Lithium rechargeable batteries composed of octacyanophthalocyaninatoiron and its polymer complex as cathode

Kim, Soo‐Jong; Onishi, K.; Matsumoto, Michiko; Shigehara, Kiyotaka

doi:10.1002/jpp.336

Cited by 10 publications

(8 citation statements)

References 13 publications

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“…Although it was later clarifi ed that each phthalocyanine molecule actually accepts only four electrons and the major part of the previously found capacity comes from catalytic decomposition of the solvent carbonates, [ 207 ] the intercalation mechanism should not be denied. [ 209 ] Totally insoluble two-dimensional polymers of cyano-substituted phthalocyancine met with partial irreversible lithium intercalation unless shallow discharge was carefully maintained. Consequently, the octacyano-substituted phthalocyanine 163 can be cycled at a three-electron discharge depth.…”

Section: Layered Compoundsmentioning

confidence: 99%

“…Consequently, the octacyano‐substituted phthalocyanine 163 can be cycled at a three‐electron discharge depth 208. When discharge passes three‐electron, considerable dissolution occurs, and this could not be avoided by the use of a coordination polymer 209. Totally insoluble two‐dimensional polymers of cyano‐substituted phthalocyancine met with partial irreversible lithium intercalation unless shallow discharge was carefully maintained 210.…”

Section: Miscellaneousmentioning

confidence: 99%

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Organic Electrode Materials for Rechargeable Lithium Batteries

Liang

Tao

Chen

2012

Advanced Energy Materials

1,176

1,016

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Organic compounds offer new possibilities for high energy/power density, cost-effective, environmentally friendly, and functional rechargeable lithium batteries. For a long time, they have not constituted an important class of electrode materials, partly because of the large success and rapid development of inorganic intercalation compounds. In recent years, however, exciting progress has been made, bringing organic electrodes to the attention of the energy storage community. Herein thirty years' research efforts in the fi eld of organic compounds for rechargeable lithium batteries are summarized. The working principles, development history, and design strategies of these materials, including organosulfur compounds, organic free radical compounds, organic carbonyl compounds, conducting polymers, non-conjugated redox polymers, and layered organic compounds are presented. The cell performances of these materials are compared, providing a comprehensive overview of the area, and straightforwardly revealing the advantages/disadvantages of each class of materials.

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Section: Layered Compoundsmentioning

confidence: 99%

Section: Miscellaneousmentioning

confidence: 99%

Organic Electrode Materials for Rechargeable Lithium Batteries

Liang

Tao

Chen

2012

Advanced Energy Materials

1,176

1,016

View full text Add to dashboard Cite

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“…The refractive index of CuPcTs/PSS film was assumed to be 1.80 þ 10.3. Peaks at around 0.9 V and 0.05 V were observed and they were considered to be due to oxidization and reduction of CuPcTs, respectively [7][8][9][10]. The poor depositions on ITO substrates until 6th bilayers and those on Si wafer until 12th bilayers were probably due to the initial inhomogeneity in the substrate surfaces, i.e., surface charges, which eventually became homogenous with deposition.…”

Section: Resultsmentioning

confidence: 99%

“…For secondary batteries, phthalocyanines are quite useful for developing electrodes [7,8]. Furthermore, electrochromism of phthalocyanines have been investigated for developing new type displays [9,10].…”

Section: Introductionmentioning

confidence: 99%

Fabrication and Electrochromic Properties of Layer-by-Layer Self-Assembled Ultrathin Films Containing Water-Soluble Phthalocyanine

Shinbo

Kato

Kaneko

et al. 2003

Molecular Crystals and Liquid Crystals

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Alternate ultrathin films of water-soluble copper (II) phthalocyanine-3,4 0 ,4 00 ,4 000 -tetrasulfonic acid (CuPcTs) and poly(diallyldimethylammonium chloride) (PDADMAC) were fabricated using the electrostatic layer-by-layer self-assembly technique. Linear depositions of the bilayers were observed from the UV-vis absorption spectra and ellipsometry. The average thickness of the CuPcTs monolayer obtained from ellipsometry was about 1.2 nm and CuPcTs molecules were estimated to be tilted to the film surface. The cyclic votammogram (C-V) of the fabricated films in aqueous solution containing 0.1 M KCl suggested the oxidation and reduction of the CuPcTs at around þ0.9 V and 0.05 V respectively. UV-vis absorption spectra were observed for the films at applied voltages of 0.8 V and 0 V in the KCl aqueous solution and reversible absorption changes were observed.

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“…6 The structure was confirmed by time-of-flight ͑TOF͒ mass spectroscopy with a Perspective Biosystems Voyager Liner DE NT-1 spectrometer that gave only one designated peak at (m/z) ϭ 769.…”

Section: Methodsmentioning

confidence: 99%

Octacyanophthalocyaninatoiron Polymer as Cathode Material for a Secondary Lithium Battery

Asai

Onishi

Miyata

et al. 2001

J. Electrochem. Soc.

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The one-dimensional coordination polymers based on octacyanophthalocyanatoiron ͑FePcOC͒ and bidentate axial bridging ligands such as pyrazine, tetrazine, and diisocyanobenzene ͑dib͒ were synthesized and used as the cathode material of secondary lithium batteries. The lithium//electrolyte solution//FePcOC-dib polymer cell gave the best performance due to its stability upon discharging process. Especially when the 0.5 M LiPF 6 /dimethoxyethane solution was used as the electrolyte, the cell exhibited the energy density of 475 Wh kg Ϫ1 with the average output voltage of 3.2 V.Metallophthalocyanine ͑MPc͒ derivatives have been known to promote Li ϩ -intercalation 1-2 that can be utilized in cathodic reactions of lithium ͑or lithium-ion͒ rechargeable batteries. Yamaki et al. have reported cathode materials containing unsubstituted MPc or freebase phthalocyanine (H 2 Pc) in secondary lithium batteries. 3,4 For 1 V cutoff, the discharge voltage and the discharge capacity of these cells were reported to be 1.4 V and 870 mAh g Ϫ1 ͑g Ϫ1 : per gram of active cathode material͒, respectively. However, the results revealed problems of relatively low average voltage due to too negative formal potential of MPc or H 2 Pc for Li ϩ -intercalation and almost no recovery of cell capacity upon recharging.We have reported lithium rechargeable cells composed of freebase octacyanophthalocyanine (H 2 PcOC) 5 and octacyanophthalocyaninatoiron ͑FePcOC͒ 6 cathodes in the hope to improve battery properties due to their strong acceptor nature and relatively high conductivity. The cycle life of cells, Li//electrolyte solution// MPcOC ͑M ϭ H 2 or Fe͒, was elongated to 50 times, because the existence of peripheral 8 cyano groups gave the electric conductivity and reduction formal potential of 10 Ϫ6 to 10 Ϫ8 S cm Ϫ1 and about 0 V vs. normal hydrogen electrode ͑NHE͒, larger by 10 3 to 10 5 times and more positive by 0.5-0.8 V than those of corresponding unsubstituted derivatives, respectively. In these cells, the multielectron reduction of MPcOC yielding Li 3 ϩ ͑H 2 PcOC͒ 3Ϫ or Li 4 ϩ ͑FePcOC͒ 4Ϫ is the origin of the cathodic reaction. Unfortunately, because MPcOC was partially soluble as it is and became soluble upon reduction in the electrolyte solution, the coulombic efficiency decreased gradually with the discharge/charge cycles due to the loss of cathode-active material. In the present study, FePcOC was insolubilized in the electrolyte solutions by the polymerization with bidentate bridging ligands via axial coordination spheres and the properties of resulting one-dimensional coordination polymers as cathodeactive materials were examined. ExperimentalMaterials.-Either battery-grade or reagent-grade chemicals of lithium hexafluorophosphate ͑LiPF 6 ; Kishida Chemicals͒, poly͑vi-nylidene fluoride͒ ͑PVDF; Wako Chemicals͒ and iron͑II͒ acetate ͑Kanto Chemicals͒ were used as received. Acetylene black ͑AB; Denkikagaku Kogyo Co.͒ was dried in vacuo at 60°C for a day. Reagent grade chemicals ͑Tokyo Chemical Ind.͒ of tetracyanobenzene ͑TCB͒, pyrazine ͑pyz͒...

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Lithium rechargeable batteries composed of octacyanophthalocyaninatoiron and its polymer complex as cathode

Cited by 10 publications

References 13 publications

Organic Electrode Materials for Rechargeable Lithium Batteries

Organic Electrode Materials for Rechargeable Lithium Batteries

Fabrication and Electrochromic Properties of Layer-by-Layer Self-Assembled Ultrathin Films Containing Water-Soluble Phthalocyanine

Octacyanophthalocyaninatoiron Polymer as Cathode Material for a Secondary Lithium Battery

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