Composition-gradient Design of Silicon Electrodes to Mitigate Mechanochemical Coupling Degradation

doi:10.15541/jim20240472

Abstract

Abstract:

As an anode for lithium-ion batteries, silicon material has the advantage of high energy density. However, the volume effect during charge-discharge cycles causes instability in the active coating's surfaces and diffusion stress induced by internal polarization, leading to inevitable structural degradation and capacity fading. Inspired by functionally gradient materials, this study proposed a five-layer composite gradient silicon electrode. Experiments and multi-scale electro-chemo-mechanical coupled model demonstrate that the designed symmetric and linear gradient silicon electrodes effectively mitigate mechanochemical coupled degradation, showing superior cycling and rate performance compared to traditional uniform electrode. Specifically, the symmetric gradient electrode retains a specific capacity of 2065 mAh·g^-1 after 100 cycles at 0.2C (1C=2.65 mA·cm^-2) rate, with a capacity retention rate of 81%, while that of uniform electrode is 51%. The linear gradient electrode exhibits an average discharge capacity 1.5 times that of the uniform electrode at 1C rate. Moreover, both types of gradient electrodes demonstrate smaller impedance variations before and after cycling compared to the uniform electrode. These composite gradient electrodes are implemented through an innovative multi-layer coating process, and improved structural stability and electrochemical performance without material modifications, providing a reference for designing and fabricating high-performance silicon electrodes.

Key words: lithium-ion battery, silicon electrode, functionally gradient material, multi-physics field coupling

CLC Number:

TM912

TAN Bowen, GENG Shuanglong, ZHANG Kai, ZHENG Bailin. Composition-gradient Design of Silicon Electrodes to Mitigate Mechanochemical Coupling Degradation[J]. Journal of Inorganic Materials, 2025, 40(7): 772-780.

Figures/Tables 12

Fig. 1 Mass fraction distributions of Si in 3 types of electrodes

Table 1 Composition ratios of different Si mass fractions (%, in mass)

Si/%	SP/%	SA/%
10	70	20
20	60	20
30	50	20
40	40	20
50	30	20

Fig. 2 Schematic of electrode preparation and battery assembly

Fig. 3 Schematic of PPM of Si electrode half-cell

Fig. 4 Electrochemical performance of different lithium-ion batteries (a) Cycling performance at 0.2C; (b) Capacity retentions after 100 cycles; (c-e) Charging-discharging curves of (c) UD-Si, (d) LG-Si and (e) SG-Si. Colorful figures are available on website

Fig. 5 Characterization of Si nanoparticles (a) SEM image; (b) XRD pattern

Fig. 6 SEM images of the electrode surfaces and cross-sections after cycling (a-c) Surface: (a) SG-Si, (b) UD-Si, and (c) LG-Si; (d-f) Cross-section: (d) SG-Si, (e) UD-Si, and (f) LG-Si

Fig. 7 Rate performance of lithium-ion batteries and resistances of electrodes (a, b) Nyquist plots of the electrode after (a) formation and (b) cycling; (c) Rate performance of the electrode

Fig. 8 Results of multi-scale electro-chemo-mechanical coupled model (a) Stress distribution of CBD in the surface layer of LG-Si; (b) Stress-strain plots of Si electrodes; (c) Comparison of tangential stresses at the active layer & current collector interfaces; (d) Electrolyte concentration distributions of Si electrodes; (e) Comparison of electrolyte concentration gradients in the thickness direction. Colorful figures are available on website

Table S1 Parameters of lithium-ion battery

Fig. S1 Schematic of PPM of Si electrode half-cell

Fig. S2 Schematic diagram of the electrode scale model

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