CN101892530B - Preparation of polyaniline/polypyrrole composite nano fiber electrode materials with core-shell structure - Google Patents
Preparation of polyaniline/polypyrrole composite nano fiber electrode materials with core-shell structure Download PDFInfo
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Abstract
The invention relates to preparation of polyaniline/polypyrrole composite nano fiber electrode materials with core-shell structure, comprising the following steps: (1) respectively dissolving aniline and an aniline monomer initiator into a polyaniline doping agent, then merging the mixed liquor, shaking the mixed liquor to ensure the mixed liquor to react under room temperature, centrifuging and washing the reactants to obtain fibers; and (2) adding the fibers to a polypyrrole doping agent, carrying out ultrasonic dispersion and adding a pyrrole monomer under ultrasonic action, then dropwise adding the polypyrrole doping agent solution of a pyrrole monomer initiator, keeping the system temperature at 0-5 DEG C to react, centrifuging and washing the products and drying the products, thus obtaining the electrode materials. The method is simple, low in cost and suitable for industrial production. The obtained materials show higher specific capacitance and good chemical performance stability when being used in super capacitors.
Description
Technical field
The invention belongs to the preparation field of composite nano fiber electrode materials, particularly relate to a kind of preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure.
Background technology
Ultracapacitor is a kind of novel energy-storing device, and it has characteristics such as charging interval weak point, long service life, good temp characteristic, energy savings and environmental protection.Ultracapacitor has huge using value and market potential in various fields such as electric automobile, fuel combination automobile, exceptional load automobile, electric power, railway, communication, national defence, consumption electronic products.Conducting polymer is because of the dynamic process of its charge discharge fast (promptly mix and go doping process rapid), and electric charge can store in whole material volume, and cost is low than metal oxide containing precious metals, has caused people's great attention.Wherein polyaniline (being suitable for acidic electrolysis bath) and polypyrrole (being suitable for neutral electrolyte and alkaline electrolyte) have excellent chemical property, environmental friendliness, characteristics such as synthetic simple and the material that is considered to have most using value.
Research shows that the electric capacity behavior of the conducting polymer that low dimension is orderly obviously is superior to unordered conducting polymer, and its reason can ascribe its aggregated structure high-sequential to, thereby has improved its carrier mobility greatly.The common method of synthesized polyaniline and polypyrrole nano-fiber material has interfacial polymerization, template, emulsion polymerization and electrochemical polymerization method etc.; Bad prolonging like Central South University waited the preparation method who has invented a kind of polyaniline nano fiber clearly; With aniline monomer and oxidant ammonium persulfate is raw material; Utilize the polymerisation that oil/water two-phase interface takes place to prepare polyaniline material; Through optimization and control to interfacial polymerization technology, prepare diameter between 30～120nm, length is that 500nm is to several microns polyaniline nano fiber materials that do not wait (publication number is CN101016660A); Yellow border is bravely waited and is adopted template that a kind of polypyrrole nano structure electrode is provided, and on electrode base material, only covers equally distributed polypyrrole nano line array, and this array proper alignment (publication number is CN101635201A) on described base material; As compound emulsifying agent, n-butanol is an assistant for emulsifying agent to Ma Li etc. with neopelex and hydrochloric acid, and ammonium persulfate is an oxidant, and through the micro-emulsion polymerization reaction, through breakdown of emulsion, washing, drying have been synthesized nano polyaniline powder (publication number is CN1709941A); Wang Jixiao etc. are mixed with electrolyte with pyrroles, polyanion adulterant or anion doped dose of high price and supporting electrolyte; Adopt combination electrode, directly generate the polypyrrole nano line (publication number is CN1465748A) of different length and diameter with potentiostatic method or cyclic voltammetry at electrode surface.Though yet existing these methods are obtaining success aspect the preparation conductive polymer nanometer fiber; But more or less exist the some shortcomings part; Like needs in the interfacial polymerization with an organic solvent, synthetic output is lower, and need reclaim organic solvent in order to avoid cause environmental pollution; The general cost of manufacture of template is higher, when the preparation electrode, need remove template; The a large amount of emulsifying agent of normal employing in the emulsion polymerization course of reaction, last handling process is more loaded down with trivial details; And electrochemical polymerization method needs conductive base, and synthetic product is limited by electrode area.What deserves to be mentioned is the time as electrode material for super capacitor; The conducting polymer of one-component often can only just can show excellent chemical property in acidity or alkaline electrolyte; As being applicable to acidic electrolysis bath owing to polyaniline; Polypyrrole is applicable to alkaline electrolyte, though polypyrrole also can be used for neutral electrolyte, in free from corrosion neutral electrolyte, often shows relatively poor.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure, and this method is simple, and cost is low, is suitable for suitability for industrialized production; The gained material is used for ultracapacitor, shows higher specific capacitance and good stable chemical performance property.
A kind of preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure of the present invention comprises:
(1) gets aniline and aniline monomer initator and be dissolved in respectively in the Polyaniline Doped agent, merge mixed liquor then; Rock, react 5～90min under the room temperature; Product through centrifugal with the washing until neutrality, prepare polyaniline nano fiber;
(2) get above-mentioned polyaniline nano fiber and add in the doped polypyrrole agent, ultrasonic dispersion, and under ultrasonication, add pyrrole monomer, at the uniform velocity drip the doped polypyrrole agent solution of pyrrole monomer initator then; Keep system temperature at 0～5 ℃ in the ultrasonic procedure, reaction 10～60min; Product through centrifugal with the washing after being neutrality, drying promptly gets the polyaniline/polypyrrole composite nano fiber electrode materials with nucleocapsid structure;
The mol ratio of said aniline and initator is 1～6: 1; The mol ratio of aniline and Polyaniline Doped agent is 1: 5～20; The mol ratio of aniline and pyrrole monomer is 1～10: 1; The mol ratio of pyrrole monomer and initator is 1～6: 1; The mol ratio of pyrrole monomer and doped polypyrrole agent is 1: 5～20.
Polyaniline Doped agent in the said step (1) is a kind of in hydrochloric acid, sulfuric acid, phosphoric acid, sulfosalicylic acid, p-methyl benzenesulfonic acid, camphorsulfonic acid, the DBSA.
Aniline monomer initator in the said step (1) is a kind of in ammonium persulfate, ferric trichloride, hydrogen peroxide, bichromate, the benzoyl peroxide.
The speed that said step (1) is rocked is per second 1～5 time.
Doped polypyrrole agent in the said step (2) is a kind of in hydrochloric acid, potassium chloride, sodium chloride, ammonium chloride, sodium nitrate, sodium sulphate, sodium phosphate, DBSA, neopelex, p-methyl benzenesulfonic acid, the p-methyl benzenesulfonic acid sodium etc.
Pyrrole monomer initator in the said step (2) is ammonium sulfate or ferric trichloride.
The doped polypyrrole agent solution of the pyrrole monomer initator in the said step (2) is dissolved in the solution that obtains in the doped polypyrrole agent for the pyrrole monomer initator.
Rate of addition in the said step (2) is 1～5ml/min.
Drying condition in the said step (2) is dry 24h-48h in the 60-80 ℃ of vacuum.
Electrode material in the said step (2) hot pressing 30min under 60 ℃, the pressure of 5MPa is pressed into electrode on nickel foam; With the Pt electrode for being that reference electrode is formed three-electrode system to electrode, Ag/AgCl; Electrolyte is the aqueous solution of potassium chloride, sodium chloride, lithium sulfate, sodium sulphate, potassium sulfate, phosphorus hexafluoride acid lithium, lithium perchlorate, potassium hyperchlorate or their mixture.
As electrode material for super capacitor the time, the strong interaction power height-oriented and that exist between the two of polyaniline and polypyrrole has improved electric charge transfer rate and the charge storage capacity in the charge and discharge process, greatly particularly in neutral electrolyte; Its chemical property and cyclical stability can be regulated and control through the polypyrrole thickness of polyaniline fiber size and polyaniline superficial deposit.
The present invention earlier in the aqueous solution under oscillating condition in-situ polymerization prepare polyaniline nano fiber, again with polyaniline nano fiber be " seed " at the aqueous polymerization polypyrrole, be formed with the polyaniline/polypyrrole composite nano fiber of nucleocapsid structure.
Beneficial effect
(1) preparation method of the present invention is simple and easy to operate, and is with low cost, is suitable for suitability for industrialized production;
(2) the present invention compares with existing conductive polymer nanometer fiber production method and has distinguishing feature; Whole polymerisation is carried out at aqueous phase; Need not template and surfactant; What prepare is the polyaniline/polypyrrole composite nano fiber that nucleocapsid structure is arranged, and the structure of nanofiber can be regulated and control through the monomer concentration of polyaniline and polypyrrole.
(3) polyaniline/polypyrrole composite nano fiber electrode materials with nucleocapsid structure that the present invention makes combines polyaniline and the excellent performance of polypyrrole effectively, and brings into play its cooperative effect; This material is specially adapted to neutral electrolyte, has avoided acidity or alkaline electrolyte to leak corrosion and the pollution that is brought; This composite nano fiber electrode materials shows good electrochemical behavior in neutral potassium sulfate electrolyte, its high specific capacitance can reach 430F/g, after circulation 1000 times, is no more than 20% than the decay of capacitance.
Description of drawings
Fig. 1 has the sem photograph of the polyaniline/polypyrrole composite nano fiber of nucleocapsid structure;
Fig. 2 has the cyclic voltammetry curve of polyaniline/polypyrrole composite nano fiber electrode materials in potassium sulfate solution of nucleocapsid structure.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Accurately take by weighing 0.02mol aniline and 0.02mol ammonium persulfate and be dissolved in respectively in the 1M hydrochloric acid solution of 100ml, two kinds of solution are mixed, the speed with per second 1 time under the room temperature is rocked, and the reaction time is controlled at 5min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M hydrochloric acid solution of 100ml; Ultrasonic 30min; Then the 0.005mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 0 ℃, the 0.005mol ferric trichloride in the 1M hydrochloric acid solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 40min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 60 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, sodium chloride is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 254F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 25% after 1000 times.
Accurately take by weighing 0.005mol aniline and 0.005mol ferric trichloride and be dissolved in respectively in the 1M hydrochloric acid solution of 100ml, two kinds of solution are mixed, the speed with per second 3 times under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M hydrochloric acid solution of 100ml; Ultrasonic 30min; Then the 0.005mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 0 ℃, the 0.005mol ferric trichloride in the 1M hydrochloric acid solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 40min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 60 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, potassium chloride is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 263F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 25% after 1000 times.
Embodiment 3
Accurately take by weighing 0.02mol aniline and 0.02mol potassium bichromate and be dissolved in respectively in the 1M hydrochloric acid solution of 100ml, two kinds of solution are mixed, the speed with per second 5 times under the room temperature is rocked, and the reaction time is controlled at 20min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M hydrochloric acid solution of 100ml; Ultrasonic 30min; Then the 0.005mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 5 ℃, the 0.005mol ferric trichloride in the 1M hydrochloric acid solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 40min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 60 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, lithium perchlorate is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 333F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 21% after 1000 times.
Accurately take by weighing 0.02mol aniline and 0.01mol Ammonium Persulfate 98.5 and be dissolved in respectively in the 1M p-methyl benzenesulfonic acid solution of 100ml, two kinds of solution are mixed, the speed with per second 1 time under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M hydrochloric acid solution of 100ml; Ultrasonic 30min; Then the 0.005mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 5 ℃, the 0.005mol ferric trichloride in the 1M hydrochloric acid solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 40min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 60 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, sodium chloride is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 298F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 24% after 1000 times.
Embodiment 5
Accurately take by weighing 0.02mol aniline and 0.005mol ammonium persulfate and be dissolved in respectively in the 1M dodecylbenzenesulfonic acid solution of 100ml, two kinds of solution are mixed, the speed with per second 5 times under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M hydrochloric acid solution of 100ml; Ultrasonic 30min; Then the 0.005mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 0 ℃, the 0.005mol ferric trichloride in the 1M hydrochloric acid solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 40min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 60 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, potassium chloride is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 287F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 22% after 1000 times.
Embodiment 6
Accurately take by weighing 0.01mol aniline and 0.01mol ferric trichloride and be dissolved in respectively in the 1M hydrochloric acid solution of 100ml, two kinds of solution are mixed, the speed with per second 5 times under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M sodium chloride solution of 100ml; Ultrasonic 30min; Then the 0.005mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 5 ℃, the 0.0025mol ferric trichloride in the 1M sodium chloride solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 40min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 60 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, potassium sulfate is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 345F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 20% after 1000 times.
Embodiment 7
Accurately take by weighing 0.02mol aniline and 0.02mol Ammonium Persulfate 98.5 and be dissolved in respectively in the 1M camphorsulfonic acid solution of 100ml, two kinds of solution are mixed, the speed with per second 3 times under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M sodium chloride solution of 100ml; Ultrasonic 30min; Then the 0.01mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 0 ℃, the 0.0025mol ferric trichloride in the 1M sodium chloride solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 40min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 60 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, potassium hyperchlorate is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 377F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 22% after 1000 times.
Embodiment 8
Accurately take by weighing 0.02mol aniline and 0.02mol ferric trichloride and be dissolved in respectively in the 1M camphorsulfonic acid solution of 100ml, two kinds of solution are mixed, the speed with per second 1 time under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M dodecylbenzenesulfonic acid solution of 100ml; Ultrasonic 30min; Then the 0.02mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 0 ℃, the 0.0025mol ferric trichloride in the 1M sodium chloride solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 40min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 60 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, potassium chloride is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 288F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 25% after 1000 times.
Embodiment 9
Accurately take by weighing 0.02mol aniline and 0.02mol ferric trichloride and be dissolved in respectively in the 1M hydrochloric acid solution of 100ml, two kinds of solution are mixed, the speed with per second 5 times under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M sodium chloride solution of 100ml; Ultrasonic 30min; Then the 0.02mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 0 ℃, the 0.005mol ferric trichloride in the 1M hydrochloric acid solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 40min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 60 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, sodium sulphate is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 403F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 20% after 1000 times.
Embodiment 10
Accurately take by weighing 0.02mol aniline and 0.02mol ammonium persulfate and be dissolved in respectively in the 1M hydrochloric acid solution of 100ml, two kinds of solution are mixed, the speed with per second 3 times under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M hydrochloric acid solution of 100ml; Ultrasonic 30min; Then the 0.02mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 0 ℃, the 0.01mol ferric trichloride in the 1M hydrochloric acid solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 40min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 60 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, potassium hyperchlorate is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 399F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 21% after 1000 times.
Embodiment 11
Accurately take by weighing 0.02mol aniline and 0.02mol ammonium persulfate and be dissolved in respectively in the 1M dodecylbenzenesulfonic acid solution of 100ml, two kinds of solution are mixed, the speed with per second 5 times under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M p-methyl benzenesulfonic acid sodium solution of 100ml; Ultrasonic 30min; Then the 0.02mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 0 ℃, the 0.02mol ammonium persulfate in the 1M hydrochloric acid solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 30min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 60 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, potassium sulfate is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 419F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 20% after 1000 times.
Embodiment 12
Accurately take by weighing 0.02mol aniline and 0.02mol ammonium persulfate and be dissolved in respectively in the 1M dodecylbenzenesulfonic acid solution of 100ml, two kinds of solution are mixed, the speed with per second 1 time under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M sodium chloride solution of 100ml; Ultrasonic 30min; Then the 0.02mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 0 ℃, the 0.02mol ammonium persulfate in the 1M hydrochloric acid solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 50min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 60 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, sodium chloride is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 366F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 21% after 1000 times.
Embodiment 13
Accurately take by weighing 0.02mol aniline and 0.02mol ammonium persulfate and be dissolved in respectively in the 1M dodecylbenzenesulfonic acid solution of 100ml, two kinds of solution are mixed, the speed with per second 5 times under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M p-methyl benzenesulfonic acid sodium solution of 100ml; Ultrasonic 30min; Then the 0.02mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 0 ℃, the 0.02mol ammonium persulfate in the 1M hydrochloric acid solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 60min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 80 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, potassium hyperchlorate is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 299F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 22% after 1000 times.
Embodiment 14
Accurately take by weighing 0.02mol aniline and 0.02mol ammonium persulfate and be dissolved in respectively in the 1M hydrochloric acid solution of 100ml, two kinds of solution are mixed, the speed with per second 3 times under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M p-methyl benzenesulfonic acid sodium solution of 100ml; Ultrasonic 30min; Then the 0.02mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 0 ℃, the 0.02mol ammonium persulfate in the 1M hydrochloric acid solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 40min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 48h in 80 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, the mixed liquor of potassium hyperchlorate and potassium chloride is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 347F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 22% after 1000 times.
Embodiment 15
Accurately take by weighing 0.02mol aniline and 0.02mol ammonium persulfate and be dissolved in respectively in the 1M sulfosalicylic acid solution of 100ml, two kinds of solution are mixed, the speed with per second 5 times under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M hydrochloric acid solution of 100ml; Ultrasonic 30min; Then the 0.02mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 0 ℃, the 0.02mol ferric trichloride in the 1M hydrochloric acid solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 40min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 80 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.With the Pt electrode for being reference electrode to electrode, Ag/AgCl; The mixed liquor of potassium sulfate and potassium chloride is that electrolyte is formed three-electrode system; Under the sweep speed of 1mV/s, the ratio capacitance that records is about 357F/g, and circulating, the decay than capacitance is no more than 24% after 1000 times.
Claims (10)
1. preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure comprises:
(1) gets aniline and aniline monomer initator and be dissolved in respectively in the Polyaniline Doped agent, merge mixed liquor then; Rock, react 5～90min under the room temperature; Product through centrifugal with the washing until neutrality, prepare polyaniline nano fiber;
(2) get above-mentioned polyaniline nano fiber and add in the doped polypyrrole agent, ultrasonic dispersion, and under ultrasonication, add pyrrole monomer, at the uniform velocity drip the doped polypyrrole agent solution of pyrrole monomer initator then; Keep system temperature at 0～5 ℃ in the ultrasonic procedure, reaction 10～60min; Product through centrifugal with the washing after being neutrality, drying promptly gets the polyaniline/polypyrrole composite nano fiber electrode materials with nucleocapsid structure;
The mol ratio of said aniline and initator is 1～6: 1; The mol ratio of aniline and Polyaniline Doped agent is 1: 5～20; The mol ratio of aniline and pyrrole monomer is 1～10: 1; The mol ratio of pyrrole monomer and initator is 1～6: 1; The mol ratio of pyrrole monomer and doped polypyrrole agent is 1: 5～20.
2. a kind of preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure according to claim 1 is characterized in that: the Polyaniline Doped agent in the said step (1) is a kind of in hydrochloric acid, sulfuric acid, phosphoric acid, sulfosalicylic acid, p-methyl benzenesulfonic acid, camphorsulfonic acid, the DBSA.
3. a kind of preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure according to claim 1 is characterized in that: the aniline monomer initator in the said step (1) is a kind of in ammonium persulfate, ferric trichloride, hydrogen peroxide, bichromate, the benzoyl peroxide.
4. a kind of preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure according to claim 1 is characterized in that: the speed that said step (1) is rocked is per second 1～5 time.
5. a kind of preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure according to claim 1 is characterized in that: the doped polypyrrole agent in the said step (2) is a kind of in hydrochloric acid, potassium chloride, sodium chloride, ammonium chloride, sodium nitrate, sodium sulphate, sodium phosphate, DBSA, neopelex, p-methyl benzenesulfonic acid, the p-methyl benzenesulfonic acid sodium.
6. a kind of preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure according to claim 1 is characterized in that: the pyrrole monomer initator in the said step (2) is ammonium persulfate or ferric trichloride.
7. a kind of preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure according to claim 1 is characterized in that: the rate of addition in the said step (2) is 1～5ml/min.
8. a kind of preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure according to claim 1 is characterized in that: the drying condition in the said step (2) is dry 24h-48h in the 60-80 ℃ of vacuum.
9. a kind of preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure according to claim 1 is characterized in that: the electrode material that makes in the said step (2) hot pressing 30min under 60 ℃, the pressure of 5MPa is pressed into electrode on nickel foam; With the Pt electrode for being that reference electrode is formed three-electrode system to electrode, Ag/AgCl; Electrolyte is the aqueous solution of potassium chloride, sodium chloride, lithium sulfate, sodium sulphate, potassium sulfate, phosphorus hexafluoride acid lithium, lithium perchlorate, potassium hyperchlorate or their mixture.
10. a kind of preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure according to claim 1 is characterized in that: the electrode material that said step (2) makes is used for ultracapacitor.
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