CN102280265A - Method for preparing metatitanic acid doped polyaniline combined electrode nanomaterial for super capacitor - Google Patents
Method for preparing metatitanic acid doped polyaniline combined electrode nanomaterial for super capacitor Download PDFInfo
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- CN102280265A CN102280265A CN2011101377919A CN201110137791A CN102280265A CN 102280265 A CN102280265 A CN 102280265A CN 2011101377919 A CN2011101377919 A CN 2011101377919A CN 201110137791 A CN201110137791 A CN 201110137791A CN 102280265 A CN102280265 A CN 102280265A
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Abstract
The invention relates to a method for preparing a metatitanic acid doped polyaniline combined electrode nanomaterial for a super capacitor and electrochemical performance analysis for the nanomaterial, belonging to the field of preparation of electrode materials of the super capacitor. In the invention, an in-situ chemical polymerization method is used for preparing the metatitanic acid doped polyaniline combined electrode nanomaterial with a coralliform shape and a uniform dimension to serve as an anode material, activated carbon serves as a cathode material, the anode material and the cathode material are assembled into an asymmetrical super capacitor, and a comprehensive performance analysis test is performed. Results from the embodiment of the invention show that the metatitanic acid doped polyaniline combined electrode nanomaterial has the discharge specific capacitance reaching over 90F/g and the cycle life reaching over 2000 times, the specific capacitance value of the metatitanic acid doped polyaniline combined electrode nanomaterial is always stabilized to be over 90% of an initial value in a cyclic process, and the metatitanic acid doped polyaniline combined electrode nanomaterial has a practical application value.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the nanometer metatitanic acid doped polyaniline combination electrode material of ultracapacitor, belong to the electrode material preparation field of ultracapacitor.
Background technology
The performance of ultracapacitor is between secondary lithium battery and traditional capacitor, its power density is far above common batteries (10～100 times), energy density is far above traditional capacitor (＞100 times), can emit the electric current of hundreds of at short notice, be suitable for very much the occasion of short time high power output to several kiloamperes.
The multiphase solid material that composite material is normally formed by the combinations of substances of two or more different physics and chemical property.Though wherein each component keeps relative independentability, character be not simply adding of each component property and, but on the basis of some characteristic that keeps each component material, have the combination property that acts synergistically and produced between component.Because learning from other's strong points to offset one's weaknesses between each component of composite material fully remedied the shortcoming of homogenous material, produced the not available new capability of homogenous material.Therefore, the application of composite material in ultracapacitor can improve the deficiency of unitary electrode material.
In recent years, conducting polymer is swift and violent as a kind of new function macromolecule development, and it has broken organic polymer can not be as this traditional concept of conductor.In all conducting polymer composites, polyaniline is cheap and easy to get because of its raw material, and synthetic method is simple, and environmental stability and good light, electrical characteristics are preferably arranged, and becomes one of the most promising conducting polymer gradually.Electrically conductive polyaniline has attracted a large amount of researchers as a kind of application of novel polymer material in chemical power source and electrochemical capacitor of excellent performance, theory reaches 750F/g than capacitance, become current research focus, be considered to the conducting polymer that is hopeful to be applied in practice most.
Though conducting polymer materials is easy to processing and manufacturing, specific energy height, its cyclical stability is relatively poor, must in polyaniline, mix other cyclical stabilities preferably material improve the combination property of conducting polymer.
Nano material has bigger specific area and stronger interface interaction, and nano composite material shows mechanics, calorifics, electricity, magnetics and the optical property that is different from general macroscopical composite material especially, also may have property and function that stock blend does not possess.Nanometer metatitanic acid particle electrochemical properties is more stable, can be applicable in the energy storage device.
The present invention combines the characteristic of conducting polymer and nano material, adopt the in-situ chemical polymerization that the raw material of industry nanometer metatitanic acid of cheapness is doped in the polyaniline, prepared nanometer metatitanic acid doped polyaniline combination electrode material, with it is positive pole, active carbon is a negative pole, be assembled into the ultracapacitor of mixed type, analyze its charge-discharge performance and cyclical stability.Compare with single polyaniline electrode material, the ratio electric capacity of nanometer metatitanic acid doped polyaniline combination electrode material is higher, and charge-discharge performance and cyclical stability under big electric current are better.Therefore, nanometer metatitanic acid doped polyaniline combination electrode material is fit to the electrode material of development as ultracapacitor.
Summary of the invention
The objective of the invention is to prepare a kind of combination electrode material, for the present problem of the cyclical stability difference of ultracapacitor conductive polymer electrodes material provides a kind of effective solution.Technology of the present invention is simple, and is with low cost, is easy to commercial the application.
The preparation method and the performance evaluation of the nanometer metatitanic acid doped polyaniline combination electrode material that is used for ultracapacitor that the present invention proposes are achieved through the following technical solutions:
1, aniline (Ani) is added to the acid solution that is made into aniline in the deionized water with acid.
2, the acid solution with the Ani of step 1 is moved in the there-necked flask of 0～5 ℃ of ice-water bath, add the metatitanic acid nano particle (raw material of industry therein, the preparation method: with industrial sulphuric acid oxygen titanium is raw material, get 100～125 ℃ of pyrohydrolysis a few hours), the solidliquid mixture of formation aniline-acid-metatitanic acid nano particle.
3, with the solidliquid mixture in the step 2 at 0.2～0.5W/cm
2Ultrasonic 0.5～1h under the power carries out mechanical agitation to it simultaneously, and the metatitanic acid nano particle is uniformly dispersed in solution.
4, logical nitrogen to remove the air in the there-necked flask, is avoided the influence of air to polymerization reaction in the solidliquid mixture that is fully disperseed in step 3, simultaneously this solidliquid mixture of high-speed stirred.
5, initator and acid are added to the acid solution that is made into initator in the deionized water of 100ml together.
6, the acid solution with initator in the step 5 slowly is added dropwise in the solidliquid mixture of step 4 high speed stirring by dropping funel, and the control rate of addition is 10d/min, and guarantees that the solution in the dropping funel drips end in 3h.
7, the entire reaction device of step 6 is put in low-temp reaction a period of time in 0～5 ℃ the ice-water bath, when the acid solution of the initator in the dropping funel drip finish after, the temperature remains within the normal range again stirs a period of time, and polymerization reaction is carried out fully.
8, the product in the suction filtration step 7, earlier colourless to filtrate with the acid elution of 0.01mol/L, again with the acetone cyclic washing to remove unreacted organic substance and oligomer completely, be colourless until filtrate, wash with a large amount of alcohol at last.
9, the washed product in 60 ℃ of vacuum drying step 8 is ground, 200 orders sieve again, and finally obtaining blackish green powder is nanometer metatitanic acid doped polyaniline combination electrode material.
10, with the nanometer metatitanic acid doped polyaniline combination electrode material in the step 9 as active material, add a certain proportion of conductive agent acetylene black and binding agent Kynoar (PVDF).Three's mass ratio is 7～8: 1.5～2.5: 0.5.
11, all material in the step 10 is placed an amount of N-methyl pyrrolidone (NMP), after mechanical high-speed stirs 3～6h, with the method for scraper coating with the slurry curtain coating on aluminium foil, diaphragm thickness is 100～400um, and 60 ℃ of drying 1～3h obtain the electrode diaphragm A of nanometer metatitanic acid doped polyaniline combination electrode material.
12, be active material with the commerce active carbon, add a certain proportion of conductive agent acetylene black and binding agent Kynoar (PVDF).Three's mass ratio is 8: 1.5: 0.5.With the method for step 11, make the electrode diaphragm B of active carbon.
13, be positive pole with the electrode diaphragm A in the step 11, the electrode diaphragm B in the step 12 is a negative pole, is assembled into asymmetric ultracapacitor in glove box.Organic solvent in the electrolyte is one or both mixed liquors in ethyl carbonate, dimethyl carbonate, propene carbonate, the acetonitrile; Electrolyte is LiClO
4, in the tetraethyl tetrafluoro boric acid amine, trimethyl ethyl tetrafluoro boric acid amine one or more.Barrier film is the polypropylene porous membrane of ultracapacitor special use.
14, the ultracapacitor with assembling in the step 13 carries out electrochemical property test.The test condition that discharges and recharges: current density is that 0.1～10A/g, operating voltage interval are 0～0.8V; The cyclic voltammetric test condition: sweep speed is that 10～100mV/s, operating voltage are-0.8～0.8V.
The addition of aniline is 2～4.56ml in the described step 1, and the addition of acid is 8.3～16.5ml, and the addition of deionized water is 100～200ml;
The addition of the nanometer metatitanic acid particle in the described step 2 is 0.225～0.9g;
The addition of the initator in the described step 5 is 2.567～4.56g, and the addition of acid is 8.3～16.5ml, and the addition of deionized water is 100～200ml;
The low-temp reaction time in the described step 7 is 2～3h, and the stirring at normal temperature time is 16～24h;
Acid in described step 1, step 5 and the step 8 is that mass fraction is one or more of 38% concentrated hydrochloric acid, sulfuric acid, dodecyl sodium sulfonate, DBSA, camphorsulfonic acid;
Initator in the described step 5 is one or more of ammonium persulfate, hydrogen peroxide, cerous sulfate, Potassiumiodate, potassium bichromate.
By the enforcement of above scheme, the present invention compared with prior art has following advantage:
1, the nanometer metatitanic acid doped polyaniline combination electrode material of the present invention preparation has higher ratio electric capacity and energy density when being used for the positive electrode of ultracapacitor, and good cycling stability is better than single polyaniline electrode material.
2, the present invention is raw material with aniline, ammonium persulfate and the industrial metatitanic acid nano particle of cheapness, prepares combination electrode material with the in-situ chemical polymerization, and technology is simple, and is with low cost, is easy to commercial the application.
Description of drawings
Fig. 1 is the stereoscan photograph of the nanometer metatitanic acid doped polyaniline combination electrode material of preparation among this method embodiment 2;
Fig. 2 is the charging and discharging curve of nanometer metatitanic acid doped polyaniline combination electrode material under different multiplying of preparation among this method embodiment 2;
Fig. 3 is the cycle characteristics curve of the nanometer metatitanic acid doped polyaniline combination electrode material of preparation among this method embodiment 2;
Fig. 4 is the cyclic voltammetry scan curve of the nanometer metatitanic acid doped polyaniline combination electrode material of preparation among this method embodiment 2;
Fig. 5 is the ac impedance measurement curve of the nanometer metatitanic acid doped polyaniline combination electrode material of preparation among this method embodiment 2.
Embodiment
Embodiment 1
Be made into the sulfuric acid solution of Ani in the deionized water that aniline (Ani) and the 8.3ml sulfuric acid of 2ml is added to 100ml together, and be moved in the there-necked flask of ice-water bath, the nanometer metatitanic acid particle that adds 0.225g therein, the solidliquid mixture of formation aniline-sulfuric acid-nanometer metatitanic acid particle.This solidliquid mixture is at 0.2W/cm
2Ultrasonic 0.5h under the power carries out mechanical agitation to it simultaneously, and nanometer metatitanic acid particle is uniformly dispersed in solution.Disperse to finish back logical nitrogen in solidliquid mixture, to remove the air in the there-necked flask, avoid the influence of air, simultaneously this solidliquid mixture of high-speed stirred polymerization reaction.Be made into the sulfuric acid solution of APS in the deionized water that ammonium persulfate (APS) and the 8.3ml sulfuric acid of 2.567g is added to 100ml together, move in the dropping funel, slowly be added dropwise in the solidliquid mixture in the there-necked flask and high-speed stirred, the control rate of addition is 10d/min, drips end to guarantee the solution in the dropping funel in 3h.The entire reaction device is put in the ice-water bath, and the low-temp reaction time is 2h.After the sulfuric acid solution of the APS in the dropping funel dripped end, the temperature remains within the normal range again stirred 16h.The suction filtration product, earlier colourless to filtrate with the sulfuric acid scrubbing of 0.01mol/L, again with the acetone cyclic washing to remove unreacted organic substance and oligomer completely, be colourless until filtrate, wash with a large amount of alcohol at last.60 ℃ of vacuumize washed product, grinding, 200 orders sieve again, and finally obtaining blackish green powder is nanometer metatitanic acid doped polyaniline combination electrode material.
With the preparation nanometer metatitanic acid doped polyaniline combination electrode material as active material, according to the mass ratio of active material, acetylene black and Kynoar (PVDF) is to join in an amount of NMP at 7: 2.5: 0.5, after mechanical high-speed stirs 3h, with the method for scraper coating with the slurry curtain coating on aluminium foil, diaphragm thickness is 100um, and 60 ℃ of dry 3h can obtain the electrode diaphragm A of nanometer metatitanic acid doped polyaniline combination electrode material.With the commerce active carbon is active material, is 8: 1.5: 0.5 according to the mass ratio of active material, acetylene black and Kynoar (PVDF), makes the electrode diaphragm B of active carbon with identical method.With electrode diaphragm A is positive pole, and electrode diaphragm B is a negative pole, is assembled into asymmetric ultracapacitor in glove box.The organic electrolyte that adopts is 1mol/L LiClO
4Be dissolved in the propene carbonate.Barrier film is the polypropylene porous membrane of ultracapacitor special use.The ultracapacitor of assembling is carried out electrochemical property test.The test condition that discharges and recharges: current density is that 0.1A/g, operating voltage interval are 0～0.8V; The cyclic voltammetric test condition: sweep speed is that 10mV/s, operating voltage are-0.8～0.8V.
Embodiment 2
With the aniline (Ani) of 4.5ml and 16.5ml mass fraction is that 38% concentrated hydrochloric acid is added to the hydrochloric acid solution that is made into Ani in the deionized water of 100ml together, and be moved in the there-necked flask of ice-water bath, the nanometer metatitanic acid particle that adds 0.9g therein, the solidliquid mixture of formation aniline-watery hydrochloric acid-nanometer metatitanic acid particle.This solidliquid mixture is at 0.5W/cm
2Ultrasonic 1h under the power carries out mechanical agitation to it simultaneously, and nanometer metatitanic acid particle is uniformly dispersed in solution.Disperse to finish back logical nitrogen in solidliquid mixture, to remove the air in the there-necked flask, avoid the influence of air, simultaneously this solidliquid mixture of high-speed stirred polymerization reaction.With the ammonium persulfate (APS) of 4.56g and 16.5ml mass fraction is that 38% concentrated hydrochloric acid is added to the hydrochloric acid solution that is made into APS in the deionized water of 100ml together, move in the dropping funel, slowly be added dropwise in the solidliquid mixture of there-necked flask high speed stirring, the control rate of addition is 10d/min, drips end to guarantee the solution in the dropping funel in 3h.In the ice-water bath that the entire reaction device is put in, its reaction time is 3h.After the hydrochloric acid solution of the APS in the dropping funel dripped end, the temperature remains within the normal range again stirred 24h.The suction filtration product, earlier colourless to filtrate with the salt acid elution of 0.01mol/L, again with the acetone cyclic washing to remove unreacted organic substance and oligomer completely, be colourless until filtrate, wash with a large amount of alcohol at last.60 ℃ of vacuumize washed product, grinding, 200 orders sieve again, and finally obtaining blackish green powder is nanometer metatitanic acid doped polyaniline combination electrode material.
With the preparation nanometer metatitanic acid doped polyaniline combination electrode material as active material, according to the mass ratio of active material, acetylene black and Kynoar (PVDF) is to join in an amount of NMP at 8: 1.5: 0.5, after mechanical high-speed stirs 3h, with the method for scraper coating with the slurry curtain coating on aluminium foil, diaphragm thickness is 300um, and 60 ℃ of dry 3h can obtain the electrode diaphragm A of nanometer metatitanic acid doped polyaniline combination electrode material.With the commerce active carbon is active material, is 8: 1.5: 0.5 according to the mass ratio of active material, acetylene black and Kynoar (PVDF), makes the electrode diaphragm B of active carbon with identical method.With electrode diaphragm A is positive pole, and electrode diaphragm B is a negative pole, is assembled into asymmetric ultracapacitor in glove box.The organic electrolyte that adopts is 1mol/L LiClO
4Be dissolved in the propene carbonate.Barrier film is the polypropylene porous membrane of ultracapacitor special use.The ultracapacitor of assembling is carried out electrochemical property test.The test condition that discharges and recharges: current density is that 0.5A/g, operating voltage interval are 0～0.8V; The cyclic voltammetric test condition: sweep speed is that 50mV/s, operating voltage are-0.8～0.8V.The SEM sign photo of nanometer metatitanic acid doped polyaniline combination electrode material, charging and discharging curve, cycle characteristics curve, cyclic voltammetry curve and ac impedance measurement figure under the different multiplying are respectively as Fig. 1, Fig. 2, Fig. 3, Fig. 4 and shown in Figure 5.
Embodiment 3
Be made into the dodecyl sodium sulfonate solution of Ani in the deionized water that aniline (Ani) and the 8.3g dodecyl sodium sulfonate of 3.5ml is added to 200ml together, and be moved in the there-necked flask of ice-water bath, the nanometer metatitanic acid particle that adds 0.6g therein, the solidliquid mixture of formation aniline-dodecyl sodium sulfonate-nanometer metatitanic acid particle.This solidliquid mixture is at 0.5W/cm
2Ultrasonic 0.5h under the power carries out mechanical agitation to it simultaneously, and nanometer metatitanic acid particle is uniformly dispersed in solution.Disperse to finish back logical nitrogen in solidliquid mixture, to remove the air in the there-necked flask, avoid the influence of air, simultaneously this solidliquid mixture of high-speed stirred polymerization reaction.Be made into the dodecyl sodium sulfonate solution of cerous sulfate in the deionized water that cerous sulfate and the 8.3g dodecyl sodium sulfonate of 3.8g is added to 100ml together, move in the dropping funel, slowly be added dropwise in the solidliquid mixture of there-necked flask high speed stirring, the control rate of addition is 10d/min, drips end to guarantee the solution in the dropping funel in 3h.The entire reaction device is put in the ice-water bath, and the low-temp reaction time is 2h.After the dodecyl sodium sulfonate solution of the cerous sulfate in the dropping funel dripped end, the temperature remains within the normal range again stirred 24h.The suction filtration product, earlier colourless to filtrate with the dodecyl sodium sulfonate solution washing of 0.01mol/L, again with the acetone cyclic washing to remove unreacted organic substance and oligomer completely, be colourless until filtrate, wash with a large amount of alcohol at last.60 ℃ of vacuumize washed product, grinding, 200 orders sieve again, and finally obtaining blackish green powder is nanometer metatitanic acid doped polyaniline combination electrode material.
With the preparation nanometer metatitanic acid doped polyaniline combination electrode material as active material, according to the mass ratio of active material, acetylene black and Kynoar (PVDF) is to join in an amount of NMP at 7.5: 2: 0.5, after mechanical high-speed stirs 3h, with the method for scraper coating with the slurry curtain coating on aluminium foil, diaphragm thickness is 300um, and 60 ℃ of dry 3h can obtain the electrode diaphragm A of nanometer metatitanic acid doped polyaniline combination electrode material.With the commerce active carbon is active material, is 8: 1.5: 0.5 according to the mass ratio of active material, acetylene black and Kynoar (PVDF), makes the electrode diaphragm B of active carbon with identical method.With electrode diaphragm A is positive pole, and electrode diaphragm B is a negative pole, is assembled into asymmetric ultracapacitor in glove box.The organic electrolyte that adopts is that 1mol/L tetraethyl tetrafluoro boric acid amine is dissolved in the acetonitrile.Barrier film is the polypropylene porous membrane of ultracapacitor special use.The ultracapacitor of assembling is carried out electrochemical property test.The test condition that discharges and recharges: current density is that 2A/g, operating voltage interval are 0～0.8V; The cyclic voltammetric test condition: sweep speed is that 30mV/s, operating voltage are-0.8～0.8V.
Embodiment 4
Be made into the phosphoric acid solution of Ani in the deionized water that aniline (Ani) and the 16.5g phosphoric acid of 4ml is added to 100ml together, and be moved in the there-necked flask of ice-water bath, the nanometer metatitanic acid particle that adds 0.75g therein, the solidliquid mixture of formation aniline-phosphoric acid-nanometer metatitanic acid particle.This solidliquid mixture is at 0.5W/cm
2Ultrasonic 1h under the power carries out mechanical agitation to it simultaneously, and nanometer metatitanic acid particle is uniformly dispersed in solution.Disperse to finish back logical nitrogen in solidliquid mixture, to remove the air in the there-necked flask, avoid the influence of air, simultaneously this solidliquid mixture of high-speed stirred polymerization reaction.Be made into the phosphoric acid solution of Potassiumiodate in the deionized water that Potassiumiodate and the 16.5g phosphoric acid of 4.2g is added to 100ml together, move in the dropping funel, slowly be added dropwise in the solidliquid mixture of there-necked flask high speed stirring, the control rate of addition is 10d/min, drips end to guarantee the solution in the dropping funel in 3h.The entire reaction device is put in the ice-water bath, and the low-temp reaction time is 3h.After the phosphoric acid solution of the Potassiumiodate in the dropping funel dripped end, the temperature remains within the normal range again stirred 24h.The suction filtration product, wash to filtrate earlier with the phosphoric acid solution of rare 0.01mol/L colourless, again with the acetone cyclic washing to remove unreacted organic substance and oligomer completely, be colourless until filtrate, wash with a large amount of alcohol at last.60 ℃ of vacuumize washed product, grinding, 200 orders sieve again, and finally obtaining blackish green powder is nanometer metatitanic acid doped polyaniline combination electrode material.
With the preparation nanometer metatitanic acid doped polyaniline combination electrode material as active material, according to the mass ratio of active material, acetylene black and Kynoar (PVDF) is to join in an amount of NMP at 8: 1.5: 0.5, after mechanical high-speed stirs 3h, with the method for scraper coating with the slurry curtain coating on aluminium foil, diaphragm thickness is 200um, and 60 ℃ of dry 3h can obtain the electrode diaphragm A of nanometer metatitanic acid doped polyaniline combination electrode material.With the commerce active carbon is active material, is 8: 1.5: 0.5 according to the mass ratio of active material, acetylene black and Kynoar (PVDF), makes the electrode diaphragm B of active carbon with identical method.With electrode diaphragm A is positive pole, and electrode diaphragm B is a negative pole, is assembled into asymmetric ultracapacitor in glove box.The organic electrolyte that adopts is that the tetraethyl tetrafluoro boric acid amine of 1mol/L is dissolved in the propene carbonate.Barrier film is the polypropylene porous membrane of ultracapacitor special use.The ultracapacitor of assembling is carried out electrochemical property test.The test condition that discharges and recharges: current density is that 10A/g, operating voltage interval are 0～0.8V; The cyclic voltammetric test condition: sweep speed is that 100mV/s, operating voltage are-0.8～0.8V.
Embodiment 5
Be made into the camphorsulfonic acid solution of Ani in the deionized water that aniline (Ani) and the 12g camphorsulfonic acid of 2.5ml is added to 150ml together, and be moved in the there-necked flask of ice-water bath, the metatitanic acid nano particle that adds 0.35g therein, the solidliquid mixture of formation aniline-camphorsulfonic acid-ultra-fine metatitanic acid nano particle.This solidliquid mixture is at 0.5W/cm
2Ultrasonic 0.5h under the power carries out mechanical agitation to it simultaneously, and nanometer metatitanic acid particle is uniformly dispersed in solution.Disperse to finish back logical nitrogen in solidliquid mixture, to remove the air in the there-necked flask, avoid the influence of air, simultaneously this solidliquid mixture of high-speed stirred polymerization reaction.Be made into the camphorsulfonic acid solution of potassium bichromate in the deionized water that potassium bichromate and the 12g camphorsulfonic acid of 2.8g is added to 2000ml together, move in the dropping funel, slowly be added dropwise in the solidliquid mixture of there-necked flask high speed stirring, the control rate of addition is 10d/min, drips end to guarantee the solution in the dropping funel in 3h.The entire reaction device is put in the ice-water bath, and the low-temp reaction time is 2h.After the camphorsulfonic acid solution of the potassium bichromate in the dropping funel dripped end, the temperature remains within the normal range again stirred 16h.The suction filtration product, wash to filtrate earlier with the camphorsulfonic acid of rare 0.01mol/L colourless, again with the acetone cyclic washing to remove unreacted organic substance and oligomer completely, be colourless until filtrate, wash with a large amount of alcohol at last.60 ℃ of vacuumize washed product, grinding, 200 orders sieve again, and finally obtaining blackish green powder is nanometer metatitanic acid doped polyaniline combination electrode material.
With the preparation nanometer metatitanic acid doped polyaniline combination electrode material as active material, according to the mass ratio of active material, acetylene black and Kynoar (PVDF) is to join in an amount of NMP at 7: 2.5: 0.5, after mechanical high-speed stirs 3h, with the method for scraper coating with the slurry curtain coating on aluminium foil, diaphragm thickness is 200um, and 60 ℃ of dry 3h can obtain the electrode diaphragm A of nanometer metatitanic acid doped polyaniline combination electrode material.With the commerce active carbon is active material, is 8: 1.5: 0.5 according to the mass ratio of active material, acetylene black and Kynoar (PVDF), makes the electrode diaphragm B of active carbon with identical method.With electrode diaphragm A is positive pole, and electrode diaphragm B is a negative pole, is assembled into asymmetric ultracapacitor in glove box.The organic electrolyte that adopts is that the tetraethyl tetrafluoro boric acid amine of 1mol/L is dissolved in the acetonitrile.Barrier film is the polypropylene porous membrane of ultracapacitor special use.The ultracapacitor of assembling is carried out electrochemical property test.The test condition that discharges and recharges: current density is that 5A/g, operating voltage interval are 0～0.8V; The cyclic voltammetric test condition: sweep speed is that 40mV/s, operating voltage are-0.8～0.8V.
Claims (3)
1. preparation method who is used for the nanometer metatitanic acid doped polyaniline combination electrode material of ultracapacitor is characterized in that may further comprise the steps:
(1) aniline is added to the acid solution that is made into aniline in the deionized water with acid;
(2) acid solution with the aniline of step (1) is moved in the there-necked flask of ice-water bath, adds the metatitanic acid nano particle therein, forms the solidliquid mixture of aniline-acid-metatitanic acid nano particle;
(3) with the solidliquid mixture in the step (2) at 0.2～0.5W/cm
2Ultrasonic under the power-mechanical agitation 0.5～1h;
(4) logical nitrogen in the solidliquid mixture that step (3) high speed stirs is removed the air in the there-necked flask;
(5) initator and acid are added to the acid solution that is made into initator in the deionized water together;
(6) acid solution with the initator in the step (5) slowly is added dropwise in the solidliquid mixture of step (4) high speed stirring by dropping funel, and the control rate of addition is 10d/min;
(7) the entire reaction device with step (6) is put in the ice-water bath, low-temp reaction a period of time, when the acid solution of the initator in the dropping funel drip finish after, stirring at normal temperature a period of time again;
(8) product in the suction filtration step (7), wash to filtrate earlier with the acid solution of rare 0.01mol/L colourless, again with the acetone cyclic washing to remove unreacted organic substance and oligomer completely, be colourless until filtrate, wash with a large amount of alcohol at last;
Washed product in (9) 60 ℃ of vacuum drying step (8), grinding, 200 orders sieve again, obtain nanometer metatitanic acid doped polyaniline combination electrode material.
2. method according to claim 1 is characterized in that:
(1) addition of aniline is 2～4.56ml in claim 1 step (1), and the addition of acid is 8.3～16.5ml, and the addition of deionized water is 100～200ml;
(2) addition of the metatitanic acid nano particle in claim 1 step (2) is 0.225～0.9g;
(3) addition of initator is 2.567～4.56g in claim 1 step (5), and the addition of acid is 8.3～16.5ml, and the addition of deionized water is 100～200ml;
(4) the low-temp reaction time in claim 1 step (7) is 2～3h, and the stirring at normal temperature time is 16～24h.
3. method according to claim 1 is characterized in that:
(1) acid in claim 1 step (1) and the step (5) is that mass fraction is one or more of 38% concentrated hydrochloric acid, sulfuric acid, phosphoric acid, dodecyl sodium sulfonate, camphorsulfonic acid;
(2) initator in claim 1 step (5) is one or more of ammonium persulfate, hydrogen peroxide, cerous sulfate, Potassiumiodate, potassium bichromate.
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| CN104992846A (en) * | 2015-06-29 | 2015-10-21 | 温州大学 | Hetero-atom doped titanium composite material, and preparation method and application thereof |
| CN116510709A (en) * | 2023-05-15 | 2023-08-01 | 成都理工大学 | Preparation method of conductive hydrogel adsorption material of metatitanic acid type ion sieve |
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| CN101633779A (en) * | 2009-08-21 | 2010-01-27 | 昆明理工大学 | Conductive polyaniline composite electrode material and preparation method thereof |
| CN101735610A (en) * | 2009-12-17 | 2010-06-16 | 华东理工大学 | Hybrid of dedoping-state polyaniline/metallic oxide |
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| CN101633779A (en) * | 2009-08-21 | 2010-01-27 | 昆明理工大学 | Conductive polyaniline composite electrode material and preparation method thereof |
| CN101735610A (en) * | 2009-12-17 | 2010-06-16 | 华东理工大学 | Hybrid of dedoping-state polyaniline/metallic oxide |
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| 陈忠平，褚道葆，黎少君，张平，吴何珍: "碳纳米管/纳米TiO2-聚苯胺复合膜电极的制备及电容性能研究", 《塑料工业》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104992846A (en) * | 2015-06-29 | 2015-10-21 | 温州大学 | Hetero-atom doped titanium composite material, and preparation method and application thereof |
| CN104992846B (en) * | 2015-06-29 | 2017-11-14 | 温州大学 | A kind of Heteroatom doping titanium composite material and preparation method thereof and purposes |
| CN116510709A (en) * | 2023-05-15 | 2023-08-01 | 成都理工大学 | Preparation method of conductive hydrogel adsorption material of metatitanic acid type ion sieve |
| CN116510709B (en) * | 2023-05-15 | 2024-01-30 | 成都理工大学 | Preparation method of conductive hydrogel adsorption material of metatitanic acid type ion sieve |
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