Plasma enhanced atomic layer deposition of a (nitrogen doped) Ti phosphate coating for improved energy storage in Li-ion batteries

Abstract

The use of Ti phosphate as a functional coating for Li ion battery electrodes has been investigated, as well as the effect of nitrogen doping on its electrochemical properties. First, previous knowledge on PE-ALD of Ti phosphate (using an exposure sequence of trimethylphosphate plasma-oxygen plasma-titaniumisopropoxide) was used to study an altered process using a nitrogen plasma, i.e. TMP* - N-2* - TTIP. This enabled the deposition of a nitrogen doped (6 at.%) Ti phosphate with a growth per cycle of 0.4 nm/cycle. Next, a dual-source precursor (diethylphosphoramidate plasma, or DEPA*) was introduced instead of TMP*, allowing for a higher growth rate (0.6 nm/cycle) and a higher nitrogen level (8.6 at.%). The ionic transparency of the phosphate slightly decreased due to nitrogen incorporation, but the effective transversal electronic conductivity showed to be three times higher after nitrogen doping. A 2 nm coating of (un)doped Ti phosphate significantly improved the rate capability of a lithium nickel manganese cobalt oxide (NMC) electrode, increasing the amount of energy that can be stored at high (dis)charging speeds with a factor 10 (at 5C). In addition, the undoped titanium phosphate coating offered increased stability, retaining 84% of the capacity after 100 cycles at 1C with respect to 79% for the uncoated electrode.