The incorporation of foreign atoms in trace amounts modifies electronic properties and spectral response by the so-called band gap engineering 1. Among different dopants, the incorporation of Li+ cations into TiO2 is important for expanding the oxide’s technological applications. Li+ and H+ doping of TiO2 was carried out using electrochemical processes or salt impregnation, which improved solar to electricity efficiency of Dye Sensitized Solar cells and Perovskite solar cells (where a TiO2 layer is used as electronic transporting layer), as well as photocatalytic performance 2-3. Thermochemical treatments, N and V doping by standard ion implantation or Ag doping by metal plasma ion implantation was also reported 4-6.
We recently reported 7 that Li+ is incorporated in the bulk of compact TiO2 layers during the anodization of Ti in lithium perchlorate (LiClO4), moving in the opposite direction expected for a cation under the applied electric field. Using Elastic Recoil Detection Analysis (ERDA) we observed that Li+ is accumulated in the form of more or less flat concentration profile along the thickness of compact layer (Fig. 1). Moreover, cell voltage profiles are strongly affected when Li+ is added to the electrolyte independent of anion of the salt. When the Li+ concentration is increased from 0.1 M to 0.5 M by addition of perchlorate or nitrate, the cell voltage transient changes from a curve typical for a compact anodizing with sparking to that of porous anodizing (Fig. 2). This transient change and the fact that the potential plateau during anodizing decreases as [Li+] is increased indicates that Li+ incorporation into the oxide greatly increases ionic conductivity and Ti oxide dissolution. Preliminary results show that a thick irregular tubular oxide structure is formed. The direct incorporation of Li+ into tubular TiO2 during its formation opens new possibilities for techniques of tubular oxide preparation. A mechanism for Li incorporation against the electric field is presented, as well as for the enhanced oxide dissolution.
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