Synthesis and Charge/Discharge Properties of Polyacetylenes Carrying 2,2,6,6‐Tetramethyl‐1‐piperidinoxy Radicals

Abstract

The 2,2,6,6-tetramethyl-1-piperidinoxy (TEMPO)-containing acetylenic monomers HC[triple bond]CC(6)H(3)-p,m-(CONH-4-TEMPO)(2) (1), HC[triple bond]CC(6)H(3)-p,m-(COO-4-TEMPO)(2) (2), (S,S,S,S)-HC[triple bond]CC(6)H(3)-p,m-[CO-NHCH{COO-(4-TEMPO)}CH(2)COO-(4-TEMPO)](2) (3), (S,S)-HC[triple bond]CC(6)H(4)CO-NHCH{COO-(4-TEMPO)}CH(2)COO-(4-TEMPO) (4), HC[triple bond]CC(6)H(4)-p-OCO-4-TEMPO (5), HC[triple bond]CCH(2)C(CH(3))(CH(2)OCO-4-TEMPO)(2) (6), HC[triple bond]CCH(2)NHCO-4-TEMPO (7), and HC[triple bond]CCH(2)OCO-4-TEMPO (8) were polymerized to afford novel polymers containing the TEMPO radical at high densities. Monomers 1, 3-6, and 8 provided polymers with average molecular weights of 10 000-136 500 in 62-99 % yield in the presence of a rhodium catalyst, whereas monomers 2 and 7 gave insoluble polymers in 100 % yield. The formed polymers were thermally stable up to approximately 274 degrees C according to thermogravimetric analysis (TGA). All the TEMPO-containing polymers demonstrated reversible charge/discharge processes, whose discharge capacities were 21.3-108 A h kg(-1). In particular, the capacity of poly(1)-, poly(4)-, and poly(5)-based cells reached 108, 96.3, and 89.3 A h kg(-1), respectively, which practically coincided with their theoretical values.

From Biomass to a Renewable LiXC6O6 Organic Electrode for Sustainable Li‐Ion Batteries

“…Thus, our motivation is to develop new Li-ion batteries only based on the use of organic electrodes by searching for electrochemically active organic monomers/polymers that Li-ion batteries presently operate on inorganic insertion compounds. The newly described polyA C H T U N G T R E N N U N G (radical) [14][15][16] IV also uses anion "insertion" as it contains discrete nitroxide redox centres that show high reversibility. To address the issue of sustainability of electrode materials, a radically different approach from the conventional route has been adopted to develop new organic electrode materials.…”

Organic Radical Battery Approaching Practical Use

“…The polymer should also have affinity for the electrolyte to support the ionic conductivity. To date, various backbone polymers, such as polymethacrylate, 8,9 poly(vinyl ether), 12 polystyrene, 16,17 polyether, 13 polynorbornene, 1820 polysiloxane, 21 polyacetylene, 22,23 cellulose, 24 and DNA complexes 25 have been reported. The polymer used must be dense in a thick electrode to obtain sufficient capacity.…”

Substituted Polyacetylenes: Synthesis, Properties, and Functions

“…76 Poly(PA) containing many TEMPO radicals 14 has been prepared, which is useful as a positive electrode material for organic radical batteries. 77 Lee et al found that the film of poly[1-phenyl-2-(p-trimethylsilyl)phenylacetylene] (15) exhibits emission enhancement due to swelling in solvents, which might be applied to viscosity sensor. 78 They studied also the effect of alkyl chain length of poly(diphenylacetylene) derivative 15 to find that 16 displays strong blue-green emission being promising as a PL material.…”