Doping is a well-known method to enhance the electronic conductivity of semiconductors, even if the dopant activity is lower in amorphous semiconductors than in crystalline ones. 2% boron doping increases the conductivity of 10% methylated amorphous silicon by five orders of magnitude compared to the undoped material.
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 exhibits a capacity retention of 70% after 500 cycles of full lithiation/delithiation, an improved performance as compared to the undoped material (see Figure 1a). Interestingly, boron doping allows for using higher methyl content without demanding pre-conditioning procedures for the electrochemical cycling of the material. The stability upon cycling is found to be further increased for 15% and 20% methylated electrodes, with a capacity retention exceeding 80% over 1000 cycles of full lithiation/delithiation (Figure 1b). This figure comes at the expense of a decreased total capacity (which remains 3 to 4 times larger than that of the current carbon electrodes). The SEI evolution and structural changes are currently investigated using operando ATR FTIR and ex-situ Raman spectroscopies, in order to rationalize the factors limiting the Coulombic efficiency to 99.7%.
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