Nick Peys

From liquid to thin film: colloidal suspensions for tungsten oxide as an electrode material for Li-ion batteries

Using a colloidal suspension, tungsten oxide thin films (150 nm) have been prepared via ultrasonic spray deposition using two different current collectors, namely TiN and Pt. First, the precursor chemistry was studied, revealing that the tungsten present is reduced due to the formation of chlorine gas. Due to a dehydrogenation 1,1-diethoxyethane (DEE) and hydrogen chloride (HCl) evolve from the precursor, reducing the chloride content of the precursor. The thin films were annealed at 400 and 500 °C, yielding tetragonal tungsten oxide without the presence of chlorides. Electrochemical analysis indicated that the TiN current collector has a pronounced positive effect on cycling behavior of the WO3 thin film. A higher annealing temperature yields an improved performance, but annealing at temperatures as low as 400 °C also yielded electrochemically active WO3. The current study presents a versatile method to produce electrochemically active tungsten oxide thin films with a high volumetric capacity (640 mA h cm−3) at relatively low temperature to be applied in all-solid-state Li-ion batteries.

Chemical Composition of an Aqueous Oxalato-/Citrato-VO2+ Solution as Determinant for Vanadium Oxide Phase Formation

Aqueous solutions of oxalato- and citrato-VO(2+) complexes are prepared, and their ligand exchange reaction is investigated as a function of the amount of citrate present in the aqueous solution via continuous-wave electron paramagnetic resonance (CW EPR) and hyperfine sublevel correlation (HYSCORE) spectroscopy. With a low amount of citrate, monomeric cis-oxalato-VO(2+) complexes occur with a distorted square-pyramidal geometry. As the amount of citrate increases, oxalate is gradually exchanged for citrate. This leads to (i) an intermediate situation of monomeric VO(2+) complexes with a mix of oxalate/citrate ligands and (ii) a final situation of both monomeric and dimeric complexes with exclusively citrato ligands. The monomeric citrato-VO(2+) complexes dominate (abundance > 80%) and are characterized by a 6-fold chelation of the vanadium(IV) ion by 4 RCO2(-) ligands at the equatorial positions and a H2O/R-OH ligand at the axial position. The different redox stabilities of these complexes, relative to that of dissolved O2 in the aqueous solution, is analyzed via (51)V NMR. It is shown that the oxidation rate is the highest for the oxalato-VO(2+) complexes. In addition, the stability of the VO(2+) complexes can be drastically improved by evacuation of the dissolved O2 from the solution and subsequent storage in a N2 ambient atmosphere. The vanadium oxide phase formation process, starting with the chemical solution deposition of the aqueous solutions and continuing with subsequent processing in an ambient 0.1% O2 atmosphere, differs for the two complexes. The oxalato-VO(2+) complexes turn into the oxygen-deficient crystalline VO2 B at 400 °C, which then turns into crystalline V6O13 at 500 °C. In contrast, the citrato-VO(2+) complexes form an amorphous film at 400 °C that crystallizes into VO2 M1 and V6O13 at 500 °C.