Photocrosslinked nitroxide polymer cathode-active materials for application in an organic-based paper battery

Suga, Takeo; Konishi, Hiroaki; Nishide, Hiroyuki

doi:10.1039/b618710b

Cited by 308 publications

(263 citation statements)

References 16 publications

Supporting

Mentioning

263

Contrasting

Order By: Relevance

“…Previously, we have investigated the correlation of film thickness of 2 and its redox profile, and reported the transition (from surface-confined to diffusion-controlled) at a film thickness of 250 nm. 10,26 Further optimization of the fiber diameters and configuration of overlayed fibrous membranes are still necessary; however, direct electrospinning of radical polymers without any radical defects is promising. Fibrous composite formation with current conductor additives such as multi-walled carbon nanotubes 29 will also explore the potential of radical polymers as flexible and mechanically-durable battery electrodes.…”

Section: Electrospinning Of Radical Polymersmentioning

confidence: 99%

See 1 more Smart Citation

Electrospinning of radical polymers: redox-active fibrous membrane formation

Suga

Hunley

Long

et al. 2011

Polym J

Self Cite

View full text Add to dashboard Cite

Redox-active but highly durable nitroxide radicals, that is, 2,2,6,6-tetramethylpiperidinyl-4-oxy (TEMPO), enabled direct electrospinning of radical-containing polymers without additional processing aids (such as polymer blends, post-doping, or protection/deprotection) and produced redox-active fibrous membranes with high surface area. The solution rheological behavior of the TEMPO-substituted polymethacrylate was similar to the neutral conventional polymers, and electrospinning of the radical polymers yielded submicrometer-scaled fibrous membranes without any defects on the radical moiety. The obtained membrane exhibited stable redox response, leading to redox catalysts or electrode-active materials toward organic-based flexible rechargeable battery. Polymer Journal (2012) 44, 264-268; doi:10.1038/pj.2011.120; published online 7 December 2011Keywords: electrospinning; functional polymers; radical; redox INTRODUCTION Among stable organic radical molecules that possess an unpaired electron, nitroxide radicals (such as 2,2,6,6-tetramethylpiperidinyl-4-oxy (TEMPO)) have attracted much attention due to their utilization as spin-labels, spin traps, and capping agents for controlled radical polymerization. 1 Besides, based on the stable redox couple between the nitroxide radical and its oxidized form (oxoammonium cation, Scheme 1), nitroxide-functionalized polymers and organic/inorganic composites have been employed as heterogeneous redox reagents, which catalyze the oxidation of alcohols into aldehydes and ketones. 2 This metal-free oxidation process has resurfaced as a green or environmentally-compatible chemical process. 3 Recently, we have explored and utilized nitroxide polymers as cathode-active, charge-storage materials for secondary Li-ion batteries. [4][5][6][7][8][9] The organic radical battery composed of a radical polymer cathode has several advantages: high charge capacity (ca. 100-140 mAh g À1 ), high-charging and discharging rate performance (30 s for complete charge), and long cycle life often exceeding 1000 cycles. For both applications, to enhance the turnover cycles for catalysts or charge/discharge performance for electrode-active materials, construction of nitroxide supports with high surface area has an important role due to efficient mass (substrate or counter ion) transfer accompanied by the redox reaction. 10 Prompted by the design of soft portable electronic equipments, such as roll-up displays and wearable devices, the development of bendable and flexible batteries has attracted increased interest. 11 A fibrous membrane morphology improves mechanical flexibility and possesses an enhanced surface area to volume ratio.

show abstract

Section: Electrospinning Of Radical Polymersmentioning

confidence: 99%

“…25 Poly(TEMPO-substituted norbornene) 2 (M w ¼16 000, M w /M n ¼1.3) was also synthesized via ring-opening metathesis polymerization by reference to our previous papers. 26 Chloroform and N,N-dimethylformamide (DMF) were used as solvents without further purification.…”

Section: Experimental Procedures Materialsmentioning

confidence: 99%

Electrospinning of radical polymers: redox-active fibrous membrane formation

Suga

Hunley

Long

et al. 2011

Polym J

Self Cite

View full text Add to dashboard Cite

show abstract

“…4 Because this reaction is very similar to surface confined pseudocapacitive reaction of metal oxide, an extremely fast charging/discharging performance has been observed in this material (about 70% charging for 1 min). 4,5 In addition, this charge storage reaction is highly reversible, indicative of very long cycle life. As a typical polymer for ORP, poly(2,2,6,6-tetramethyl-1-piperidinyloxy-4-yl methacrylate) (PTMA) has been widely investigated, which has additional strong merits such as high energy density, nontoxicity, high safety and good fabrication property.…”

Section: Introductionmentioning

confidence: 99%

“…E-mail: being@cau.ac.kr; yoonshun@cau.ac.kr 폴리머, 제38권 제6호, 2014년 radical was prepared. 5 In this preparation, oxidation process is very important since the radical concentration of PTMA is determined by this process. In spite of several oxidation methods suggested in the literatures, comparison between proposed methods has been not investigated.…”

Section: Introductionmentioning

confidence: 99%

“…1,2 Organic radical polymers (ORPs) have been considered as one of the most promising cathode materials for extremely high power lithium ion batteries (LIBs). [3][4][5] Especially, ORPs are based on the electrochemical reaction of nitroxyl radical with the anion at 3.5 V vs. Li/Li + , which produced oxo-ammonium cation. 4 Because this reaction is very similar to surface confined pseudocapacitive reaction of metal oxide, an extremely fast charging/discharging performance has been observed in this material (about 70% charging for 1 min).…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Investigation of Oxidation Methods of Organic Radical Polymer for Cathode Material in Lithium Ion Batteries

Lee¹,

Kim²,

Moon³

et al. 2014

Polymer Korea

View full text Add to dashboard Cite

An organic radical polymer (ORP) was prepared by radical polymerization and following oxidation into nitroxyl radical. Two different oxidation methods were employed and their radical concentrations were measured using electroparamagnetic resonance spectroscopy (EPR) and UV-visible absorption (UV-vis) spectroscopy. From these measurements, H 2 O 2 -Na 2 WO 4 oxidation method exhibited a complete oxidation, which resulted in 97.6% spin concentration. Also, it was revealed that convenient and cheap UV-vis measurement was useful for preliminary radical concentration comparison. After applied as a cathode material in lithium ion batteries, ORP electrode showed a high initial capacity (110 mAh g -1 ), a good initial efficiency (96%), a very high rate performance (70% charging during 1.2 min) and stable cycle performance.

show abstract