The tungsten oxides and bronzes have been extensively studied since their discovery in the last century, because of their brilliant colors and high electrical conductivity. More recently the driving interest resulted from their potential use in electrochromic displays and other electrochemical systems. Their crystalline structures are generally based on the corner sharing of WO 6 octahedra giving tunnels of variable size and shape leading to exciting intercalation chemistry. These structures readily undergo redox reactions, and in the last quarter century these reactions have often involved soft chemistry. Most recently hydrothermal techniques have been used to prepare new sodium tungstates with the hexagonal tungsten bronze and the pyrochlore structures. The phase formed is a function of the pH of the reaction medium. The pyrochlore phase readily undergoes ion-exchange with a wide range of monovalent cations giving the compounds, M x W 2 O 6+x/2 · y H 2 O ; the value of y is strongly dependent on the identity of the cation, M. WO 3 with the pyrochlore structure could be formed from the hydronium and ammonium complexes. Lithium can be readily intercalated either chemically and electrochemically into both these phases, just as in the previously-known bronze phases. Surprisingly more lithium is incorporated in most cases in the hexagonal than in the pyrochlore phase. The ions in the pyrochlore structure show rapid ionic mobility, with the hydronium ion showing the greatest mobility.
