Laser-assisted structuring and modification of LiCoO2 thin films

The material development of improved lithium ion batteries will play an important role in future mobile applications and energy storage systems. Electrode materials made of nano-composited materials are expected to improve battery lifetime and will lead to an enhancement of lithium diffusion and thus improve battery capacity and cyclability. In this study, research was conducted to further improve the electrochemical properties of thin film cathodes by increasing the surface to volume ratio and thereby the lithium intercalation rate. Cathode materials were synthesised by r.f. magnetron sputtering of LiCoO2 targets in a pure argon plasma. LiCoO2 films 3 μm thick and with a grain size of 10 to 500 nm were deposited on silicon and stainless steel substrates. The deposition parameters (argon pressure, substrate bias) were varied to create stoichiometric films with controlled nano-crystalline texture and morphology. During laser-assisted surface treatment, cone-shaped periodic surface structures were produced. For this purpose high repetition excimer laser radiation at wavelengths of 193 nm and 248 nm and with short laser pulse widths (4-6 ns) were used. Structure sizes varied with laser and processing parameters, e.g. laser fluences, pulse number, wavelength and processing gas. Laser annealing in air or furnace annealing in a controlled argon/oxygen environment were then used to create the high temperature phase of LiCoO2 (HT-LiCoO2). The sputtered films were studied with Raman spectroscopy, x-ray photoelectron spectroscopy and x-ray diffraction to determine their stoichiometry and crystallinity before and after laser treatment. The development of HT-LiCoO2 and also the formation of a Co3O4 phase were discussed. By means of electrochemical cycling, the performance of the manufactured films was investigated.

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