Simultaneous polymerization and formation of polyacetylene film on the surface of concentrated soluble Ziegler‐type catalyst solution

Itô, Takeo; Shirakawa, Hideki; Ikeda, Sakuji

doi:10.1002/pol.1974.170120102

Cited by 1,139 publications

(75 citation statements)

References 29 publications

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“…Polyacetylene films for the light doping experiments were prepared by the procedure of Ito et al 17 The preparation of the thin films on Csl substrates has been described previously. 8 All samples were predominantly cis before doping.…”

Section: Methodsmentioning

confidence: 99%

Fourier transform infrared study of the polymer-dopant interaction in polyacetylene

Rabolt

Clarke

Street

1982

The Journal of Chemical Physics

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MM Research Laboratory0f-San Jone, CalifroJ 95193 ABSTRA47 Foer Traorm Infrared (FTIR) measurements of AsP 5 doped (CH!), with dopant concentrations 1),ich vary over three orders of magnitude have been obtained in both the mid (4000-400 cm) and far (400-15 cm-1 ) infrared. The bandwidths of the strong bandscaatrsi of the doped polyme have been observed to be invariant with dopant concentration. However, the frequency shitious of these now IR bands are found to be a sensitive function of the dopant level. In te far infrared, no evidence of the predicted soliton pinning mode was found for any the dopant concentrations studied. The consequnce of these results in view of nt theoretical models of the polymer-dopant interaction is discussed./11

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Section: Methodsmentioning

confidence: 99%

Fourier transform infrared study of the polymer-dopant interaction in polyacetylene

Rabolt

Clarke

Street

1982

The Journal of Chemical Physics

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“…Appearance of conductive polymers in the late 1970s, and of conjugated semiconductors and photoemission polymers in the 1980s, greatly accelerated development in the field of organic electronics [8]. Polyacetylene was one of the earliest polymer materials known to be potential as conducting electricity [9], and one could find that oxidative dopant with iodine could greatly increase conductivity by 12 orders of magnitude [10]. This discovery and development of highly conductive organic materials were attributed to three scientists: Alan J. Heeger, Alan G. MacDiarmid and Hideki Shirakawa, who were jointly awarded the Nobel Prize in Chemistry in 2000 for their discovery in 1977 and development of oxidized, iodine-doped polyacetylene.…”

Section: Historymentioning

confidence: 99%

Thermoelectric Effect and Application of Organic Semiconductors

Lu¹,

Li²,

Liu³

2016

Thermoelectrics for Power Generation - A Look at Trends in the Technology

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Human development and society progress require solving many pressing issues, including sustainable energy production and environmental conservation. Thermoelectric power generation looks like promising opportunity converting huge heat from the sun and waste heat from industrial sector, housing appliances and infrastructure and automobile and other fuel combustion exhaust directly to electrical energy. Thermoelectric power generation will be of high demand, when technology will be affordable, providing low price, high conversion efficiency, reliability, easy applicability and advanced ecological properties of end products. In this context, organic thermoelectric materials attract great interest caused by non-scarcity of raw materials, non-toxicity, potentially low costs in high-scale production, low thermal conductivity and wide capabilities to control thermoelectric properties. In this chapter, we focus mainly on thermoelectric effect in several organic semiconductors, both crystalline and disordered. We present theory of some transport phenomena determining thermoelectric properties of organic semiconductors, including general expression of thermoelectric effect, percolation theory of Seebeck coefficient, hybrid model of Seebeck coefficient, Monte Carlo simulation and first-principle theory. Finally, a future outlook of this field is briefly discussed.

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“…There are initial indications (1I, 12) that films doped with AsFs-and C104-are somewhat more stable. The polyacetylene films used in these experiments were prepared by the technique first described by Shirakawa (4). Polyacetylene was transferred and stored under vacuum, and manipulated and studied in an inert atmosphere dry box.…”

Section: Stabilitymentioning

confidence: 99%

The Electrochemical Oxidation of Polyacetylene and Its Battery Applications

Farrington

Scrosati

Frydrych

et al. 1984

J. Electrochem. Soc.

124

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When oxidized in a nonaqueous cell containing 1.0M LiC104 in propylene carbonate, polyacetylene develops a voltage of 3.4-4.0V vs. Li/Li + C10(. Oxidation levels at least as high as [CH(C104)0.1o]x can be produced electrochemically and then reduced to the undoped state with nearly 100~ coulombic efficiency. The electrochemical doping (oxidation) process is only efficient when carried out with a minimum of liquid electrolyte under ultraclean conditions. Similar results are observed with a LiAsF6 electrolyte. Polyacetylene is an extraordinary material of great importance for electrochemistry. However, on the basis of this and other published research, it is not yet clear that it offers major advantages over current electrodes for high energy density nonaqueous batteries.Polyaeetylene is a fascinating new material with extraordinary electrochemical properties. It is a simple conjugated organic polymer which can easily be synthesized by the catalytic polymerization of acetylene. Polyacetylene films can be chemically oxidized and reduced by a variety of species, such as halogens (I and Br) and various organo-alkali metal reagents, such as n-butyl lithium and sodium naphthalide. These reactions are generally referred to as p-doping (oxidation) or n-doping (reduction). They produce compounds of the type (CHXy)x and (MuCH)x, in which y is typically in the range of 0-0.1. What is most unusual about polyacetylene is that p-or n-doping transforms it from a virtual electronic insulator into a lustrous polymer with an electronic conductivity typical of metals (1).The reversible oxidation and reduction of polyacetylene can also be carried out electrochemically in nonaqueous electrolytes containing appropriate dissolved anions or cations. These reactions were first described by Nigrey etal. (2). The electrochemical potentials of oxidized polyacetylene films (X ----I, AsF6, Br, C104) are typically 3-4V vs. the Li/Li + electrode. The potentials of the reduced films (M --Li, Na) are about 0.5-1.5V vs. that of Li/Li+. Nigrey etal. (2) and MacInnes etal. (3) first suggested that the oxidized and reduced polyacetylenes might be used as high voltage anode/cathode couples in nonaqueous electrochemical cells.The general goals of our research have been to examine those aspects of the chemistry and electrochemistry of polyacetylene which influence its potential application in batteries. This paper summarizes our investigations of the stability and electrochemical oxidation of polyacetylene in propylene carbonate containing LiC104~or LiAsF6. StabilityPolyacetylene exists in eis and trans isomers (Fig. 1). Trans polyacetylene is the thermodynamically stable form. The cis isomer can be produced by polymerization at low (--78~ temperatures, but it is unstable toward isomerization, which can be induced by heating or by doping wiLh various chemical species (5,6,7). Polyacetylene also self-reacts, forming cross-links and defects. These reactions occur rapidly at elevated temperatures (150~176 (5).

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Simultaneous polymerization and formation of polyacetylene film on the surface of concentrated soluble Ziegler‐type catalyst solution

Cited by 1,139 publications

References 29 publications

Fourier transform infrared study of the polymer-dopant interaction in polyacetylene

Fourier transform infrared study of the polymer-dopant interaction in polyacetylene

Thermoelectric Effect and Application of Organic Semiconductors

The Electrochemical Oxidation of Polyacetylene and Its Battery Applications

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