Polyacetylene and Polynorbornene Derivatives Carrying TEMPO. Synthesis and Properties as Organic Radical Battery Materials

✍ Scribed by Toru Katsumata; Masaharu Satoh; Jun Wada; Masashi Shiotsuki; Fumio Sanda; Toshio Masuda

• Publisher: John Wiley and Sons
• Year: 2006
• Tongue: English
• Weight: 177 KB
• Volume: 27
• Category: Article
• ISSN: 1022-1336
• DOI: 10.1002/marc.200600286

✦ Synopsis

Abstract

Summary: 2,2,6,6‐Tetramethylpiperidine 1‐oxyl (TEMPO)‐containing N‐propargylamide HCCCH~2~NHCO‐4‐TEMPO (1), propargyl ester HCCCH~2~OCO‐4‐TEMPO (2), phenylacetylene derivative HCCC~6~H~3~‐3,4‐(CO~2~‐4‐TEMPO)~2~ (3), and norbornene diester monomers, NB‐2,3‐exo,exo‐(CH~2~OCO‐4‐TEMPO)~2~ (4), NB‐2,3‐endo,exo‐(COO‐4‐TEMPO)~2~ (5a), NB‐2,3‐endo,endo‐(COO‐4‐TEMPO)~2~ (5b) (NB = norbornene, TEMPO = 2,2,6,6‐tetramethyl‐1‐piperidinyloxyl) were synthesized and polymerized with rhodium and ruthenium catalysts. Monomers 2, 5a, and 5b gave polymers with number‐average molecular weights of 47 000–185 000 in 59–100% yields, while 1, 3, and 4 gave polymers insoluble in common organic solvents in 88–100% yields. The capacities of cells fabricated with poly(1), poly(2), and poly(3) were 67, 82, and 23 Ah · kg^−1^ based on the weight, respectively. The capacity of poly(5a)‐based cell reached the theoretical value (109 Ah · kg^−1^) of the polymer.

Charge–discharge curves of poly(5a) at a current density of 0.13 mA · cm^−2^ (100 mA · g^−1^~‐cathode active material~) in the voltage range of 2.5–4.2 V.

magnified imageCharge–discharge curves of poly(5a) at a current density of 0.13 mA · cm^−2^ (100 mA · g^−1^~‐cathode active material~) in the voltage range of 2.5–4.2 V.