Charge-Discharge with Rocking-Chair-Type Li+ Migration Characteristics in a Zwitterionic Radical Copolymer Composed of TEMPO and Trifluoromethanesulfonylimide with Carbonate Electrolytes for a High-Rate Li-Ion Battery

Hiroshi Tokue, Tomoaki Murata, Haruka Agatsuma, Hiroyuki Nishide, Kenichi Oyaizu

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

Redox-active copolymer containing organic robust radical, 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO), and charge neutralizing anion, trifluoromethanesulfonylimide (TFSI-) was synthesized as a cathode material of a Li-ion battery. The copolymer, poly(2,2,6,6-tetramethylpiperidin-1-oxy-4-yl methacrylate-co-styrenesulfonyl(trifluoromethanesulfonyl)imide) (P(TMA-co-TFSI)), was designed to give rise to the Li+ migration during its charge-discharge process, based on the self-charge compensation of TEMPO with TFSI- bound to the polymer chain in a widely used electrolyte system for Li-ion battery, organic carbonate mixtures. Copolymerization was performed to achieve efficient self-charge compensation with uniformly distributed TFSI- units. The P(TMA-co-TFSI) layer electrode exhibited reversible redox reaction at 0.73 V vs Ag/AgCl. Electrochemical measurements combined with quartz crystal microbalance analysis evidenced that the redox reaction involved the Li+ migration in binary system of ethylene carbonate and diethyl carbonate. A test cell fabricated with the P(TMA-co-TFSI) cathode exhibited high discharging voltage of 3.7 V and high-rate charge-discharge capability at 30 C (i.e., full charging in 2 min).

Original languageEnglish
Pages (from-to)1950-1958
Number of pages9
JournalMacromolecules
Volume50
Issue number5
DOIs
Publication statusPublished - 2017 Mar 14

Fingerprint

Redox reactions
Carbonates
Electrolytes
Cathodes
Copolymers
Imides
Methacrylates
Quartz crystal microbalances
Copolymerization
Anions
Polymers
Electrodes
Ethylene
Electric potential
Negative ions
Compensation and Redress
Lithium-ion batteries
ethylene carbonate
ethyl carbonate
Oxidation-Reduction

ASJC Scopus subject areas

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

Cite this

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title = "Charge-Discharge with Rocking-Chair-Type Li+ Migration Characteristics in a Zwitterionic Radical Copolymer Composed of TEMPO and Trifluoromethanesulfonylimide with Carbonate Electrolytes for a High-Rate Li-Ion Battery",
abstract = "Redox-active copolymer containing organic robust radical, 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO), and charge neutralizing anion, trifluoromethanesulfonylimide (TFSI-) was synthesized as a cathode material of a Li-ion battery. The copolymer, poly(2,2,6,6-tetramethylpiperidin-1-oxy-4-yl methacrylate-co-styrenesulfonyl(trifluoromethanesulfonyl)imide) (P(TMA-co-TFSI)), was designed to give rise to the Li+ migration during its charge-discharge process, based on the self-charge compensation of TEMPO with TFSI- bound to the polymer chain in a widely used electrolyte system for Li-ion battery, organic carbonate mixtures. Copolymerization was performed to achieve efficient self-charge compensation with uniformly distributed TFSI- units. The P(TMA-co-TFSI) layer electrode exhibited reversible redox reaction at 0.73 V vs Ag/AgCl. Electrochemical measurements combined with quartz crystal microbalance analysis evidenced that the redox reaction involved the Li+ migration in binary system of ethylene carbonate and diethyl carbonate. A test cell fabricated with the P(TMA-co-TFSI) cathode exhibited high discharging voltage of 3.7 V and high-rate charge-discharge capability at 30 C (i.e., full charging in 2 min).",
author = "Hiroshi Tokue and Tomoaki Murata and Haruka Agatsuma and Hiroyuki Nishide and Kenichi Oyaizu",
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T1 - Charge-Discharge with Rocking-Chair-Type Li+ Migration Characteristics in a Zwitterionic Radical Copolymer Composed of TEMPO and Trifluoromethanesulfonylimide with Carbonate Electrolytes for a High-Rate Li-Ion Battery

AU - Tokue, Hiroshi

AU - Murata, Tomoaki

AU - Agatsuma, Haruka

AU - Nishide, Hiroyuki

AU - Oyaizu, Kenichi

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N2 - Redox-active copolymer containing organic robust radical, 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO), and charge neutralizing anion, trifluoromethanesulfonylimide (TFSI-) was synthesized as a cathode material of a Li-ion battery. The copolymer, poly(2,2,6,6-tetramethylpiperidin-1-oxy-4-yl methacrylate-co-styrenesulfonyl(trifluoromethanesulfonyl)imide) (P(TMA-co-TFSI)), was designed to give rise to the Li+ migration during its charge-discharge process, based on the self-charge compensation of TEMPO with TFSI- bound to the polymer chain in a widely used electrolyte system for Li-ion battery, organic carbonate mixtures. Copolymerization was performed to achieve efficient self-charge compensation with uniformly distributed TFSI- units. The P(TMA-co-TFSI) layer electrode exhibited reversible redox reaction at 0.73 V vs Ag/AgCl. Electrochemical measurements combined with quartz crystal microbalance analysis evidenced that the redox reaction involved the Li+ migration in binary system of ethylene carbonate and diethyl carbonate. A test cell fabricated with the P(TMA-co-TFSI) cathode exhibited high discharging voltage of 3.7 V and high-rate charge-discharge capability at 30 C (i.e., full charging in 2 min).

AB - Redox-active copolymer containing organic robust radical, 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO), and charge neutralizing anion, trifluoromethanesulfonylimide (TFSI-) was synthesized as a cathode material of a Li-ion battery. The copolymer, poly(2,2,6,6-tetramethylpiperidin-1-oxy-4-yl methacrylate-co-styrenesulfonyl(trifluoromethanesulfonyl)imide) (P(TMA-co-TFSI)), was designed to give rise to the Li+ migration during its charge-discharge process, based on the self-charge compensation of TEMPO with TFSI- bound to the polymer chain in a widely used electrolyte system for Li-ion battery, organic carbonate mixtures. Copolymerization was performed to achieve efficient self-charge compensation with uniformly distributed TFSI- units. The P(TMA-co-TFSI) layer electrode exhibited reversible redox reaction at 0.73 V vs Ag/AgCl. Electrochemical measurements combined with quartz crystal microbalance analysis evidenced that the redox reaction involved the Li+ migration in binary system of ethylene carbonate and diethyl carbonate. A test cell fabricated with the P(TMA-co-TFSI) cathode exhibited high discharging voltage of 3.7 V and high-rate charge-discharge capability at 30 C (i.e., full charging in 2 min).

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