Solution-processed conducting polymers(CPs)are emerging as promising multifunctional materials and are motivating the development of several electronic applications.However,there are fewer highperformance electron con...Solution-processed conducting polymers(CPs)are emerging as promising multifunctional materials and are motivating the development of several electronic applications.However,there are fewer highperformance electron conduction-dominated n-type CPs than p-types.Thus,the exploration of other material designs and synthesis methods is required.Accordingly,we developed a facile metal catalystfree method by combining polymerization and in situ n-doping to produce an n-type conducting polymer,poly(benzodithiophenedione)(PBTDO).The doping procedure enabled interaction between the charged conjugated backbones and solvent,dimethyl sulfoxide,making the doped conducting polymer soluble without the assistance of side chains or surfactants.PBTDO exhibited an extremely low-lying reduction level,moderate conductivity,and good air stability with potential applications in n-type organic thermoelectric devices.Moreover,it was found that the in situ doping efficiency in the reaction was highly dependent on the energy level and backbone planarity.Doping cannot occur for polymers with a high lowest unoccupied molecular orbital level and distorted conjugated chains prevent a high doping efficiency from being obtained.This study gains deeper insight into the n-doping mechanisms of conjugated polymers,with guidance for the design of highperformance n-type CPs.展开更多
Conducting polymers （CPs） have been widely investigated due to their extraordinary advantages over the traditional materials, including wide and tunable electrical conductivity, facile production approach, high mech...Conducting polymers （CPs） have been widely investigated due to their extraordinary advantages over the traditional materials, including wide and tunable electrical conductivity, facile production approach, high mechanical stability, light weight, low cost and ease in material processing. Compared with bulk CPs, nanostructured CPs possess higher electrical conductivity, larger surface area, superior electro- chemical activity, which make them suitable for various ap- plications. Hybridization of CPs with other nanomaterials has obtained promising functional nanocomposites and achieved improved performance in different areas, such as energy sto- rage, sensors, energy harvesting and protection applications. In this review, recent progress on nanostructured CPs and their composites is summarized from research all over the world in more than 400 references, especially from the last three years. The relevant synthesizing experiences are outlined and abundant application examples are illustrated. The ap- proaches of production of nanostructured CPs are discussed and the efficacy and benefits of newest trends for the pre- paration of multifunctional nanomaterials/nanocomposites are presented. Mechanism of their electrical conductivity and the ways to tailor their properties are investigated. The re- maining challenges in developing better CPs based nanoma- terials are also elaborated.展开更多
The title polymers PMS 8Pz,M=Mn Ⅱ,Fe Ⅱ,Co Ⅱ,Ni Ⅱ,Cu Ⅱ,Zn Ⅱ,were synthesized by teaction of 2,3,5,6 tetracyano 1,4 dithiin with corresponding metal salts ,respectively.The styucture and properties of th...The title polymers PMS 8Pz,M=Mn Ⅱ,Fe Ⅱ,Co Ⅱ,Ni Ⅱ,Cu Ⅱ,Zn Ⅱ,were synthesized by teaction of 2,3,5,6 tetracyano 1,4 dithiin with corresponding metal salts ,respectively.The styucture and properties of these polyers were characterized by elemental analysis,transmission electron microscope,DTA,IR, UV Vis,fluorescence and EPR spectra. It has been found that these conjugated polymers have the property of intrinsic semiconductor. The conductivity σ 298K of these polymers is in the range of 10 -9 ￣10 -3 S · cm -1 under pressure 10.63 MPa and incremental in the metal orderMn < Co<Fe<Zn<Cu<Ni.\ The photosensitivity of the MS 8Pz to the CdS PVA films is incremental in the metal order Zn < Mn < Co < Fe < Cu < Ni.展开更多
We report for the first time highly conductive poly（3,4-ethylenedioxythiophene）： poly（4-styrenesulfonate） （PEDOT：PSS）/graphene composites fabricated by in situ polymerization and their applications in a thermo...We report for the first time highly conductive poly（3,4-ethylenedioxythiophene）： poly（4-styrenesulfonate） （PEDOT：PSS）/graphene composites fabricated by in situ polymerization and their applications in a thermoelectric device and a platinum （Pt）-free dye-sensitized solar cell （DSSC） as energy harvesting systems. Graphene was dispersed in a solution of poly（4-styrenesulfonate） （PSS） and polymerization was directly carried out by addition of 3,4-ethylenedioxythiophene （EDOT） monomer to the dispersion. The content of the graphene was varied and optimized to give the highest electrical conductivity. The composite solution was ready to use without any reduction process because reduced graphene oxide was used. The fabricated film had a conductivity of 637 S.cm-1, corresponding to an enhancement of 41%, after the introduction of 3 wt.% graphene without any further complicated reduction processes of graphene being required. The highly conductive composite films were employed in an organic thermoelectric device, and the device showed a power factor of 45.7 μW·m^-1K^-2 which is 93% higher than a device based on pristine PEDOT：PSS. In addition, the highly conductive composite films were used in Pt-free DSSCs, showing an energy conversion efficiency of 5.4%, which is 21% higher than that of a DSSC based on PEDOT：PSS.展开更多
Organic semiconductors,especially polymer semiconductors,have attracted extensive attention as organic thermoelectric materials due to their capabilities for flexibility,low-cost fabrication,solution processability an...Organic semiconductors,especially polymer semiconductors,have attracted extensive attention as organic thermoelectric materials due to their capabilities for flexibility,low-cost fabrication,solution processability and low thermal conductivity.However,it is challenging to obtain high-performance organic thermoelectric materials because of the low intrinsic carrier concentration of organic semiconductors.The main method to control the carrier concentration of polymers is the chemical doping process by charge transfer between polymer and dopant.Therefore,the deep understanding of doping mechanisms from the point view of chemical structure has been highly desired to overcome the bottlenecks in polymeric thermoelectrics.In this contribution,we will briefly review the recently emerging progress for discovering the structure–property relationship of organic thermoelectric materials with high performance.Highlights include some achievements about doping strategies to effectively modulate the carrier concentration,the design rules of building blocks and side chains to enhance charge transport and improve the doping efficiency.Finally,we will give our viewpoints on the challenges and opportunities in the field of polymer thermoelectric materials.展开更多
A novel organic disulfide, N, N′-dithiobis(3-nitroaniline)(1) was prepared by the reaction of 3-nitroaniline with sulfur monochloride in chloroform. Compound 1 was reduced by zinc powder to give N, N′-dithiobis(1,3-...A novel organic disulfide, N, N′-dithiobis(3-nitroaniline)(1) was prepared by the reaction of 3-nitroaniline with sulfur monochloride in chloroform. Compound 1 was reduced by zinc powder to give N, N′-dithiobis(1,3-phenylenediamine) (2). Poly N, N′-dithiobis (1,3-phenylenediamine) (3) was prepared by electrochemical polymerization of compound 2 and its basic electrochemical behavior is discussed.展开更多
We prepared conducting polyaniline （PAn） co-doped with sulfosalicylic acid （SSA） and dodecylbenzoyl sultonic acid （DBSA） in micro-emulsive polymerization, and studied its charge transport behaviors based on the ...We prepared conducting polyaniline （PAn） co-doped with sulfosalicylic acid （SSA） and dodecylbenzoyl sultonic acid （DBSA） in micro-emulsive polymerization, and studied its charge transport behaviors based on the measurement of its electrical conductivity in the temperature range between 203 K and 298 K. The conductivity was found to increase with temperature, similar to the case in semiconductors. Analyzing the experimental data with three models, namely the charge-energy-limitedtunneling model, Kivelson model and the three-dimensional variable range hopping （3D-VRH） model demonstrated that these models all describe well the charge transport behaviors of PAn co-doped with SSA and DBSA within the mentioned temperature range. From calculation with the 3D-VRH model, the hopping distance of the conducting PAn is obviously larger than its localization length. The PAn doped with SSA and DBSA enjoys desirable crystallinity due to the co-doping of two functional sulfonic acids. The macroscopic conductivity may correspond to three-dimensional transport in the network of the bundles, and the metallic islands may be attributed to quasi-one-dimensional bundles.展开更多
The conduct mechanism of the doped polymer is considered. In an asymmetrysystem composed of high polymer and doping conductive matte, chain or congeries framework will beformed between the conductive particles to impr...The conduct mechanism of the doped polymer is considered. In an asymmetrysystem composed of high polymer and doping conductive matte, chain or congeries framework will beformed between the conductive particles to improve the conductance characteristic. In thisprocession, the conductive particles interact to each other. In this paper, we describe theconductance of the doped polymer by Monte Carlo method. The results accord with the experimentsquite well. It can be concluded that there is an evident change of doped polymer from nonconductorto metal.展开更多
I. INTRODUCTION Electrical conductive polymers have attracted considerable attention since the metallic conducting polyacetylene was reported. A relatively large number of conjugated polymers are now known which can b...I. INTRODUCTION Electrical conductive polymers have attracted considerable attention since the metallic conducting polyacetylene was reported. A relatively large number of conjugated polymers are now known which can be doped with either strong electron acceptors or donors to yield conducting complexes. The preparation of conducting polymer is usually展开更多
Polyaniline（PANI） nanofiber was synthesized by interfacial polymerization utilizing the interface between HC1 and CCl4. The hybrid type supercapacitors （PLi/C） based on Li-doping polyaniline and activated carbon e...Polyaniline（PANI） nanofiber was synthesized by interfacial polymerization utilizing the interface between HC1 and CCl4. The hybrid type supercapacitors （PLi/C） based on Li-doping polyaniline and activated carbon electrode were fabricated and compared with the redox type capacitors （PLi/PLi） based on two uniformly Li-doping polyaniline electrodes. The electrochemical performances of the two types of supercapacitors were characterized in non-aqueous electrolyte. PLi/C supercapacitors have a wider effective energy storage potential range and a higher upper potential. At the same time, the PLi/C supercapacitor exhibits a specific capacity of 120.93 F/g at initial discharge and retains 80% after 500 cycles. The ohmic internal resistance （REs） of PLi/C supercapacitor is 5.0 Ω, which is smaller than that of PLi/PLi capacitor （5.5 Ω）. Moreover, it can be seen that EtgNBF4 organic solution is more suitable for using as organic electrolyte of PLi/C capacitor compared with organic solution containing LiPFr.展开更多
基金grant from the Ministry of Science and Technology of the People’s Republic of China(MOST),the Basic and Applied Basic Research Major Program of Guangdong Province(grant no.2019B030302007)the National Natural Science Foundation of China(grant no.U21A6002)the Guangdong-Hong Kong-Macao Joint Laboratory of Optoelectronic and Magnetic Functional Materials(grant no.2019B121205002).
文摘Solution-processed conducting polymers(CPs)are emerging as promising multifunctional materials and are motivating the development of several electronic applications.However,there are fewer highperformance electron conduction-dominated n-type CPs than p-types.Thus,the exploration of other material designs and synthesis methods is required.Accordingly,we developed a facile metal catalystfree method by combining polymerization and in situ n-doping to produce an n-type conducting polymer,poly(benzodithiophenedione)(PBTDO).The doping procedure enabled interaction between the charged conjugated backbones and solvent,dimethyl sulfoxide,making the doped conducting polymer soluble without the assistance of side chains or surfactants.PBTDO exhibited an extremely low-lying reduction level,moderate conductivity,and good air stability with potential applications in n-type organic thermoelectric devices.Moreover,it was found that the in situ doping efficiency in the reaction was highly dependent on the energy level and backbone planarity.Doping cannot occur for polymers with a high lowest unoccupied molecular orbital level and distorted conjugated chains prevent a high doping efficiency from being obtained.This study gains deeper insight into the n-doping mechanisms of conjugated polymers,with guidance for the design of highperformance n-type CPs.
基金supported by the National Institute of Food and Agriculture,USDA and AU-IGP award
文摘Conducting polymers （CPs） have been widely investigated due to their extraordinary advantages over the traditional materials, including wide and tunable electrical conductivity, facile production approach, high mechanical stability, light weight, low cost and ease in material processing. Compared with bulk CPs, nanostructured CPs possess higher electrical conductivity, larger surface area, superior electro- chemical activity, which make them suitable for various ap- plications. Hybridization of CPs with other nanomaterials has obtained promising functional nanocomposites and achieved improved performance in different areas, such as energy sto- rage, sensors, energy harvesting and protection applications. In this review, recent progress on nanostructured CPs and their composites is summarized from research all over the world in more than 400 references, especially from the last three years. The relevant synthesizing experiences are outlined and abundant application examples are illustrated. The ap- proaches of production of nanostructured CPs are discussed and the efficacy and benefits of newest trends for the pre- paration of multifunctional nanomaterials/nanocomposites are presented. Mechanism of their electrical conductivity and the ways to tailor their properties are investigated. The re- maining challenges in developing better CPs based nanoma- terials are also elaborated.
文摘The title polymers PMS 8Pz,M=Mn Ⅱ,Fe Ⅱ,Co Ⅱ,Ni Ⅱ,Cu Ⅱ,Zn Ⅱ,were synthesized by teaction of 2,3,5,6 tetracyano 1,4 dithiin with corresponding metal salts ,respectively.The styucture and properties of these polyers were characterized by elemental analysis,transmission electron microscope,DTA,IR, UV Vis,fluorescence and EPR spectra. It has been found that these conjugated polymers have the property of intrinsic semiconductor. The conductivity σ 298K of these polymers is in the range of 10 -9 ￣10 -3 S · cm -1 under pressure 10.63 MPa and incremental in the metal orderMn < Co<Fe<Zn<Cu<Ni.\ The photosensitivity of the MS 8Pz to the CdS PVA films is incremental in the metal order Zn < Mn < Co < Fe < Cu < Ni.
文摘We report for the first time highly conductive poly（3,4-ethylenedioxythiophene）： poly（4-styrenesulfonate） （PEDOT：PSS）/graphene composites fabricated by in situ polymerization and their applications in a thermoelectric device and a platinum （Pt）-free dye-sensitized solar cell （DSSC） as energy harvesting systems. Graphene was dispersed in a solution of poly（4-styrenesulfonate） （PSS） and polymerization was directly carried out by addition of 3,4-ethylenedioxythiophene （EDOT） monomer to the dispersion. The content of the graphene was varied and optimized to give the highest electrical conductivity. The composite solution was ready to use without any reduction process because reduced graphene oxide was used. The fabricated film had a conductivity of 637 S.cm-1, corresponding to an enhancement of 41%, after the introduction of 3 wt.% graphene without any further complicated reduction processes of graphene being required. The highly conductive composite films were employed in an organic thermoelectric device, and the device showed a power factor of 45.7 μW·m^-1K^-2 which is 93% higher than a device based on pristine PEDOT：PSS. In addition, the highly conductive composite films were used in Pt-free DSSCs, showing an energy conversion efficiency of 5.4%, which is 21% higher than that of a DSSC based on PEDOT：PSS.
基金supported by the National Natural Science Foundation of China(Grant No.21905294)the Shanghai Sailing Program。
文摘Organic semiconductors,especially polymer semiconductors,have attracted extensive attention as organic thermoelectric materials due to their capabilities for flexibility,low-cost fabrication,solution processability and low thermal conductivity.However,it is challenging to obtain high-performance organic thermoelectric materials because of the low intrinsic carrier concentration of organic semiconductors.The main method to control the carrier concentration of polymers is the chemical doping process by charge transfer between polymer and dopant.Therefore,the deep understanding of doping mechanisms from the point view of chemical structure has been highly desired to overcome the bottlenecks in polymeric thermoelectrics.In this contribution,we will briefly review the recently emerging progress for discovering the structure–property relationship of organic thermoelectric materials with high performance.Highlights include some achievements about doping strategies to effectively modulate the carrier concentration,the design rules of building blocks and side chains to enhance charge transport and improve the doping efficiency.Finally,we will give our viewpoints on the challenges and opportunities in the field of polymer thermoelectric materials.
文摘A novel organic disulfide, N, N′-dithiobis(3-nitroaniline)(1) was prepared by the reaction of 3-nitroaniline with sulfur monochloride in chloroform. Compound 1 was reduced by zinc powder to give N, N′-dithiobis(1,3-phenylenediamine) (2). Poly N, N′-dithiobis (1,3-phenylenediamine) (3) was prepared by electrochemical polymerization of compound 2 and its basic electrochemical behavior is discussed.
文摘We prepared conducting polyaniline （PAn） co-doped with sulfosalicylic acid （SSA） and dodecylbenzoyl sultonic acid （DBSA） in micro-emulsive polymerization, and studied its charge transport behaviors based on the measurement of its electrical conductivity in the temperature range between 203 K and 298 K. The conductivity was found to increase with temperature, similar to the case in semiconductors. Analyzing the experimental data with three models, namely the charge-energy-limitedtunneling model, Kivelson model and the three-dimensional variable range hopping （3D-VRH） model demonstrated that these models all describe well the charge transport behaviors of PAn co-doped with SSA and DBSA within the mentioned temperature range. From calculation with the 3D-VRH model, the hopping distance of the conducting PAn is obviously larger than its localization length. The PAn doped with SSA and DBSA enjoys desirable crystallinity due to the co-doping of two functional sulfonic acids. The macroscopic conductivity may correspond to three-dimensional transport in the network of the bundles, and the metallic islands may be attributed to quasi-one-dimensional bundles.
文摘The conduct mechanism of the doped polymer is considered. In an asymmetrysystem composed of high polymer and doping conductive matte, chain or congeries framework will beformed between the conductive particles to improve the conductance characteristic. In thisprocession, the conductive particles interact to each other. In this paper, we describe theconductance of the doped polymer by Monte Carlo method. The results accord with the experimentsquite well. It can be concluded that there is an evident change of doped polymer from nonconductorto metal.
基金Project supported by the National Natural Science Foundation of China
文摘I. INTRODUCTION Electrical conductive polymers have attracted considerable attention since the metallic conducting polyacetylene was reported. A relatively large number of conjugated polymers are now known which can be doped with either strong electron acceptors or donors to yield conducting complexes. The preparation of conducting polymer is usually
基金Project(2008AA03Z207) supported by the National High-Tech Research and Development Program of China
文摘Polyaniline（PANI） nanofiber was synthesized by interfacial polymerization utilizing the interface between HC1 and CCl4. The hybrid type supercapacitors （PLi/C） based on Li-doping polyaniline and activated carbon electrode were fabricated and compared with the redox type capacitors （PLi/PLi） based on two uniformly Li-doping polyaniline electrodes. The electrochemical performances of the two types of supercapacitors were characterized in non-aqueous electrolyte. PLi/C supercapacitors have a wider effective energy storage potential range and a higher upper potential. At the same time, the PLi/C supercapacitor exhibits a specific capacity of 120.93 F/g at initial discharge and retains 80% after 500 cycles. The ohmic internal resistance （REs） of PLi/C supercapacitor is 5.0 Ω, which is smaller than that of PLi/PLi capacitor （5.5 Ω）. Moreover, it can be seen that EtgNBF4 organic solution is more suitable for using as organic electrolyte of PLi/C capacitor compared with organic solution containing LiPFr.
