Enhancing Methylated Amorphous Silicon Anode Performances in Li-Ion Batteries By Boron Doping

Abstract

Methylated amorphous silicon has already demonstrated some advantages as compared to silicon in terms of mechanical properties and cyclability for Li-ion batteries (LIB) [1]. However, the conductivity of methylated amorphous silicon drops by several orders of magnitude when increasing the methyl content in the material, which prevents investigating methyl contents higher than 10%. It is well known that doping significantly improves the conductivity of crystalline or amorphous silicon, and has sometimes been reported to improve the material cyclability when used as a LiB anode [2].Here, boron-doped methylated amorphous silicon electrodes with different methyl contents were investigated as anodes for LiB in half-cell configuration. Boron doped methylated silicon thin films (100nm thick) with various methyl content were cycled in the range 0.025V – 1V at C/2 rate (electrolyte: LP30 with 5%FEC). 10% methylated amorphous silicon with 2% boron doping performs a capacity retention of 77% after 1000 cycles (exhibiting a capacity around 1800 mAh.g-1) of full lithiation/delithiation. Figure 1a shows a clearly improved performance as compared to the undoped material. The stability upon cycling of higher methyl contents (15% and 20%) electrodes is further increased, with a capacity retention exceeding 80% over 1000 cycles of full lithiation/delithiation.The evolution of the SEI thickness can be quantitatively determined from IR spectra during cycling. The thickness in the delithiated state is found to increase from cycle to cycle, but with a lower rate for the doped 10% methylated electrodes (thickness lower than 25 nm after 40 cycles and 30 nm after 80 cycles) than for the undoped ones (thickness larger than 35 nm after 40 cycles), see Figure 1b. The SEI evolution upon cycling for higher methyl content is currently under investigation. Reference [1] L. Touahir, A. Cheriet, D. A. D. Corte, J.-N. Chazalviel, C. H. Villeneuve, F. Ozanam, I. Solomon, A. Keffous, N. Gabouze et M. Rosso, «Methylated silicon: A longer cycle-life material for Li-ion batteries,» Journal of Power Sources, vol. 240, pp. 551-557, 10 2013. [2] M. Salah, C. Hall, P. Murphy, C. Francis, R. Kerr, B. Stoehr, S. Rudd et M. Fabretto, «Doped and reactive silicon thin film anodes for lithium ion batteries: A review,» Journal of Power Sources, vol. 506, p. 230194, 9 2021. Figure 1