CN106565971A - Method for preparing polyaniline graft-modified silicon dioxide composite electrode material for supercapacitors - Google Patents
Method for preparing polyaniline graft-modified silicon dioxide composite electrode material for supercapacitors Download PDFInfo
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- CN106565971A CN106565971A CN201611014813.1A CN201611014813A CN106565971A CN 106565971 A CN106565971 A CN 106565971A CN 201611014813 A CN201611014813 A CN 201611014813A CN 106565971 A CN106565971 A CN 106565971A
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- ultracapacitor
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 32
- 239000007772 electrode material Substances 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title abstract description 8
- 238000000034 method Methods 0.000 title abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 49
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001291 vacuum drying Methods 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 239000005543 nano-size silicon particle Substances 0.000 claims description 37
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000013019 agitation Methods 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 14
- 238000005119 centrifugation Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 150000003613 toluenes Chemical class 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 230000000640 hydroxylating effect Effects 0.000 claims description 3
- 229910000085 borane Inorganic materials 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 2
- -1 Butyldimethylsilyl epoxide Chemical class 0.000 claims 1
- 229910003978 SiClx Inorganic materials 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 abstract description 3
- 239000006087 Silane Coupling Agent Substances 0.000 abstract 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 abstract 1
- 230000033444 hydroxylation Effects 0.000 abstract 1
- 238000005805 hydroxylation reaction Methods 0.000 abstract 1
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 230000008901 benefit Effects 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Silicon Compounds (AREA)
Abstract
The invention relates to a method for preparing a polyaniline graft-modified silicon dioxide composite electrode material for supercapacitors. The method comprises the following specific steps: dispersing nano-silica in a hydroxylation solution in a novel stirring mode, so as to prepare hydroxyl-enriched nano-silica; carrying out a reaction with silane coupling agent, so as to obtain active reactive group containing modified nano-silica; dispersing the active reactive group containing modified nano-silica in an acidic aqueous solution, and carrying out ultrasonic dispersion; then, adding aniline into the dispersion, and carrying out uniform dispersing in a novel stirring mode; and dispersing an oxidant in an acidic aqueous solution, carrying out cold storage, then, dropwise adding the dispersion into the aniline and active reactive group containing modified nano-silica mixed solution, washing the mixed solution sequentially with water and anhydrous ethanol until the filter liquor is colorless, and carrying out vacuum drying, thereby obtaining the composite electrode material for the supercapacitors.
Description
Technical field
The present invention relates to the preparation field of the electrode material of ultracapacitor, more particularly to a kind of ultracapacitor polyphenyl
The preparation method of amine graft modified silicon dioxide combination electrode material.
Background technology
Ultracapacitor as a kind of new energy storage device, with its high power density, long life and fast discharge and recharge
The advantages of speed, is widely used in hybrid-electric car and portable electric appts, it has also become study hotspot in recent years.
Used as the core part of ultracapacitor, polyaniline is one of common electrode material to electrode material, with it is nontoxic,
Low cost, the advantages of be easily-synthesized.But polyaniline is after prolonged discharge and recharge, the contraction or expansion of material can be caused, be caused
Its bad stability.Therefore, in order to improve the cyclical stability of polyaniline, can attempt being combined other materials with polyaniline, from
And improve the structural stability of composite.Silica is because its source is wide, low cost and it is thermally-stabilised good the advantages of, be often used as
The filler of polyaniline composite material.But due to the small-size effect of nano-particle, agglomeration is easily produced, so as to affect
The homogeneity of composite property.Therefore, the agglomeration of nano silicon how is avoided, while improving electrode composite material
Combination property, and by researcher extensive concern.
The content of the invention
Goal of the invention：The method that this patent is related to is that a kind of polyaniline grafted improved silica of ultracapacitor is combined
The preparation method of electrode material.
Technical scheme：To achieve these goals, the present invention relates to a kind of ultracapacitor is with polyaniline grafted modified two
The preparation method of silica combination electrode material, the method comprises the steps：
(1) preparation of surface richness oh type nano silicon；
(2) preparation of the modified manometer silicon dioxide containing active reactive group；
(3) preparation of polyaniline grafted improved silica combination electrode material.
The preparation of the surface richness oh type nano silicon described in step (1) is referred to and nano silicon is added to hydroxyl
In base solution, disperse under a kind of new agitating mode, 0.5～2h is reacted at 50～80 DEG C and obtains rich oh type nanometer
Silica.After reaction terminates, mixed liquor centrifugation is washed 3～5 times successively with water and absolute ethyl alcohol, after vacuum drying
To surface richness oh type nano silicon.The concentration of nano silicon be 0.5～10wt%, the particle diameter of nano silicon
For 10～50nm.
A kind of new agitating mode described in step (1) is the dispersion mixing mode of mechanical agitation and ultrasonic wave,
Mechanical agitation rotating speed is 200～400rpm, and ultrasonic frequency is 30～50kHz.
Hydroxylating solution described in step (1) refers to the mixed solution containing hydrogen peroxide and ammoniacal liquor, or refers to containing the concentrated sulfuric acid
With the mixed solution of hydrogen peroxide.
The preparation of the modified manometer silicon dioxide containing active reactive group described in step (2) is referred to and will obtained in step (1)
To surface richness oh type nano silicon be dispersed in 30～100mL dry toluenes, instill 1～5mL of silane coupler, rise
Temperature after 2～5h of reaction, mixed liquor centrifugation is washed 3～5 times successively with water and absolute ethyl alcohol to 70～100 DEG C, and vacuum is done
The nano silicon containing active reactive group is obtained after dry.The concentration of rich oh type nano silicon is 0.5～20wt%.
Silane coupler is N- phenyl -3- TSL 8330s, VTES and 2- ((tert-butyl group diformazans
Base silicyl epoxide) methyl) -3- (4,4,5,5- tetramethyl -1,3,2- bis- Evil borine -2- bases) aniline.
The preparation of the polyaniline grafted improved silica combination electrode material described in step (3) is referred in step (2)
The improved silica containing active reactive group for obtaining is dispersed in the acidic aqueous solution of 0.05～2mol/L, ultrasonic disperse
0.5～2h, its concentration is 0.01～1wt%, and supersonic frequency is 30～50kHz, and acidic aqueous solution is hydrochloric acid, sulfuric acid, perchloric acid
Or the aqueous solution of DBSA；Aniline is added in above-mentioned mixed solution, the temperature control of mixed solution at 0～4 DEG C,
Disperse 0.5～2h under a kind of new agitating mode, the concentration of aniline is 0.05～0.5mol/L；Disperse oxidant is existed
In the acidic aqueous solution of 0.05～2mol/L, 0.5～2h is refrigerated at 0～4 DEG C, the concentration of oxidant is 0.05～0.5mol/L,
Oxidant is ammonium persulfate, potassium peroxydisulfate and hydrogen peroxide；Under a kind of new agitating mode, in the mixed liquor containing aniline
Oxidant mixed solution is added dropwise over, keeping temperature is 0～4 DEG C；After to be oxidized dose of completion of dropping, in a kind of new stirring side
Under formula, the reaction time is 0.5～2h.After reaction terminates, by mixed liquor colourless, the vacuum that is washed till filtrate with water and absolute ethyl alcohol successively
Ultracapacitor is obtained after drying with polyaniline grafted improved silica combination electrode material.
A kind of new agitating mode described in step (3) is the dispersion mixing mode of mechanical agitation and ultrasonic wave,
Mechanical agitation rotating speed is 200～400rpm, and ultrasonic frequency is 30～50kHz.
It is an advantage of the current invention that：The agitating mode of mechanical agitation and ultrasonic wave used by the present invention has dispersion effect
Fruit is notable, the advantages of improving reaction efficiency and be prevented effectively from the agglomeration of nano particle.The rich oh type that the present invention is obtained is received
The advantages of rice silica has easy to operate, yield is high, is capable of achieving industrialization.Present invention design lives polyaniline molecule with containing
The modified manometer silicon dioxide of property reactive group can improve the combination property of composite by way of chemical bonds.This
The ultracapacitor that invention is obtained has process is simple, low cost with polyaniline grafted improved silica combination electrode material
Honest and clean, electric conductivity is good, good cycling stability, excellent heat stability the advantages of, with good prospects for commercial application.
Description of the drawings
Fig. 1 is the polyaniline grafted improved silica (PANI/M-SiO of embodiment 12) combination electrode material Electronic Speculum shine
Piece.
Fig. 2 is the polyaniline grafted improved silica (PANI/M-SiO of embodiment 12) combination electrode material is in 100mV/s
The cyclic voltammetry curve of sweep speed, wherein abscissa are current potential, and ordinate is electric current.
Specific embodiment
Embodiment 1：
(1) add nano silicon in the mixed solution of hydrogen peroxide and ammoniacal liquor, be warming up to 40 DEG C, in mechanical agitation and
Lower reaction 1h by the way of ultrasonic wave, mechanical agitation rotating speed is 300rpm, and ultrasonic frequency is 40kHz.After reaction terminates, will
Mixed liquor centrifugation, is washed 3 times successively with water and absolute ethyl alcohol, and rich oh type nano silicon is obtained after vacuum drying.Receive
The concentration of rice silica is 10wt%, and the particle diameter of nano silicon is 20nm.
(2) in the case where mechanical agitation rotating speed is the 300rpm and ultrasonic frequency dispersing mode common for 40kHz, by rich hydroxyl
Type nano silicon is dispersed in 50mL dry toluenes, instills N- phenyl -3- TSL 8330 2mL, is heated up
And to 80 DEG C, after reaction 3h, mixed liquor centrifugation is washed 3 times successively with water and absolute ethyl alcohol, obtain after vacuum drying containing work
The nano silicon of property reactive group (is denoted as M-SiO2).The concentration of rich oh type nano silicon is 8wt%.
(3) silica containing active reactive group is dispersed in the aqueous hydrochloric acid solution of 1mol/L, ultrasonic disperse 0.5h,
The concentration of the silica containing active reactive group is 0.05wt%, and supersonic frequency is 40kHz.Add in above-mentioned mixed solution
Aniline, at 0 DEG C, in mechanical agitation rotating speed be 300rpm to the temperature control of mixed solution and ultrasonic frequency is that 40kHz is common
Mix 0.5h under dispersing mode, the concentration of aniline is 0.5mol/L；Ammonium persulfate is dispersed in the aqueous hydrochloric acid solution of 1mol/L,
0.5h is refrigerated at 0 DEG C, the concentration of ammonium persulfate is 0.5mol/L.In mechanical agitation rotating speed be 300rpm and ultrasonic frequency is
Under the dispersing mode of 40kHz, the mixed solution of ammonium persulfate is added dropwise in the mixed liquor containing aniline, keeping temperature is 0 DEG C；
After ammonium persulfate mixed liquor completion of dropping, in the dispersion side that mechanical agitation rotating speed is 300rpm and ultrasonic frequency is 40kHz
Under formula, the reaction time is 1h.After reaction terminates, mixed liquor is washed till into filtrate with water and absolute ethyl alcohol successively colourless, vacuum drying
After obtain ultracapacitor with polyaniline grafted improved silica combination electrode material.
Embodiment 2：
(1) nano silicon is added in the mixed solution of hydrogen peroxide and the concentrated sulfuric acid, 80 DEG C is warming up to, in mechanical agitation
With lower reaction 1h by the way of ultrasonic wave, mechanical agitation rotating speed is 300rpm, and ultrasonic frequency is 40kHz.After reaction terminates,
By mixed liquor centrifugation, washed 3 times with water and absolute ethyl alcohol successively, rich oh type nano silicon is obtained after vacuum drying.
The concentration of nano silicon is 10wt%, and the particle diameter of nano silicon is 20nm.
(2) in the case where mechanical agitation rotating speed is the 300rpm and ultrasonic frequency dispersing mode common for 40kHz, by rich hydroxyl
Type nano silicon is dispersed in 50mL dry toluenes, instills N- phenyl -3- TSL 8330 2mL, is heated up
And to 80 DEG C, after reaction 3h, mixed liquor centrifugation is washed 3 times successively with water and absolute ethyl alcohol, obtain after vacuum drying containing work
The nano silicon of property reactive group (is denoted as M-SiO2).The concentration of rich oh type nano silicon is 8wt%.
(3) silica containing active reactive group is dispersed in the aqueous hydrochloric acid solution of 1mol/L, ultrasonic disperse 0.5h,
The concentration of the silica containing active reactive group is 0.1wt%, and supersonic frequency is 40kHz.Add in above-mentioned mixed solution
Aniline, at 0 DEG C, in mechanical agitation rotating speed be 300rpm to the temperature control of mixed solution and ultrasonic frequency is that 40kHz is common
Mix 0.5h under dispersing mode, the concentration of aniline is 0.5mol/L；Ammonium persulfate is dispersed in the aqueous hydrochloric acid solution of 1mol/L,
0.5h is refrigerated at 0 DEG C, the concentration of ammonium persulfate is 0.5mol/L.In mechanical agitation rotating speed be 300rpm and ultrasonic frequency is
Under the dispersing mode of 40kHz, the mixed solution of ammonium persulfate is added dropwise in the mixed liquor containing aniline, keeping temperature is 0 DEG C；
After ammonium persulfate mixed liquor completion of dropping, in the dispersion side that mechanical agitation rotating speed is 300rpm and ultrasonic frequency is 40kHz
Under formula, the reaction time is 1h.After reaction terminates, mixed liquor is washed till into filtrate with water and absolute ethyl alcohol successively colourless, vacuum drying
After obtain ultracapacitor with polyaniline grafted improved silica combination electrode material.
Embodiment 3：
(1) add nano silicon in the mixed solution of hydrogen peroxide and ammoniacal liquor, be warming up to 80 DEG C, in mechanical agitation and
Lower reaction 1h by the way of ultrasonic wave, mechanical agitation rotating speed is 300rpm, and ultrasonic frequency is 40kHz.After reaction terminates, will
Mixed liquor centrifugation, is washed 3 times successively with water and absolute ethyl alcohol, and rich oh type nano silicon is obtained after vacuum drying.Receive
The concentration of rice silica is 10wt%, and the particle diameter of nano silicon is 20nm.
(2) in the case where mechanical agitation rotating speed is the 300rpm and ultrasonic frequency dispersing mode common for 40kHz, by rich hydroxyl
Type nano silicon is dispersed in 50mL dry toluenes, instills N- phenyl -3- TSL 8330 2mL, is heated up
And to 80 DEG C, after reaction 3h, mixed liquor centrifugation is washed 3 times successively with water and absolute ethyl alcohol, obtain after vacuum drying containing work
The nano silicon of property reactive group (is denoted as M-SiO2).The concentration of rich oh type nano silicon is 8wt%.
(3) silica containing active reactive group is dispersed in the aqueous hydrochloric acid solution of 1mol/L, ultrasonic disperse 0.5h,
The concentration of the silica containing active reactive group is 0.2wt%, and supersonic frequency is 40kHz.Add in above-mentioned mixed solution
Aniline, at 0 DEG C, in mechanical agitation rotating speed be 300rpm to the temperature control of mixed solution and ultrasonic frequency is that 40kHz is common
Mix 0.5h under dispersing mode, the concentration of aniline is 0.5mol/L；Ammonium persulfate is dispersed in the aqueous hydrochloric acid solution of 1mol/L,
0.5h is refrigerated at 0 DEG C, the concentration of ammonium persulfate is 0.5mol/L.In mechanical agitation rotating speed be 300rpm and ultrasonic frequency is
Under the dispersing mode of 40kHz, the mixed solution of ammonium persulfate is added dropwise in the mixed liquor containing aniline, keeping temperature is 0 DEG C；
After ammonium persulfate mixed liquor completion of dropping, in the dispersion side that mechanical agitation rotating speed is 300rpm and ultrasonic frequency is 40kHz
Under formula, the reaction time is 1h.After reaction terminates, mixed liquor is washed till into filtrate with water and absolute ethyl alcohol successively colourless, vacuum drying
After obtain ultracapacitor with polyaniline grafted improved silica combination electrode material.
The intersection example of the present invention is the foregoing is only, not to limit the present invention, to those skilled in the art
For can obviously do many improvement, all any modifications within the spirit and principles in the present invention, made, replace on an equal basis
Change, improve, should be included within the scope of protection of the invention.
Claims (7)
1. a kind of ultracapacitor preparation method of polyaniline grafted improved silica combination electrode material, include successively with
Lower step：
(1) preparation of surface richness oh type nano silicon；
(2) preparation of the modified manometer silicon dioxide containing active reactive group；
(3) preparation of polyaniline grafted improved silica combination electrode material.
2. a kind of ultracapacitor as claimed in claim 1 system of polyaniline grafted improved silica combination electrode material
Preparation Method, it is characterised in that：The preparation of the surface richness oh type nano silicon described in step (1) is referred to nanometer titanium dioxide
Silicon is added into hydroxylating solution, is disperseed under a kind of new agitating mode, 0.5～2h is reacted at 50～80 DEG C and obtains richness
Oh type nano silicon.After reaction terminates, by mixed liquor centrifugation, 3～5 times are washed with water and absolute ethyl alcohol successively, very
Sky obtains surface richness oh type nano silicon after being dried.The concentration of nano silicon be 0.5～10wt%, nano-silica
The particle diameter of SiClx is 10～50nm.
3. a kind of ultracapacitor as claimed in claim 2 system of polyaniline grafted improved silica combination electrode material
Preparation Method, it is characterised in that：A kind of new agitating mode described in step (1) is the dispersion of mechanical agitation and ultrasonic wave
Hybrid mode, mechanical agitation rotating speed is 200～400rpm, and ultrasonic frequency is 30～50kHz.
4. a kind of ultracapacitor as claimed in claim 2 system of polyaniline grafted improved silica combination electrode material
Preparation Method, it is characterised in that：Hydroxylating solution described in step (1) refers to the mixed solution containing hydrogen peroxide, ammoniacal liquor and water, or
Refer to the mixed solution containing the concentrated sulfuric acid and hydrogen peroxide.
5. a kind of ultracapacitor as claimed in claim 1 system of polyaniline grafted improved silica combination electrode material
Preparation Method, it is characterised in that：The preparation of the modified manometer silicon dioxide containing active reactive group described in step (2) is referred to step
Suddenly the surface richness oh type nano silicon for obtaining in (1) is dispersed in 30～100mL dry toluenes, instills silane coupler
1～5mL, is warming up to 70～100 DEG C, after 2～5h of reaction, by mixed liquor centrifugation, washes 3～5 with water and absolute ethyl alcohol successively
It is secondary, the nano silicon containing active reactive group is obtained after vacuum drying.The concentration of rich oh type nano silicon is 0.5
～20wt%.Silane coupler is N- phenyl -3- TSL 8330s, VTES and 2- ((uncles
Butyldimethylsilyl epoxide) methyl) -3- (4,4,5,5- tetramethyl -1,3,2- bis- Evil borine -2- bases) aniline.
6. a kind of ultracapacitor as claimed in claim 1 system of polyaniline grafted improved silica combination electrode material
Preparation Method, it is characterised in that：The preparation of the polyaniline grafted improved silica combination electrode material described in step (3) refer to by
The improved silica containing active reactive group obtained in step (2) is dispersed in the acidic aqueous solution of 0.05～2mol/L,
0.5～2h of ultrasonic disperse, its concentration is 0.01～1wt%, and supersonic frequency is 30～50kHz, and acidic aqueous solution is hydrochloric acid, sulphur
The aqueous solution of acid, perchloric acid or DBSA；Aniline, the temperature control of mixed solution are added in above-mentioned mixed solution
At 0～4 DEG C, 0.5～2h is disperseed under a kind of new agitating mode, the concentration of aniline is 0.05～0.5mol/L；Will oxidation
Agent is dispersed in the acidic aqueous solution of 0.05～2mol/L, refrigerates 0.5～2h at 0～4 DEG C, and the concentration of oxidant is 0.05～
0.5mol/L, oxidant is ammonium persulfate, potassium peroxydisulfate and hydrogen peroxide；Under a kind of new agitating mode, containing aniline
Mixed liquor in be added dropwise over oxidant mixed solution, keeping temperature is 0～4 DEG C；After to be oxidized dose of completion of dropping, a kind of new
Under the agitating mode of type, the reaction time is 0.5～2h.After reaction terminates, mixed liquor is washed till into filter with water and absolute ethyl alcohol successively
Liquid is colourless, and ultracapacitor is obtained after vacuum drying with polyaniline grafted improved silica combination electrode material.
7. a kind of ultracapacitor as claimed in claim 6 system of polyaniline grafted improved silica combination electrode material
Preparation Method, it is characterised in that：A kind of new agitating mode described in step (3) is the dispersion of mechanical agitation and ultrasonic wave
Hybrid mode, mechanical agitation rotating speed is 200～400rpm, and ultrasonic frequency is 30～50kHz.
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| CN113773556A (en) * | 2021-09-29 | 2021-12-10 | 北京化工大学 | Double-component composite reinforcing agent for hydrogenated nitrile rubber and preparation method thereof |
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| CN105789577A (en) * | 2016-03-16 | 2016-07-20 | 奇瑞汽车股份有限公司 | Preparation method for silicon negative electrode material for lithium ion battery and silicon negative electrode material |
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| CN113773556A (en) * | 2021-09-29 | 2021-12-10 | 北京化工大学 | Double-component composite reinforcing agent for hydrogenated nitrile rubber and preparation method thereof |
| CN113773556B (en) * | 2021-09-29 | 2022-05-27 | 北京化工大学 | Double-component composite reinforcing agent for hydrogenated nitrile rubber and preparation method thereof |
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