CN103346021A - Mixed type electrochemical capacitor - Google Patents
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- CN103346021A CN103346021A CN2013102618911A CN201310261891A CN103346021A CN 103346021 A CN103346021 A CN 103346021A CN 2013102618911 A CN2013102618911 A CN 2013102618911A CN 201310261891 A CN201310261891 A CN 201310261891A CN 103346021 A CN103346021 A CN 103346021A
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Abstract
The invention relates to a mixed type electrochemical capacitor, in particular to a mixed type electrochemical capacitor with high-energy density based on directional carbon nanotubes. The mixed type electrochemical capacitor structurally comprises a positive electrode, a negative electrode, a separating membrane and electrolytes, wherein the separating membrane and the electrolytes are arranged between the positive electrode and the negative electrode. The mixed type electrochemical capacitor is characterized in that the positive electrode of the mixed type electrochemical capacitor is composed of a directional carbon nanotube array directly growing on a conductive substrate and manganese oxide or polyaniline composite materials; the negative electrode of the mixed type electrochemical capacitor is composed of a modified directional carbon nanotube array or a directional carbon nanotube array directly growing on the conductive substrate and polypyrrole composite materials; the electrolytes of the mixed type electrochemical capacitor are nonaqueous electrolytes. The mixed type electrochemical capacitor has energy density capable of being compared to a secondary battery, and meanwhile has high power density and cycling stability. The current problem of energy shortage can be eased, and the mixed type electrochemical capacitor has high practical value, wide market prospect and considerable economic and social benefits.
Description
Technical field
A kind of mixed type electrochemical capacitor relates to the coupling of positive and negative electrode electrode material in a kind of high-energy-density mixed type electrochemical capacitor based on aligned carbon nanotube and the electrochemical capacitor and electrolyte.
Background technology
Electrochemical capacitor (Electrochemical Capacitor EC) is commonly called as ultracapacitor (Supercapacitor), as a kind of novel chemical power source, and its long service life (10
5Inferior circulation), specific power big (1500W/kg), can quick charge (can be the several seconds), cryogenic property good (minimum operating temperature-50 ℃), good heavy current, storage power be big, have the power density higher than battery, than the higher energy density of traditional capacitor, develop into a kind of efficient, practical energy accumulating device probably, thereby in fields such as traffic, the energy, communication, power electronics, military project national defence, industrial production very wide application prospect is arranged.Though ultracapacitor more and more demonstrates its great vitality in application, but the energy density of present ultracapacitor is compared a certain distance in addition with battery class device lithium ion battery, Ni-MH battery even lead-acid battery, so high-energy-density is one of important directions of present ultracapacitor development.
Electrochemical capacitor energy density computing formula is: E=(CU
2)/2, wherein, C is that (unit: F), U is the operating voltage (unit: V) of electrochemical capacitor to electric capacity.By this formula as can be known, the energy density that improves electrochemical capacitor has two kinds of approach: from the material angle, need high specific capacitance more and the active material of steady operation under high voltage; From device angles, the electrolyte of then need to adjust device architecture (as asymmetric electrochemical capacitor), selecting to have wideer electrochemical window reaches the purpose that improves operating voltage.
Electrochemical capacitor is by positive and negative electrode material identical symmetric form and asymmetric two kinds of can being divided into whether, and latter's both positive and negative polarity difference is called the mixed type electrochemical capacitor again.In the past, two energy storage principle that the electrode tool is inequality of mixed type electrochemical capacitor, comprising electrode and the electrolyte interface electric double layer capacitance material with electric double layer mode stored charge, and by electrode active material the Faradic electricity capacity materials that reversible redox reaction fast stores electric charge takes place.The ratio electric capacity of electric double layer capacitance material that wherein with the porous carbon materials is representative is lower, affects the energy density of integral device; Be that the Faradic electricity capacity materials of representative has higher ratio electric capacity with metal oxide (as ruthenium-oxide, manganese oxide) and conducting polymer (as polyaniline, polypyrrole), but its cycle performance and electric conductivity are relatively poor.
Therefore, have high energy density in order to prepare, the electrochemical capacitor of power density and cyclical stability need research and develop more excellent electrode material, reasonably mates positive and negative electrode and the electrolyte of mixed type electrochemical capacitor.
Summary of the invention
The objective of the invention is in order to overcome the lower defective of present electrochemical capacitor energy density, provide under a kind of situation with higher capacitance value and also can widen its operating voltage interval, make the gained electrochemical capacitor have high energy density, have the mixed type electrochemical capacitor of higher power density and cyclical stability simultaneously.
The objective of the invention is to be achieved through the following technical solutions.
A kind of mixed type electrochemical capacitor is based on the high-energy-density mixed type electrochemical capacitor of aligned carbon nanotube, and its structure comprises barrier film, electrolyte between positive pole, negative pole and the both positive and negative polarity; It is characterized in that:
(1) its positive pole is made up of with manganese oxide or polyaniline composite material the directional carbon nanotube array that is grown directly upon on the conducting base;
(2) its negative pole is formed by being grown directly upon modification directional carbon nanotube array on the conducting base or directional carbon nanotube array and Pt/Polypyrrole composite material;
(3) its electrolyte is nonaqueous electrolyte.
A kind of mixed type electrochemical capacitor of the present invention is characterized in that described conductive substrate material is plate, paper tinsel, net and the foamed metal material of a kind of metal in titanium, nickel, aluminium, copper, tantalum, platinum, gold, the stainless steel; It perhaps is the material with carbon element of graphite paper, conductive paper of carbon fiber; It perhaps is the composite material of plate, paper tinsel, net and the foamed metal material outer wrapping thin layer carbonaceous material of metal.
A kind of mixed type electrochemical capacitor of the present invention is characterized in that the described directional carbon nanotube array that is grown directly upon conductive substrate material is that length is the 5-1000 micron, is preferably the 10-800 micron; Each single-root carbon nano-tube is single wall or many walls, and diameter is the 0.4-80 nanometer, is preferably the 1-50 nanometer.
A kind of mixed type electrochemical capacitor of the present invention is characterized in that the described directional carbon nanotube array that is grown directly upon conductive substrate material is that length is the 10-800 micron; Each single-root carbon nano-tube is single wall or many walls, and diameter is the 1-50 nanometer.
A kind of mixed type electrochemical capacitor of the present invention is characterized in that described positive electrode---in directional carbon nanotube array and the manganese oxide composite material, the weight content of manganese oxide is 2%-95 %, is preferably 10-85 weight %.
Of the present invention a kind of mixed type electrochemical capacitor is characterized in that described positive electrode---in directional carbon nanotube array and the manganese oxide composite material, the weight content of manganese oxide is 10%-85%.
A kind of mixed type electrochemical capacitor of the present invention is characterized in that described positive electrode---in directional carbon nanotube array and the polyaniline composite material, the weight content of polyaniline is 2%-95 %, is preferably 10-80 weight %.
A kind of mixed type electrochemical capacitor of the present invention is characterized in that described positive electrode---in directional carbon nanotube array and the polyaniline composite material, the weight content of polyaniline is 10%-80%.
A kind of mixed type electrochemical capacitor of the present invention; it is characterized in that described negative material---modification directional carbon nanotube array material is the directional carbon nanotube array that load contains heteroatom functional group; the oxygen atom of hetero-atom for existing with carbonyl, hydroxyl, carboxy form; in the nitrogen-atoms that exists with amido, imido grpup, acid amides, imide functionality form, the sulphur atom that exists with sulfydryl, sulfonyl, sulfinyl form, the phosphorus atoms that exists with the phosphino-form one or more, wherein the weight content of non-carbon is 1%-30 %.Be preferably 2-25 weight %.
A kind of mixed type electrochemical capacitor of the present invention, the weight content that it is characterized in that described non-carbon is 2%-25%.
A kind of mixed type electrochemical capacitor of the present invention is characterized in that described negative material---in directional carbon nanotube array and the Pt/Polypyrrole composite material, the weight content of polypyrrole is 2%-95 %, is preferably 10-80 weight %.
A kind of mixed type electrochemical capacitor of the present invention is characterized in that described negative material---in directional carbon nanotube array and the Pt/Polypyrrole composite material, the weight content of polypyrrole is 10%-80 %.
A kind of mixed type electrochemical capacitor of the present invention is characterized in that described composition electrochemical capacitor nonaqueous electrolyte is organic system electrolyte, ionic liquid or solid electrolyte.
A kind of mixed type electrochemical capacitor of the present invention is characterized in that described organic system electrolyte is made up of organic solvent and salt, and electrolyte solvent is selected from one or more in ethylene carbonate, ethylene carbonate, propene carbonate and the acetonitrile; The electrolyte used salt is selected from one or more in tetraethyl tetrafluoroborate, tetraethyl tetrafluoro boric acid quaternary alkylphosphonium salt, four n-pro-pyl tetrafluoro boric acid quaternary alkylphosphonium salts, tetraethyl hexafluorophosphoric acid quaternary ammonium salt, lithium hexafluoro phosphate, lithium perchlorate and the LiBF4; Concentration is the 0.1-5 mol.
A kind of mixed type electrochemical capacitor of the present invention, it is characterized in that described ionic liquid at room temperature is the following combination in any of two or more zwitterion arbitrarily: cation is quaternary ammonium cation, quaternary phosphonium cations, pyridylium, glyoxaline cation, sulfonium cation; Anion is BF
4 -, PF
6 -, and NO
3 -, SbF
6 -, CIO
4 -, CF
3SO
3 -, C
3F
7COO
-, C
4F
9SO
3 -, F
3COO
-
A kind of mixed type electrochemical capacitor of the present invention is characterized in that described solid electrolyte is evenly mixed by polymer substrate and solute to form, and solute is a kind of of acid, alkali or salt; Polymer substrate is one or more in polyethylene glycol, polyacrylonitrile, polyethylene benzene sulfonic acid, polyvinylpyrrolidone and the polyvinyl alcohol; The selected acid of solid electrolyte is one or both mixing of phosphoric acid, perchloric acid; The selected alkali of solid electrolyte is one or more of lithium hydroxide, NaOH and potassium hydroxide; The selected salt of solid electrolyte is one or more in the perchlorate of tetraethyl tetrafluoroborate, tetraethyl tetrafluoro boric acid quaternary alkylphosphonium salt, four n-pro-pyl tetrafluoro boric acid quaternary alkylphosphonium salts, tetraethyl hexafluorophosphoric acid quaternary alkylphosphonium salt, lithium hexafluoro phosphate, LiBF4 and tetramethyl-ammonium; The concentration of solid electrolyte solute is the 0.1-2 mol.
A kind of mixed type electrochemical capacitor of the present invention, be based on the high-energy-density mixed type electrochemical capacitor of aligned carbon nanotube, comprise barrier film, electrolyte between positive pole, negative pole and the both positive and negative polarity, its positive pole is made up of with manganese oxide or polyaniline composite material the directional carbon nanotube array that is grown directly upon on the conducting base; Negative pole is formed by being grown directly upon modification directional carbon nanotube array on the conducting base or directional carbon nanotube array and Pt/Polypyrrole composite material; Electrolyte is nonaqueous electrolyte, can make product steady operation in the voltage range of 2 ~ 4.5 V.Can effectively overcome the lower defective of present electrochemical capacitor energy density, faraday's electric capacity composite material of preparation high specific capacitance is respectively as positive and negative electrode, and select in 2-4.5 V scope, to keep stable nonaqueous electrolyte, constitute the mixed type electrochemical capacitor.Product is had under the situation of higher capacitance value also can widen its operating voltage interval, make the gained electrochemical capacitor have high energy density.Simultaneously, this mixed type electrochemical capacitor has also taken full advantage of the special structural advantage of directional carbon nanotube array and splendid conductivity, makes the product device to have higher power density and cyclical stability simultaneously.
A kind of mixed type electrochemical capacitor of the present invention has the energy density of the secondary cell of can comparing, the time have higher power density and a cyclical stability.Be enough to alleviate current energy starved problem, have very high practical value and vast market prospect and considerable economical, societal benefits.
Description of drawings
Fig. 1 is electrochemical capacitor structural representation among the embodiment 1; Wherein 1 is conductive substrates, and 2 is positive electrode active materials (Faradic electricity capacity materials/carbon nano tube compound material), and 3 is barrier film, and 4 is nonaqueous electrolyte, and 5 is active group, and 6 is carbon nano-tube.
Fig. 2 is electrochemical capacitor structural representation among the embodiment 2; Wherein 1 is conductive substrates, and 2 is positive electrode active materials (Faradic electricity capacity materials/carbon nano tube compound material), and 3 is barrier film, and 4 is nonaqueous electrolyte, and 5 is negative active core-shell material (Faradic electricity capacity materials/carbon nano tube compound material).
Embodiment
A kind of mixed type electrochemical capacitor is based on the high-energy-density mixed type electrochemical capacitor of aligned carbon nanotube, and its structure comprises barrier film, electrolyte between positive pole, negative pole and the both positive and negative polarity; Its positive pole is made up of with manganese oxide or polyaniline composite material the directional carbon nanotube array that is grown directly upon on the conducting base; Its negative pole is formed by being grown directly upon modification directional carbon nanotube array on the conducting base or directional carbon nanotube array and Pt/Polypyrrole composite material; Its electrolyte is nonaqueous electrolyte.
Below the specific embodiment of the present invention is elaborated.Should be understood that embodiment described herein only is used for description and interpretation the present invention, is not limited to the present invention.
On the one hand, the invention provides a kind of high-energy-density mixed type electrochemical capacitor based on aligned carbon nanotube, comprise barrier film, electrolyte between positive pole, negative pole and the both positive and negative polarity, it is characterized in that: formed with manganese oxide or polyaniline composite material by the directional carbon nanotube array that is grown directly upon on the conducting base; Negative pole is formed by being grown directly upon modification directional carbon nanotube array on the conducting base or directional carbon nanotube array and Pt/Polypyrrole composite material; Electrolyte is nonaqueous electrolyte, can make product steady operation in the voltage range of 2 ~ 4.5 V.
Second aspect, described conductive substrate material are plate, paper tinsel, net and the foamed metal material of metals such as titanium, nickel, aluminium, copper, tantalum, platinum, gold, stainless steel; Perhaps be material with carbon elements such as graphite paper, conductive paper of carbon fiber; It perhaps is the composite material of plate, paper tinsel, net and the foamed metal material outer wrapping thin layer carbonaceous material (high conductivity carbon-coating or Graphene) of metal.
The third aspect, the directional carbon nanotube array that is grown directly upon the one or both sides of conductive substrate material is length 5-1000 micron, is preferably the 10-800 micron; Single-root carbon nano-tube is single wall or many walls, and diameter is the 0.5-80 nanometer, is preferably the 1-50 nanometer.
Fourth aspect, the positive electrode of this electrochemical capacitor are served as reasons and are grown directly upon the composite material of directional carbon nanotube array on the conducting base and manganese oxide and are grown in directional carbon nanotube array on the conducting base and wherein a kind of of the composite material of polyaniline; Negative pole is by being grown directly upon the modification directional carbon nanotube array on the conducting base and being grown directly upon directional carbon nanotube array on the conducting base and wherein a kind of of Pt/Polypyrrole composite material.
Wherein, in positive electrode---directional carbon nanotube array and the manganese oxide composite material, the content of manganese oxide is 2-95 weight %, is preferably 10-85 weight %.In positive electrode---directional carbon nanotube array and the polyaniline composite material, the content of polyaniline is 2-95 weight %, is preferably 10-80 weight %.
Wherein, negative material---modification directional carbon nanotube array material is the directional carbon nanotube array that load contains heteroatom functional group; hetero-atom can be one or more of oxygen atom (existing with forms such as carbonyl, hydroxyl, carboxyls), nitrogen-atoms (existing with functional group's forms such as amido, imido grpup, acid amides, acid imides), sulphur atom (existing with forms such as sulfydryl, sulfonyl, sulfinyls), phosphorus atoms (existing with the phosphino-form); wherein the content of non-carbon is 1-30 weight %, is preferably 2-25 weight %.In negative material---directional carbon nanotube array and the Pt/Polypyrrole composite material, the content of polypyrrole is 2-95 weight %, is preferably 10-80 weight %.Reversible redox reaction fast can take place in these functional groups of aligned carbon nanotube area load in charging and discharging process, provide faraday electric capacity, so this negative material has the ratio electric capacity far above general carbon nano-tube.
The 5th aspect, the electrolyte of forming electrochemical capacitor is nonaqueous electrolyte, is the organic system electrolyte, or ionic liquid at room temperature, or solid electrolyte.
Wherein, the organic system electrolyte is made up of organic solvent and salt, and electrolyte solvent is selected from one or more in ethylene carbonate, ethylene carbonate, propene carbonate and the acetonitrile; The electrolyte used salt is selected from one or more in tetraethyl tetrafluoroborate, tetraethyl tetrafluoro boric acid quaternary alkylphosphonium salt, four n-pro-pyl tetrafluoro boric acid quaternary alkylphosphonium salts, tetraethyl hexafluorophosphoric acid quaternary ammonium salt, lithium hexafluoro phosphate, lithium perchlorate and the LiBF4.Concentration is the 0.1-5 mol.
Wherein, ionic liquid at room temperature is for being the following combination in any of two or more zwitterion arbitrarily: cation is quaternary ammonium cation, quaternary phosphonium cations, pyridylium, glyoxaline cation, sulfonium cation; Anion is BF
4 -, PF
6 -, also have NO in addition
3 -, SbF
6 -, CIO
4 -, CF
3SO
3 -, C
3F
7COO
-, C
4F
9SO
3 -, F
3COO
-Deng.
Wherein, solid electrolyte is evenly mixed by polymer substrate and solute and forms, and solute is a kind of of acid, alkali or salt.Polymer substrate is one or more in polyethylene glycol, polyacrylonitrile, polyethylene benzene sulfonic acid, polyvinylpyrrolidone and the polyvinyl alcohol; The selected acid of solid electrolyte is one or both mixing of phosphoric acid, perchloric acid; The selected alkali of solid electrolyte is one or more of lithium hydroxide, NaOH and potassium hydroxide; The selected salt of solid electrolyte is one or more in the perchlorate of tetraethyl tetrafluoroborate, tetraethyl tetrafluoro boric acid quaternary alkylphosphonium salt, four n-pro-pyl tetrafluoro boric acid quaternary alkylphosphonium salts, tetraethyl hexafluorophosphoric acid quaternary alkylphosphonium salt, lithium hexafluoro phosphate, LiBF4 and tetramethyl-ammonium.The concentration of solid electrolyte solute is the 0.1-2 mol.
More than describe preferred implementation of the present invention in detail; but the present invention is not limited to the detail in the above-mentioned execution mode, in technical conceive scope of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
Need to prove in addition, each concrete technical characterictic described in above-mentioned embodiment under reconcilable situation, can make up by any suitable manner, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible compound modes.
In addition, also can carry out combination in any between the various execution mode of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Following embodiment will the present invention is further illustrated, but therefore do not limit the present invention.Following examples are all for explanation mixed type electrochemical capacitor provided by the invention, and anode pole piece, cathode pole piece and the electrolyte of this device of composition.Selection about barrier film belongs to the known of the art.
In following examples:
But employing power SC-144DR type carbon and sulfur analytical instrument (U.S. LECO company) is measured carbon and other content of heteroatoms in the modification directional carbon nanotube array material.
Adopt CT2001A, LAND battery test system (Wuhan Jin Nuo Electronics Co., Ltd.) and Princeton VersaSTAT MC electrochemical workstation (Ametek, Inc.), under the condition of constant current charge-discharge, measure energy density, power density and the cyclical stability of electrochemical capacitor.
(1) preparation of directional carbon nanotube array:
The Al paper tinsel is inserted in the tube furnace, at H
2/ Ar gaseous mixture (volume ratio 1:9) protection is warming up to 650 ℃ down, feeds the ethanolic solution (concentration is 0.075 mol/L) of ferrocene, adopts chemical vapour deposition technique directional carbon nanotube array to be grown directly upon the surface of Al paper tinsel.
(2) preparation of anode pole piece:
Insert the directional carbon nanotube array that obtains in the step (1) in the mixed solution of aniline and sulfuric acid as work electrode, the concentration of aniline and sulfuric acid is respectively 0.1 mol/L and 1 mol/L, be auxiliary electrode with the platinized platinum, the Ag/AgCl electrode is reference electrode, adopt electrochemical cyclic voltammetry, voltage between work electrode and the auxiliary electrode is-0.2 ~ 0.8 V, sweep speed is 50 mV/s, cycle-index is 30 times, monomer is carried out in-situ polymerization, make polymer deposition to the surface of aligned carbon nanotube, wash then, dry, the content of polyaniline is 59 weight %.
(3) preparation of cathode pole piece:
The directional carbon nanotube array that obtains in the step (1) is inserted in the plasma clean machine (female prosperous PR20L type difficult to understand), with air plasma it is carried out modification and handle, make a certain amount of oxygen-containing functional group of its area load.After testing, the content of non-carbon is 10 weight %.
(4) preparation of mixed type electrochemical capacitor test:
Be positive pole with polyaniline/aligned carbon nanotube, the directed carbon nanometer of modification is negative pole, and choosing ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate is electrolyte, microporous polypropylene membrane is barrier film, the CR2025 battery case is shell, the assembling electrochemical capacitor, and its structure is as shown in Figure 1.The operating voltage window is 0 ~ 4 V, with the energy density of measuring this electrochemical capacitor under the constant current density and power density is respectively 103 Wh/Kg and 20 kW/Kg(adjust with the electrode material quality).Circulate after 2000 times, be respectively 3% and 1% with energy density and the power density decay of identical this electrochemical capacitor of condition test.
(1) preparation of directional carbon nanotube array:
The Ti paper tinsel is inserted in the tube furnace, at H
2/ Ar gaseous mixture (volume ratio 1:9) protection is warming up to 800 ℃ down, feeds the ethanolic solution (concentration is 0.05 mol/L) of ferrocene, adopts chemical vapour deposition technique directional carbon nanotube array to be grown directly upon the surface of Ti paper tinsel.
(2) preparation of anode pole piece:
The directional carbon nanotube array that obtains in the step (1) is inserted in the metabisulfite solution that concentration is 0.1 mol/L as work electrode, is auxiliary electrode with the platinized platinum, and the Ag/AgCl electrode is reference electrode, adopts the electrochemistry galvanostatic method, and current value is 0.1 A/cm
2, the reaction cut-ff voltage is 1.0 V, to Mn
2+Ionic oxide formation prepares manganese oxide, makes manganese-oxide deposition to the surface of aligned carbon nanotube, washs then, dries, and the content of manganese oxide is 47 weight %.
(3) preparation of cathode pole piece:
The directional carbon nanotube array that obtains in the step (1) is inserted in the plasma clean machine (female prosperous PR20L type difficult to understand), with ammonia plasmas it is carried out modification and handle, make a certain amount of nitrogen-containing functional group of its area load.After testing, the content of non-carbon is 13 weight %.
(4) preparation of mixed type electrochemical capacitor test:
Be positive pole with manganese oxide/aligned carbon nanotube, the modification aligned carbon nanotube is negative pole, and choosing ionic liquid 1-ethyl-3-methyl imidazolium tetrafluoroborate is electrolyte, microporous polypropylene membrane is barrier film, the CR2025 battery case is shell, the assembling electrochemical capacitor, and its structure is as shown in Figure 1.The operating voltage window is 0 ~ 4 V, with the energy density of measuring this electrochemical capacitor under the constant current density and power density is respectively 97 Wh/Kg and 21 kW/Kg(adjust with the electrode material quality).Circulate after 2000 times, be respectively 2% and 0.8% with energy density and the power density decay of identical this electrochemical capacitor of condition test.
Embodiment 3
(1) preparation of directional carbon nanotube array:
Foam Ni is inserted in the tube furnace, at H
2/ Ar gaseous mixture (volume ratio 1:9) protection is warming up to 800 ℃ down, feeds the ethanolic solution (concentration is 0.08 mol/L) of ferrocene, adopts chemical vapour deposition technique directional carbon nanotube array to be grown directly upon the surface of foam Ni.
(2) preparation of anode pole piece:
The directional carbon nanotube array that obtains in the step (1) is inserted in the potassium permanganate that concentration is 0.1 mol/L as work electrode, be heated to 70 ℃, react 2 h, make manganese-oxide deposition to the surface of aligned carbon nanotube, wash then, dry, the content of manganese oxide is 66 weight %.
(3) preparation of cathode pole piece:
Insert the directional carbon nanotube array that obtains in the step (1) in the mixed solution of pyrroles and sodium nitrate as work electrode, the concentration of aniline and sulfuric acid is respectively 0.1 mol/L and 1 mol/L, be auxiliary electrode with the platinized platinum, the Ag/AgCl electrode is reference electrode, adopt electrochemical cyclic voltammetry, voltage between work electrode and the auxiliary electrode is-0.2 ~ 1.0 V, sweep speed is 50 mV/s, cycle-index is 20 times, monomer is carried out in-situ polymerization, make polymer deposition to the surface of aligned carbon nanotube, then washing, oven dry, the content of polypyrrole is 49 weight %.
(4) preparation of mixed type electrochemical capacitor test:
Be positive pole with manganese oxide/aligned carbon nanotube, polypyrrole/aligned carbon nanotube is negative pole, and the acetonitrile solution of choosing the tetraethyl hexafluorophosphoric acid quaternary ammonium salt of 1 mol/L is electrolyte, the cellulose microporous barrier is barrier film, the CR2025 battery case is shell, the assembling electrochemical capacitor, and its structure is as shown in Figure 2.The operating voltage window is 0 ~ 3 V, with the energy density of measuring this electrochemical capacitor under the constant current density and power density is respectively 63 Wh/Kg and 15 kW/Kg(adjust with the electrode material quality).Circulate after 2000 times, be respectively 3.5% and 2% with energy density and the power density decay of identical this electrochemical capacitor of condition test.
Embodiment 4
(1) preparation of directional carbon nanotube array:
The Ti paper tinsel is inserted in the tube furnace, at H
2/ Ar gaseous mixture (volume ratio 1:9) protection is warming up to 800 ℃ down, feeds the ethanolic solution (concentration is 0.1 mol/L) of ferrocene, adopts chemical vapour deposition technique directional carbon nanotube array to be grown directly upon the surface of Ti paper tinsel.
(2) preparation of anode pole piece:
The directional carbon nanotube array that obtains in the step (1) is inserted in the metabisulfite solution that concentration is 0.1 mol/L as work electrode, is auxiliary electrode with the platinized platinum, and the Ag/AgCl electrode is reference electrode, adopts the electrochemistry galvanostatic method, and current value is 0.1 A/cm
2, the reaction cut-ff voltage is 1.0 V, to Mn
2+Ionic oxide formation prepares manganese oxide, makes manganese-oxide deposition to the surface of aligned carbon nanotube, washs then, dries, and the content of manganese oxide is 47 weight %.
(3) preparation of cathode pole piece:
The directional carbon nanotube array that obtains in the step (1) is inserted in the plasma clean machine (female prosperous PR20L type difficult to understand), with air plasma it is carried out modification and handle, make a certain amount of oxygen-containing functional group of its area load.After testing, the content of non-carbon is 14 weight %.
(4) preparation of mixed type electrochemical capacitor test:
Be positive pole with manganese oxide/aligned carbon nanotube, the modification aligned carbon nanotube is negative pole, and the carbonic allyl ester solution (1 mol/L) of choosing lithium perchlorate is electrolyte, polyethene microporous membrane is barrier film, the CR2025 battery case is shell, the assembling electrochemical capacitor, and its structure is as shown in Figure 1.The operating voltage window is 0 ~ 3.5 V, with the energy density of measuring this electrochemical capacitor under the constant current density and power density is respectively 107 Wh/Kg and 27 kW/Kg(adjust with the electrode material quality).Circulate after 2000 times, be respectively 1% and 0.5% with energy density and the power density decay of identical this electrochemical capacitor of condition test.
(1) preparation of directional carbon nanotube array:
Graphite paper is inserted in the tube furnace, at H
2/ Ar gaseous mixture (volume ratio 1:9) protection is warming up to 800 ℃ down, feeds the ethanolic solution (concentration is 0.05 mol/L) of ferrocene, adopts chemical vapour deposition technique directional carbon nanotube array to be grown directly upon the surface of graphite paper.
(2) preparation of anode pole piece:
Insert the directional carbon nanotube array that obtains in the step (1) in the mixed solution of aniline and sulfuric acid as work electrode, the concentration of aniline and sulfuric acid is respectively 0.1 mol/L and 1 mol/L, be auxiliary electrode with the platinized platinum, the Ag/AgCl electrode is reference electrode, adopt electrochemical cyclic voltammetry, voltage between work electrode and the auxiliary electrode is-0.2 ~ 0.8 V, sweep speed is 100 mV/s, cycle-index is 50 times, monomer is carried out in-situ polymerization, make polymer deposition to the surface of aligned carbon nanotube, then washing, oven dry, the content of polyaniline is 72 weight %.
(3) preparation of cathode pole piece:
Insert the directional carbon nanotube array that obtains in the step (1) in the mixed solution of pyrroles and sodium nitrate as work electrode, the concentration of aniline and sulfuric acid is respectively 0.1 mol/L and 1 mol/L, be auxiliary electrode with the platinized platinum, the Ag/AgCl electrode is reference electrode, adopt electrochemical cyclic voltammetry, voltage between work electrode and the auxiliary electrode is-0.2 ~ 1.0 V, sweep speed is 20 mV/s, cycle-index is 20 times, monomer is carried out in-situ polymerization, make polymer deposition to the surface of aligned carbon nanotube, then washing, oven dry, the content of polypyrrole is 69 weight %.
(4) preparation of mixed type electrochemical capacitor test:
Be positive pole with polyaniline/aligned carbon nanotube, polypyrrole/aligned carbon nanotube is negative pole, choosing and getting solid electrolyte (containing 10% quality than the polyethylene benzene sulfonic acid (number-average molecular weight is about 7000) of the perchlorate of tetramethyl-ammonium) is electrolyte, do not need barrier film and shell, the assembling electrochemical capacitor, its structure as shown in Figure 2.The operating voltage window is 0 ~ 4.5V, with the energy density of measuring this electrochemical capacitor under the constant current density and power density is respectively 95 Wh/Kg and 18 kW/Kg(adjust with the electrode material quality).Circulate after 2000 times, be respectively 5% and 3% with energy density and the power density decay of identical this electrochemical capacitor of condition test.
Mixed type electrochemical capacitor provided by the invention adopts faraday's electric capacity composite material of high specific capacitance respectively as positive and negative electrode, and selects to keep stable nonaqueous electrolyte in 2-4.5 V scope, constitutes the mixed type electrochemical capacitor.Product is had under the situation of higher capacitance value also can widen its operating voltage interval, the gained electrochemical capacitor is had can compare the energy density of secondary cell, the time have higher power density and a cyclical stability.Be enough to alleviate current energy starved problem, have very high practical value and vast market prospect and considerable economical, societal benefits.
Claims (16)
1. mixed type electrochemical capacitor is based on the high-energy-density mixed type electrochemical capacitor of aligned carbon nanotube, and its structure comprises barrier film, electrolyte between positive pole, negative pole and the both positive and negative polarity; It is characterized in that:
(1) its positive pole is made up of with manganese oxide or polyaniline composite material the directional carbon nanotube array that is grown directly upon on the conducting base;
(2) its negative pole is formed by being grown directly upon modification directional carbon nanotube array on the conducting base or directional carbon nanotube array and Pt/Polypyrrole composite material;
(3) its electrolyte is nonaqueous electrolyte.
2. a kind of mixed type electrochemical capacitor according to claim 1 is characterized in that described conductive substrate material is plate, paper tinsel, net and the foamed metal material of a kind of metal in titanium, nickel, aluminium, copper, tantalum, platinum, gold, the stainless steel; It perhaps is the material with carbon element of graphite paper, conductive paper of carbon fiber; It perhaps is the composite material of plate, paper tinsel, net and the foamed metal material outer wrapping thin layer carbonaceous material of metal.
3. a kind of mixed type electrochemical capacitor according to claim 1 is characterized in that the described directional carbon nanotube array that is grown directly upon conductive substrate material is that length is the 5-1000 micron; Each single-root carbon nano-tube is single wall or many walls, and diameter is the 0.4-80 nanometer.
4. a kind of mixed type electrochemical capacitor according to claim 3 is characterized in that the described length that is grown directly upon the directional carbon nanotube array of conductive substrate material is the 10-800 micron; Each single-root carbon nano-tube is single wall or many walls, and diameter is the 1-50 nanometer.
5. a kind of mixed type electrochemical capacitor according to claim 1 is characterized in that described positive electrode---in directional carbon nanotube array and the manganese oxide composite material, the weight content of manganese oxide is 2%-95 %.
6. a kind of mixed type electrochemical capacitor according to claim 5 is characterized in that described positive electrode---in directional carbon nanotube array and the manganese oxide composite material, the weight content of manganese oxide is 10%-85%.
7. a kind of mixed type electrochemical capacitor according to claim 1 is characterized in that described positive electrode---in directional carbon nanotube array and the polyaniline composite material, the weight content of polyaniline is 2%-95 %.
8. a kind of mixed type electrochemical capacitor according to claim 7 is characterized in that described positive electrode---in directional carbon nanotube array and the polyaniline composite material, the weight content of polyaniline is 10%-80%.
9. a kind of mixed type electrochemical capacitor according to claim 1; it is characterized in that described negative material---modification directional carbon nanotube array material is the directional carbon nanotube array that load contains heteroatom functional group; the oxygen atom of hetero-atom for existing with carbonyl, hydroxyl, carboxy form; in the nitrogen-atoms that exists with amido, imido grpup, acid amides, imide functionality form, the sulphur atom that exists with sulfydryl, sulfonyl, sulfinyl form, the phosphorus atoms that exists with the phosphino-form one or more, wherein the weight content of non-carbon is 1%-30 %.
10. a kind of mixed type electrochemical capacitor according to claim 9, the preferred weight content that it is characterized in that described non-carbon is 2%-25%.
11. a kind of mixed type electrochemical capacitor according to claim 1 is characterized in that its negative material---in directional carbon nanotube array and the Pt/Polypyrrole composite material, the weight content of polypyrrole is 2%-95 %.
12. a kind of mixed type electrochemical capacitor according to claim 11 is characterized in that described negative material---in directional carbon nanotube array and the Pt/Polypyrrole composite material, the weight content of polypyrrole is 10%-80 %.
13. a kind of mixed type electrochemical capacitor according to claim 1 is characterized in that described composition electrochemical capacitor nonaqueous electrolyte is organic system electrolyte, ionic liquid or solid electrolyte.
14. a kind of mixed type electrochemical capacitor according to claim 13, it is characterized in that described organic system electrolyte is made up of organic solvent and salt, electrolyte solvent is selected from one or more in ethylene carbonate, ethylene carbonate, propene carbonate and the acetonitrile; The electrolyte used salt is selected from one or more in tetraethyl tetrafluoroborate, tetraethyl tetrafluoro boric acid quaternary alkylphosphonium salt, four n-pro-pyl tetrafluoro boric acid quaternary alkylphosphonium salts, tetraethyl hexafluorophosphoric acid quaternary ammonium salt, lithium hexafluoro phosphate, lithium perchlorate and the LiBF4; Concentration is the 0.1-5 mol.
15. a kind of mixed type electrochemical capacitor according to claim 13, it is characterized in that described ionic liquid at room temperature is the following combination in any of two or more zwitterion arbitrarily: cation is quaternary ammonium cation, quaternary phosphonium cations, pyridylium, glyoxaline cation, sulfonium cation; Anion is BF
4 -, PF
6 -, and NO
3 -, SbF
6 -, CIO
4 -, CF
3SO
3 -, C
3F
7COO
-, C
4F
9SO
3 -, F
3COO
-
16. a kind of mixed type electrochemical capacitor according to claim 13 is characterized in that described solid electrolyte is evenly mixed by polymer substrate and solute to form, solute is a kind of of acid, alkali or salt; Polymer substrate is one or more in polyethylene glycol, polyacrylonitrile, polyethylene benzene sulfonic acid, polyvinylpyrrolidone and the polyvinyl alcohol; The selected acid of solid electrolyte is one or both mixing of phosphoric acid, perchloric acid; The selected alkali of solid electrolyte is one or more of lithium hydroxide, NaOH and potassium hydroxide; The selected salt of solid electrolyte is one or more in the perchlorate of tetraethyl tetrafluoroborate, tetraethyl tetrafluoro boric acid quaternary alkylphosphonium salt, four n-pro-pyl tetrafluoro boric acid quaternary alkylphosphonium salts, tetraethyl hexafluorophosphoric acid quaternary alkylphosphonium salt, lithium hexafluoro phosphate, LiBF4 and tetramethyl-ammonium; The concentration of solid electrolyte solute is the 0.1-2 mol.
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