Silicon-based electrodes are promising candidates for the next generation of Lithium-ion batteries with cell-level volumetric energy densities above 700 Wh L^-1_cell.^1,2 However, the practical energy density of these electrodes is strongly influenced by the electrode porosity and the volume expansion during repeated charge-discharge.³ In addition, the electrode’s rate capability is largely determined by its tortuosity, which continuously increases upon cycling as a consequence of ongoing electrolyte decomposition at the silicon-electrolyte interface.⁴

In the present study, we investigate the influence of the porosity and tortuosity on the cycling performance of silicon-graphite electrodes. Hence, we prepared electrodes with a practical areal capacity of 4.0 mAh cm^‑2, comprising 35 wt% nanometer-sized silicon and 58 wt% micron-sized graphite particles. Lithium poly(acrylic acid) binder and C65 conductive carbon accounted for the remaining 7 wt%. By use of a hydraulic press, the electrode porosity was adjusted to values ranging from 30% to 50%. As electrolyte solution, 1 M LiPF₆ dissolved in a 3:7 (w:w) mixture of ethylene carbonate:ethyl methyl carbonate (LP57) with 5 wt% fluoroethylene carbonate (FEC) as additive was used.

First, the tortuosity and MacMullin number of the pristine silicon-graphite electrodes were determined by use of impedance spectroscopy on symmetrical cells in blocking conditions.⁵ The electrode polarization and rate capability of these electrodes were then investigated in coin-cells with lithium metal foil as counter electrode. After 50 cycles, the silicon-graphite electrodes were harvested from the cells and examined in terms of their thickness and morphological changes by cross-sectional scanning electron microscopy. Finally, the FEC consumption upon cycling was quantified by post-mortem ¹⁹F-NMR analysis of the residual electrolyte to estimate the pore volume of the electrodes that was occupied by electrolyte decomposition products.⁶

This contribution concludes with a comparison of silicon-graphite electrodes with different porosities and the quantification of the resulting degradation phenomena. Our research helps to better understand the limiting processes in silicon-graphite electrodes upon cycling and provides useful parameters for the modelling and simulation of these electrodes.

References:

(1) Gröger, O.; Gasteiger, H. A.; Suchsland, J.-P. J. Electrochem. Soc. 2015, 162 (14), A2605–A2622.

(2) Andre, D.; Kim, S.-J.; Lamp, P.; Lux, S. F.; Maglia, F.; Paschos, O.; Stiaszny, B. J. Mater. Chem. A 2015, 3 (13), 6709–6732.

(3) Dash, R.; Pannala, S. Sci. Rep. 2016, 6, 27449.

(4) Radvanyi, E.; Porcher, W.; De Vito, E.; Montani, A.; Franger, S.; Jouanneau Si Larbi, S. Phys. Chem. Chem. Phys. 2014, 16 (32), 17142–17153.

(5) Landesfeind, J.; Hattendorff, J.; Ehrl, A.; Wall, W. A.; Gasteiger, H. A. J. Electrochem. Soc. 2016, 163 (7), A1373–A1387.

(6) Wetjen, M.; Jung, R.; Pritzl, D.; Gasteiger, H. A. ECS Meet. 230 2016, Abstr. #280.

Acknowledgements:

The German Federal Ministry for Economic Affairs and Energy is acknowledged for funding (“LiMo” project with funding number 03ET6045D).