The development of advanced secondary lithium batteries depends on cat
hode structures that can reversibly intercalate lithium ions. The init
ial prototypical system Li/TiS2 showed the feasibility of high energy
density systems with extensive reversibility. However, with the advent
of the safe lithium-carbon anodes by Sony there is a need for higher
voltage cathodes. LiCoO2 presently fulfills this need in small cells.
However, for large systems where cost is an issue new oxides are neede
d. One approach to the formation of such oxide is low temperature hydr
othermal synthesis. Mild hydrothermal reactions lead to the formation
of new metastable transition metal oxide structures, not accessible by
conventional high temperature methods, which have relatively open cry
stal structures. The nature of the cations present in solution (the ''
templating ion'') has a dramatic effect on the crystal structure of th
e phase formed, as also does the pH of the reaction medium and the par
ticular transition metal. Thus, by appropriate choice of reaction medi
um new structures containing large tunnels or channels, similar to tho
se found in alumino-silicate zeolites, can be formed that will offer u
nique properties for the Materials Scientist. In particular, it is exp
ected to be possible to realize enhanced diffusion in such materials.
Here, the hydrothermal synthesis of tungsten, molybdenum and vanadium
oxides is considered. The role of the cation in the synthesis is descr
ibed, as well as the key interfacial reactions that are taking place.
Cases are described where the cation controls the structure formed and
is retained in the structure, to instances where the cation criticall
y controls the reactions occurring but is not retained in the lattice.