Atomic layer deposition (ALD) provides a promising route for depositing uniform thin-film electrodes for Li-ion batteries. In this work, bis(methylcyclopentadienyl) nickel(II) (Ni(MeCp)2) and bis(cyclopentadienyl) nickel(II) (NiCp2) were used as precursors for NiO ALD. Oxygen plasma was used as a counter-reactant. The films were studied by spectroscopic ellipsometry, scanning electron microscopy, atomic force microscopy, X-ray diffraction, X-ray reflectometry, and X-ray photoelectron spectroscopy. The results show that the optimal temperature for the deposition for NiCp2 was 200–300 °C, but the optimal Ni(MeCp)2 growth per ALD cycle was 0.011–0.012 nm for both precursors at 250–300 °C. The films deposited using NiCp2 and oxygen plasma at 300 °C using optimal ALD condition consisted mainly of stoichiometric polycrystalline NiO with high density (6.6 g/cm3) and low roughness (0.34 nm). However, the films contain carbon impurities. The NiO films (thickness 28–30 nm) deposited on stainless steel showed a specific capacity above 1300 mAh/g, which is significantly more than the theoretical capacity of bulk NiO (718 mAh/g) because it includes the capacity of the NiO film and the pseudo-capacity of the gel-like solid electrolyte interface film. The presence of pseudo-capacity and its increase during cycling is discussed based on a detailed analysis of cyclic voltammograms and charge–discharge curves (U(C)).
Lithium nickelate (LiNiO2) and materials based on it are attractive positive electrode materials for lithium-ion batteries, owing to their large capacity. In this paper, the results of atomic layer deposition (ALD) of lithium–nickel–silicon oxide thin films using lithium hexamethyldisilazide (LiHMDS) and bis(cyclopentadienyl) nickel (II) (NiCp2) as precursors and remote oxygen plasma as a counter-reagent are reported. Two approaches were studied: ALD using supercycles and ALD of the multilayered structure of lithium oxide, lithium nickel oxide, and nickel oxides followed by annealing. The prepared films were studied by scanning electron microscopy, spectral ellipsometry, X-ray diffraction, X-ray reflectivity, X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, energy-dispersive X-ray spectroscopy, transmission electron microscopy, and selected-area electron diffraction. The pulse ratio of LiHMDS/Ni(Cp)2 precursors in one supercycle ranged from 1/1 to 1/10. Silicon was observed in the deposited films, and after annealing, crystalline Li2SiO3 and Li2Si2O5 were formed at 800 °C. Annealing of the multilayered sample caused the partial formation of LiNiO2. The obtained cathode materials possessed electrochemical activity comparable with the results for other thin-film cathodes.
In this study, bulk samples of a CrMoNbWV high-entropy alloy (HEA) were obtained for the first time by spark plasma sintering (SPS) of mechanically alloyed (MA) powders at 1200 °C, 1300 °C, and 1400 °C. Microstructure evolution, phase formation as well as wear and corrosion behavior were investigated. The MA powders’ phase composition was found to be represented by body-centered-cubic (BCC) solid solution. The solid solution partially decomposed to Laves phases under the sintering, such as Cr2Nb and (Fe, Cr)Nb, and NbVO4-VO oxides mixture. The temperature increase to 1400 °C led to a grain coarsening of the BCC phase and decreased the Laves phase content accompanied by precipitation at the grain boundaries. The sintered samples showed high hardness and compressive strength (2700–2800 MPa) at room temperature. The wear tests demonstrated excellent results in comparison to conventional wear-resistant composites. The obtained samples also exhibited high corrosion resistance under electrochemical tests in H2SO4 solution. The CrMoNbWV HEA has comparable mechanical and corrosive properties with the WNbMoTaV type HEA, but at the same time has a reduced density: CrMoNbWV—10.55 g/cm3, WNbMoTaV—12.42 g/cm3.