Studies of the Hydration of Transition Metal Cations Dissolved in Poly(ethylene oxide) by UV/Visible Spectroscopy

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Abstract
Solid polymeric electrolytes formed by dissolving salts of Ni2+ and Co2+ in poly(ethylene oxide) (PEO) are strikingly different in their response to deliberate hydration/dehydration. Both and readily absorb about 28–30 molecules of water per cation from humid nitrogen at room temperature. Surprisingly, an anhydrous sample of after having been hydrated and dehydrated has a much higher conductivity [10−3 (Ω−1cm−1) at 150°C] than in the initial as‐cast anhydrous state [10−6 (Ω−1cm−1) at 150°C]. This unexpected effect of hydration/dehydration is not observed with samples of . UV‐visible absorption spectroscopy shows that Ni2+ in dry exists in a variety of square planar and tetrahedral complexes with PEO. The hydration of completely frees Ni2+ ions from association with the PEO chains and results in the formation of species. In contrast, absorption of water does not appear to liberate Co2+ ions from association with PEO and has no persistent effect on the properties of the electrolyte.

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