Synthesis and characterization of radical-bearing polyethers as an electrode-active material for organic secondary batteries

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Abstract

In search of polymer backbones to bind organic radical pendant groups as redox centers for high-density charge storage application, polyether was employed as a flexible chain with a low glass transition temperature and affinity to electrolyte solutions. Cyclic ethers bearing nitroxide radicals were synthesized and polymerized via ring-opening polymerization utilizing various initiators. Polyethers bearing robust radical substituents such as 2,2,6,6-tetramethylpiperidin-l-oxyl-4-yl and 2,2,5,5-tetramethyl-z2,5-dihydro- 1H-pyrrol-1-oxyl-3-yl groups with high density, i.e., per repeating unit with small equivalent weights, were prepared by the anionic polymerization of the corresponding epoxides. Cyclic voltammetry of the radical polyethers, obtained for polymer/carbon composites confined at an aluminum current collector, revealed large redox capacities comparable to the formula weight-based theoretical values, which was ascribed to the efficient swelling and yet insoluble properties of the polyethers in electrolyte solutions by virtue of their high molecular weights and adhesive properties to be held on electrode surfaces. The redox capacity also indicated that the ionophoric polyether matrix accommodated electrolyte anions to compensate positive charges produced by the oxidation of the neutral radicals at the polymer/electrode interface, allowing charge propagation deep into the polymer layer by a site-hopping mechanism. Test cells fabricated with the polymer/carbon composite as the cathode and a Li anode, sandwiching an electrolyte layer, performed as a secondary battery at output voltages near 3.6 V without substantial degradation even after 100 charging-discharging cycles.

Original languageEnglish
Pages (from-to)6646-6652
Number of pages7
JournalMacromolecules
Volume41
Issue number18
DOIs
Publication statusPublished - 2008 Sep 23

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Bearings (structural)
Secondary batteries
Polyethers
Polymers
Electrolytes
Electrodes
Carbon
Cyclic Ethers
Anionic polymerization
Epoxy Compounds
Ring opening polymerization
Composite materials
Charge density
Aluminum
Cyclic voltammetry
Anions
Swelling
Ethers
Adhesives
Anodes

ASJC Scopus subject areas

  • Organic Chemistry
  • Materials Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry

Cite this

Synthesis and characterization of radical-bearing polyethers as an electrode-active material for organic secondary batteries. / Oyaizu, Kenichi; Suga, Takeo; Yoshimura, Kentaro; Nishide, Hiroyuki.

In: Macromolecules, Vol. 41, No. 18, 23.09.2008, p. 6646-6652.

Research output: Contribution to journalArticle

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