  We report the synthesis and superconducting properties of a metastable form
of the known superconductor NaxCoO2*yH2O (x ~ 1/3, y ~ 4x). Instead of using
the conventional bromine-acetonitrile mixture for sodium deintercalation, we
use an aqueous bromine solution. Using this method, we oxidize the sample to a
point that the sodium cobaltate becomes unstable, leading to formation of other
products if not controlled. This compound has the same structure as the
reported superconductor, yet it exhibits a systematic variation of the
superconducting transition temperature (Tc) as a function of time. Immediately
after synthesis, this compound is not a superconductor, even though it contains
appropriate amounts of sodium and water. The samples become superconducting
with low Tc values after ~ 90 h. Tc continually increases until it reaches a
maximum value (4.5 K) after about 260 h. Then Tc drops drastically, becoming
non-superconducting approximately 100 h later. Corresponding time-dependent
neutron powder diffraction data shows that the changes in superconductivity
exhibited by the metastable cobaltate correspond to slow formation of oxygen
vacancies in the CoO2 layers. In effect, the formation of these defects
continually reduces the cobalt oxidation state causing the sample to evolve
through its superconducting life cycle. Thus, the dome-shaped superconducting
phase diagram is mapped as a function of cobalt oxidation state using a single
sample. The width of this dome based on the formal oxidation state of cobalt is
very narrow - approximately 0.1 valence units wide. Interestingly, the maximum
Tc in NaxCoO2*yH2O occurs when the cobalt oxidation state is near 3.5. Thus, we
speculate that the maximum Tc occurs near the charge ordered insulating state
that correlates with the average cobalt oxidation state of 3.5.
