CN103151180A - Organic high-polymer super capacitor electrode material and preparation method thereof - Google Patents
Organic high-polymer super capacitor electrode material and preparation method thereof Download PDFInfo
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- CN103151180A CN103151180A CN2013100939636A CN201310093963A CN103151180A CN 103151180 A CN103151180 A CN 103151180A CN 2013100939636 A CN2013100939636 A CN 2013100939636A CN 201310093963 A CN201310093963 A CN 201310093963A CN 103151180 A CN103151180 A CN 103151180A
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Abstract
The invention discloses an organic high-polymer super capacitor electrode material and a preparation method thereof. The electrode material comprises polyimide mixed with conductive nano copper powders with multi-skeleton structures; a particle diameter of each nano copper powder is between 1nm and 100nm; and an electrode capacity is 57-80F/g in a current density of 5mA/cm<2>.The method comprises the following steps that (1) diatomic acid anhydride and bisamine are dissolved in an organic dissolvent to obtain a solution A; (2) the nano copper powders are dispersed in the organic dissolvent, and after the mixture is subjected to stirring and ultrasonic treatment, a solution B is obtained; (3) the solution A and the solution B are rapidly mixed and placed in ultrasonic for 30min, a backflow reaction is carried out in the organic dissolvent in a stirring condition, an obtained product is subjected to filtering and alcohol washing, and amic acid mixed with nano copper is obtained after drying in a baking box; and (4) the obtained amic acid is under protection of inert gas and is subjected to heating treatment with a temperature of 300-320 DEG C for 6-8h to obtain yellow powder-shaped polyimide electrode material mixed with nano copper.
Description
Technical field
The present invention relates to the engineering plastics polyimides is applied to the technology of electrode material for super capacitor.
Background technology
[0002] ultracapacitor owing to having the incomparable high power density of conventional batteries, long circulation life and the characteristics such as pollution-free, promises to be novel green power supply in this century.Electrode material is the most key part of ultracapacitor, is also the principal element that determines its performance, and therefore developing the electrode material with excellent properties is most crucial problem in ultracapacitor research.
The organic electrode material usually can be direct or indirect synthesize by ordinary matter, be the key technology that can solve resource problem and environmental problem that Armand etc. puts forward recently.Conducting polymer is the important ultracapacitor organic electrode material of a class.In recent years, the enforcement of the synthetic technology by a large amount of advanced persons, the chemical property of conducting polymer and compound thereof has obtained larger lifting, and wherein the organic electrode such as polyaniline and polypyrrole material has progressively been realized commercialization.
Polyimides is the important but very conventional engineering plastics of a class, due to its high-insulation, is rarely used in electrode material.Yet polyimides belongs to the aroylation compound, can carry out reversible electrochemical oxidation and reduction.It contains the electro-chemical activity center amide group of quick Reversible redox reaction occurs and can stablize the skeleton structure of product, has to be applied to the primary condition that ultracapacitor carries out storage and the conversion of energy.
Summary of the invention
The purpose of this invention is to provide a kind ofOrganic polymer electrode material for super capacitor and preparation method thereof.
The present invention isOrganic polymer electrode material for super capacitor and preparation method thereof, the composition of its electrode material are the polyimides with electrical-conductive nanometer copper powder doping of multiple skeleton structure; The particle diameter of copper nanoparticle is between 1-100 nm; The electrode specific capacity is at 5 mA/cm
2Current density under be 57 ~ 80 F/g.
The organic polymer super capacitance electrode material the preparation method, the steps include:
(1) preparation of solution A: with dibasic acid anhydride and diamines according to mol ratio 1 ~ 2: 1 ~ 2 ratio is dissolved in and obtains A solution in organic solvent;
(2) preparation of solution B: copper nanoparticle is scattered in organic solvent than the ratio of 50 ml according to 0.005 ~ 0.01 mol, and through 30 min stirrings, the ultrasonic solution B that obtains;
(3) then with solution A and solution B rapid mixing, ultrasonic 30 min, at stirring condition, back flow reaction 6 ~ 8 h in organic solvent, reaction temperature is 200 ~ 210 oC; The product that obtains after filtration, ethanol washing, 120 ℃ of drying 10 ~ 12 h obtain the polyamic acid of Nanometer Copper doping in baking oven;
(4) polyamic acid that step (3) is obtained is under inert gas shielding, and 300 ~ 320 ℃ of heat treatment 6 ~ 8 h obtain the polyimides electrode material of Powdered Yellow nanometer copper doping.
Usefulness of the present invention is that a kind of engineering plastics polyimides is applied to ultracapacitor, is expected to make the organic electrode material of cheapness, high comprehensive performance, environmental protection.
The electrode material of preparation gained is carried out electro-chemical test: the ratio of active material/electrically conductive graphite=6:4 is pressed in stainless (steel) wire, then the sheet that will press is surveyed its chemical property with three-electrode system after 60 ℃ of drying 10 ~ 12 h in acidic electrolyte bath.
The organic electrode material that this Nanometer Copper doped polyimide is made, survey its cyclic voltammetry curve with three-electrode system in acidic electrolyte bath, under the sweep speed of 5 mV/s, at 0.31 V current potential place, oxidation peak is arranged, at 0.22 current potential place, reduction peak is arranged, illustrate that this electrode material is more typical fake capacitance energy storage.From 5 mA/cm
2It is 57 ~ 80 F/g than electric capacity that constant current charge-discharge curve under current density draws it.
Description of drawings
Fig. 1 is according to the present invention, the electrochemistry cyclic voltammetry curve of the polyimides of the resulting Powdered Nanometer Copper doping of embodiment 1, and in figure, abscissa is voltage, and unit is volt, and ordinate is electric current, and unit is ampere; Fig. 2 is the constant current charge-discharge curve of the polyimides of the resulting Powdered Nanometer Copper doping of the embodiment of the present invention 1, and in figure, abscissa is the time, and unit is second, and ordinate is voltage, and unit is volt.
Embodiment
The present invention isOrganic polymer electrode material for super capacitor and preparation method thereof, the composition of its electrode material are the polyimides with electrical-conductive nanometer copper powder doping of multiple skeleton structure; The particle diameter of copper nanoparticle is between 1-100 nm; The electrode specific capacity is at 5 mA/cm
2Current density under be 57 ~ 80 F/g.
The organic polymer super capacitance electrode material the preparation method, the steps include:
(1) preparation of solution A: with dibasic acid anhydride and diamines according to mol ratio 1 ~ 2: 1 ~ 2 ratio is dissolved in and obtains A solution in organic solvent;
(2) preparation of solution B: copper nanoparticle is scattered in organic solvent than the ratio of 50 ml according to 0.005 ~ 0.01 mol, and through 30 min stirrings, the ultrasonic solution B that obtains;
(3) then with solution A and solution B rapid mixing, ultrasonic 30 min, at stirring condition, back flow reaction 6 ~ 8 h in organic solvent, reaction temperature is 200 ~ 210 oC; The product that obtains after filtration, ethanol washing, 120 ℃ of drying 10 ~ 12 h obtain the polyamic acid of Nanometer Copper doping in baking oven;
(4) polyamic acid that step (3) is obtained is under inert gas shielding, and 300 ~ 320 ℃ of heat treatment 6 ~ 8 h obtain the polyimides electrode material of Powdered Yellow nanometer copper doping.
Further launch the present invention below by embodiment more specifically.
Embodiment 1:
(1) preparation of solution A: 0.01 mol Pyromellitic Acid dicarboxylic anhydride and 0.01 mol p-phenylenediamine (PPD) are dissolved in respectively in 100 ml NMP organic solvents obtain A solution respectively;
(2) preparation of solution B: copper nanoparticle 0.01 mol is scattered in 50 ml NMP organic solvents, and through 30 min stirrings, the ultrasonic solution B that obtains;
(3) then with solution A and solution B rapid mixing, ultrasonic 30 min, at stirring condition, back flow reaction 6 h in NMP, reaction temperature is 210 oC.The product that obtains after filtration, ethanol washing, dry 12 h of 120 oC obtain the polyamic acid of Nanometer Copper doping in baking oven;
(4) polyamic acid that step (3) is obtained is under argon shield, and 300 oC heat treatment 8 h obtain the polyimides of Powdered Yellow nanometer copper doping.
The electrode material of gained is carried outElectro-chemical test: the ratio of active material/electrically conductive graphite=6:4 is pressed in stainless (steel) wire, then the sheet that will press surveys its chemical property with three-electrode system after 60 dry 12 h of oC in acidic electrolyte bath, obtaining specific capacity is 80 F/g.Its cyclic voltammetry curve and constant current charge-discharge curve are with reference to accompanying drawing 1.
Embodiment 2:
(1) preparation of solution A: respectively with 0.01 mol Isosorbide-5-Nitrae, 5,8-naphthalene tetracarboxylic acid dianhydride and 0.01 mol p-phenylenediamine (PPD) are dissolved in respectively in 100 ml NMP organic solvents and obtain A solution;
(2) preparation of solution B: copper nanoparticle 0.005 mol is scattered in 50 ml NMP organic solvents, and through 30 min stirrings, the ultrasonic solution B that obtains;
(3) then with solution A and solution B rapid mixing, ultrasonic 30 min, under stirring condition, back flow reaction 8 h in DMF, reaction temperature is 200 oC.The product that obtains is through filtration, ethanol washing, and dry 12 h of 120 oC obtain the polyamic acid of Nanometer Copper doping in baking oven;
(4) polyamic acid that step (3) is obtained is under nitrogen protection, and 320 oC heat treatment 6 h obtain the polyimides of Powdered brown Nanometer Copper doping.
The electrode obtained material is carried outElectro-chemical test: the ratio of active material/electrically conductive graphite=6:4 is pressed in stainless (steel) wire, then the sheet that will press surveys its chemical property with three-electrode system after 60 dry 12 h of oC in acidic electrolyte bath, obtaining specific capacity is 64 F/g.
Embodiment 3:
(1) preparation of solution A: 0.005 mol Pyromellitic Acid dicarboxylic anhydride and 0.01 mol p-phenylenediamine (PPD) are dissolved in respectively in 100 ml NMP organic solvents obtain A solution respectively;
(2) preparation of solution B: copper nanoparticle 0.005 mol is scattered in 50ml NMP organic solvent, and through 30 min stirrings, the ultrasonic solution B that obtains;
(3) then with solution A and solution B rapid mixing, ultrasonic 30 min, under stirring condition, back flow reaction 8 h in NMP, reaction temperature is 200 oC.The product that obtains after filtration, ethanol washing, dry 12 h of 120 oC obtain the polyamic acid of Nanometer Copper doping in baking oven;
(4) polyamic acid that step (3) is obtained is under nitrogen protection, and 320 oC heat treatment 6 h obtain the polyimides of Powdered Nanometer Copper doping.
The electrode material of gained is carried outElectro-chemical test: the ratio of active material/electrically conductive graphite=6:4 is pressed in stainless (steel) wire, then the sheet that will press surveys its chemical property with three-electrode system after 60 dry 12 h of oC in acidic electrolyte bath, obtaining specific capacity is 57 F/g.
Embodiment (4):
(1) preparation of solution A: 0.01 mol Pyromellitic Acid dicarboxylic anhydride and 0.005 mol p-phenylenediamine (PPD) are dissolved in respectively in 100 ml DMF organic solvents obtain A solution respectively;
(2) preparation of solution B: copper nanoparticle 0.01 mol is scattered in 50 ml DMF organic solvents, and through 30 min stirrings, the ultrasonic solution B that obtains;
(3) then with solution A and solution B rapid mixing, ultrasonic 30 min, under stirring condition, back flow reaction 6 h in DMF, reaction temperature is 210 oC.The product that obtains is through filtration, ethanol washing, and dry 12 h of 120 oC obtain the polyamic acid of Nanometer Copper doping in baking oven;
(4) polyamic acid that step (3) is obtained is under argon shield, and 300 oC heat treatment 8 h obtain the polyimides of Powdered Nanometer Copper doping.
The electrode obtained material is carried outElectro-chemical test: the ratio of active material/electrically conductive graphite=6:4 is pressed in stainless (steel) wire, then the sheet that will press surveys its chemical property with three-electrode system after 60 dry 12 h of oC in acidic electrolyte bath, obtaining specific capacity is 72 F/g.
Embodiment 5:
(1) preparation of solution A: 0.01 mol Pyromellitic Acid dicarboxylic anhydride and 0.01 mol ethylenediamine are dissolved in respectively in 100 ml NMP organic solvents obtain A solution respectively;
(2) preparation of solution B: copper nanoparticle 0.01 mol is scattered in 50ml NMP organic solvent, and through 30 min stirrings, the ultrasonic solution B that obtains;
(3) then with solution A and solution B rapid mixing, ultrasonic 30 min, under stirring condition, back flow reaction 6 h in DMF, reaction temperature is 210 oC.The product that obtains is through filtration, ethanol washing, and dry 12 h of 120 oC obtain the polyamic acid of Nanometer Copper doping in baking oven;
(4) polyamic acid that step (3) is obtained is under argon shield, and 300 oC heat treatment 8 h obtain the polyimides of Powdered Nanometer Copper doping.
The electrode obtained material is carried outElectro-chemical test: the ratio of active material/electrically conductive graphite=6:4 is pressed in stainless (steel) wire, then the sheet that will press surveys its chemical property with three-electrode system after 60 dry 12 h of oC in acidic electrolyte bath, obtaining specific capacity is 76 F/g.
Claims (6)
1. the organic polymer electrode material for super capacitor, is characterized in that composition is the polyimides with electrical-conductive nanometer copper powder doping of multiple skeleton structure; The particle diameter of copper nanoparticle is between 1-100 nm; The electrode specific capacity is at 5 mA/cm
2Current density under be 57 ~ 80 F/g.
The organic polymer super capacitance electrode material the preparation method, the steps include:
(1) preparation of solution A: with dibasic acid anhydride and diamines according to mol ratio 1 ~ 2: 1 ~ 2 ratio is dissolved in and obtains A solution in organic solvent;
(2) preparation of solution B: copper nanoparticle is scattered in organic solvent than the ratio of 50 ml according to 0.005 ~ 0.01 mol, and through 30 min stirrings, the ultrasonic solution B that obtains;
(3) then with solution A and solution B rapid mixing, ultrasonic 30 min, at stirring condition, back flow reaction 6 ~ 8 h in organic solvent, reaction temperature is 200 ~ 210 oC; The product that obtains after filtration, ethanol washing, 120 ℃ of drying 10 ~ 12 h obtain the polyamic acid of Nanometer Copper doping in baking oven;
(4) polyamic acid that step (3) is obtained is under inert gas shielding, and 300 ~ 320 ℃ of heat treatment 6 ~ 8 h obtain the polyimides electrode material of Powdered Yellow nanometer copper doping.
Organic polymer super capacitance electrode material according to claim 2 the preparation method, it is characterized in that dibasic acid anhydride is Isosorbide-5-Nitrae, 5,8-naphthalene tetracarboxylic acid dianhydride, perhaps Pyromellitic Acid dicarboxylic anhydride.
Organic polymer super capacitance electrode material according to claim 2 the preparation method, it is characterized in that diamines is p-phenylenediamine (PPD), perhaps ethylenediamine.
Organic polymer super capacitance electrode material according to claim 2 the preparation method, it is characterized in that organic solvent is NMP, perhaps DMF.
Organic polymer super capacitance electrode material according to claim 2 the preparation method, it is characterized in that inert gas is nitrogen, perhaps argon gas.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108593737A (en) * | 2018-05-07 | 2018-09-28 | 辽宁科技大学 | Polyimides electrochemical sensing original paper and preparation method thereof and sensor |
| CN109979758A (en) * | 2019-03-01 | 2019-07-05 | 南京工业大学 | High performance electrode material for super capacitor and preparation method thereof |
| CN111634963A (en) * | 2020-07-03 | 2020-09-08 | 朱义奎 | Preparation method of iron-doped nano nickel oxide powder for super capacitor |
| CN112646181A (en) * | 2020-12-18 | 2021-04-13 | 中国电子科技集团公司第十八研究所 | Polyimide-based organic polymer cathode material polymerized in situ and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101698746A (en) * | 2009-11-20 | 2010-04-28 | 宁波今山电子材料有限公司 | Preparation method of electric-conduction polyimide film |
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- 2013-03-21 CN CN2013100939636A patent/CN103151180A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101698746A (en) * | 2009-11-20 | 2010-04-28 | 宁波今山电子材料有限公司 | Preparation method of electric-conduction polyimide film |
Non-Patent Citations (1)
| Title |
|---|
| 王淑红: "超大容量电容器的制备及性能研究", 《中国优秀硕士学位论文全文数据库（电子期刊）》, 31 January 2005 (2005-01-31), pages 042 - 135 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108593737A (en) * | 2018-05-07 | 2018-09-28 | 辽宁科技大学 | Polyimides electrochemical sensing original paper and preparation method thereof and sensor |
| CN109979758A (en) * | 2019-03-01 | 2019-07-05 | 南京工业大学 | High performance electrode material for super capacitor and preparation method thereof |
| CN111634963A (en) * | 2020-07-03 | 2020-09-08 | 朱义奎 | Preparation method of iron-doped nano nickel oxide powder for super capacitor |
| CN112646181A (en) * | 2020-12-18 | 2021-04-13 | 中国电子科技集团公司第十八研究所 | Polyimide-based organic polymer cathode material polymerized in situ and preparation method thereof |
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Application publication date: 20130612 |