig. S7 Cross-sectional SEM images of (a) Si/C anode, (b) PP-10 μm-LLZTO separator, (c) Si/C anode, (d) PP-10 μm-LLZTO separator after charge

Fig. S8 Equivalent circuit model of bare PP half-cell and PP-10 μm-LLZTO half-cell

Table S1 Bulk resistance and ionic conductivity of PP and PP-10 μm-LLZTO separators

Separator	Bulk resistance/Ω	Interfacial resistance/Ω
Bare PP	3.3	525.5
PP-10 μm-LLZTO	7.0	149.1

Fig. S9 (a, c) C1s and (b, d) F1s for SEI of the half-cells with (a, b) PP and (c, d) PP-10 μm-LLZTO separators after 100 cycles

Fig. S10 CV curves of initial 3 cycles of the LFP|PP-10 μm-LLZTO|Si/C full cell

Fig. S12 Charge-discharge curves of LFP|PP|Si/C full cell

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Mechanism Study on Garnet-type Li_6.4La₃Zr_1.4Ta_0.6O₁₂ Regulating the Solid Electrolyte Interphases of Si/C Anodes

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