CN106981372A - A kind of carbon electrode material preparation method applied to ultracapacitor - Google Patents
A kind of carbon electrode material preparation method applied to ultracapacitor Download PDFInfo
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- CN106981372A CN106981372A CN201710243057.8A CN201710243057A CN106981372A CN 106981372 A CN106981372 A CN 106981372A CN 201710243057 A CN201710243057 A CN 201710243057A CN 106981372 A CN106981372 A CN 106981372A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/32—Carbon-based
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- 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
Abstract
The invention discloses the carbon electrode material preparation method applied to ultracapacitor, the technique is by by acetylene carbon black and sulfuric acid, SSS carries out Hybrid Heating, it is warm, cooling, dilution, centrifuge, modified carbon black compound is obtained after the sequence of operations such as washing, add the lithium of phosphoric acid hydrogen two, nickel chloride is reacted in reactor, acid treatment is carried out after drying, again by itself and acrylonitrile powder, dimethyl sulfoxide (DMSO), the reactant mixing through pyroreaction such as tetraethyl orthosilicate, add distilled water ultrasonic disperse, and add the compositions such as melamine cyanurate progress pyroreaction, finally by washing, vacuum drying obtains finished product.The carbon electrode material applied to ultracapacitor being prepared from, its electrical conductivity is high, and specific capacitance is big, and cycle-index is more, with preferable application prospect.Also disclose simultaneously as application of the carbon electrode material in ultracapacitor is prepared made from the preparation technology applied to ultracapacitor.
Description
Technical field
The present invention relates to this technical field of capacitor material, the carbon electrode material applied to ultracapacitor is related specifically to
Preparation method for material.
Background technology
With the aggravation of environmental pollution and being on the rise for energy crisis, people become to the growth requirement of novel mobile power source
It is more and more urgent, ultracapacitor high power, can quickly fill and meet the mankind the characteristics of having extended cycle life to novel energy
Demand.Ultracapacitor is a kind of both with high power density as traditional capacitor, has the similar energy of electrochmical power source close again
The new type of energy storage device of degree, is generally divided into fake capacitance ultracapacitor, double electric layers supercapacitor according to its energy storage principle and mixes
Mould assembly ultracapacitor.Fake capacitance ultracapacitor mainly uses quick and reversible in electrode surface or near surface generation
Redox reaction realizes energy storage, and the electrode material of fake capacitance ultracapacitor is mainly transition metal oxide and conducting polymer
Thing.Double electric layers supercapacitor is adsorbed respectively on two interfaces between carbon electrode and electrolyte using positive and negative ion, is made
Energy storage is realized into the electrical potential difference between two electrodes, double electric layers supercapacitor is generally using the carbon-based active with high-ratio surface
Material is used as electrode material.Hybrid super capacitor is that a pole is stored and converted by electrochemical reaction using battery material
Energy, another pole then stores energy by electric double layer, with asymmetric electrode.Current research focus is its electrode material,
Including carbon material, metal oxide and conducting polymer.
Due to carbon material have higher specific surface area, excellent conductive capability, unique chemical stability, it is good into
Type, while relative low price, raw material sources are abundant, production technology also comparative maturity, it is still supercapacitor applications so far
Widest electrode material.However, traditional carbon electrode material is often present, electrical conductivity is not high, specific capacitance is not enough, cycle-index
The defect such as few, constrains the extensive use of ultracapacitor, this is accomplished by developing new carbon electrode material.
The content of the invention
In order to solve the above technical problems, the present invention provides the carbon electrode material preparation method applied to ultracapacitor, should
Technique by the way that acetylene carbon black and sulfuric acid, SSS carried out into Hybrid Heating, warm, cooling, dilution, centrifuge,
Modified carbon black compound is obtained after the sequence of operations such as washing, the lithium of phosphoric acid hydrogen two, nickel chloride is added and is carried out in reactor instead
Should, carry out acid treatment after drying, then by it with acrylonitrile powder, dimethyl sulfoxide (DMSO), tetraethyl orthosilicate etc. through the anti-of pyroreaction
Answer thing to mix, add distilled water ultrasonic disperse, and add melamine cyanurate, atomized copper powder, germanium sulfide, dipivaloylmethane
Cerium, silane coupler carry out pyroreaction, and finished product is obtained finally by washing, vacuum drying.Being applied to for being prepared from is super
The carbon electrode material of capacitor, its electrical conductivity is high, and specific capacitance is big, and cycle-index is more, with preferable application prospect.It is simultaneously also public
Open as application of the carbon electrode material in ultracapacitor is prepared made from the preparation technology applied to ultracapacitor.
The purpose of the present invention can be achieved through the following technical solutions：
Applied to the carbon electrode material preparation method of ultracapacitor, comprise the following steps：
（1）15 g acetylene carbon blacks are mixed under the conditions of 0 DEG C by liquid-solid ratio 8-12 with the sulfuric acid of mass concentration 92%, g pairs of addition 3
SSS, is heated with 8-10 DEG C/min speed, is warming up to insulation reaction after 110 DEG C and holds 2-3 h, then will reaction
Mixed liquor is cooled to room temperature, and 600 mL distilled water are added into reaction mixture and are diluted, then according to 7000-8000 rpm
Rotating speed centrifuged, separate except solution, then washed the lower sediment thing being centrifugally separating to obtain with 1000 mL absolute ethyl alcohols
2-3 times, by after washing sediment add distilled water be made into liquid-solid ratio be 15 mixed liquor and transfer to high pressure hydro-thermal reaction
In kettle, it is 1.2, the hydro-thermal process 10-15 h at 350 DEG C to keep its volumetric filling ratio, is cooled to after room temperature and washes hydrothermal product
Wash, suction filtration, until pH value is 7.0-7.2, it is to dry to constant weight in 75 DEG C of vacuum drying chamber to be then placed in temperature, is modified
Carbon black compound；
（2）By step（1）Obtained modified carbon black compound is added in distilled water with 25 KHz frequency with the lithium of 2g phosphoric acid hydrogen two
The min of rate ultrasonic disperse 30, then adds the g of nickel chloride 0.08, stirs 30 min at room temperature with 3000 rpm, by the mixed of formation
Close liquid to be transferred in reactor, 50 min are reacted at 150 DEG C；After reaction terminates, reaction mixture is placed in 80 DEG C of baking ovens
It is dried overnight, obtains desciccate；
（3）With 2.0 mol/L hydrochloric acid to step（2）Desciccate carry out acid treatment, the liquid-solid ratio of hydrochloric acid and desciccate
Be 55 DEG C for 8-10, treatment temperature, processing time be 3-5 h, it is neutrality that suction filtration to pH value, which is then washed with deionized, will be located
Product after reason is put into the vacuum drying chamber that temperature is 60 DEG C and dries 24 h, obtains the first dry reagent contained；
（4）0.6 mg polyacrylonitrile powders are dissolved in appropriate dimethyl sulfoxide (DMSO), 100 mL concentration are added for 0.5 mol/L
Ammonia spirit, 3-5 min are stirred at 70 DEG C with 200 rpm speed, 0.5 mL tetraethyl orthosilicates are then slowly added into, so
100 DEG C are warming up in polytetrafluoroethylcontainer container afterwards, the citric acid solution that 10 ml concentration are 0.2 mol/L is added, continues to heat up
8-10 h are stirred to 150 DEG C and at this temperature, obtained product are centrifuged according to 5000 rpm rotating speed, sediment is used
Deionized water is washed, and the second dry reagent contained is obtained after being dried at 120 DEG C；
（5）By step（3）Obtained the first dry reagent contained and step（4）Obtained the second dry reagent contained mixing, adds and steams
In distilled water, 45 min are handled with 50 KHz frequency ultrasound and obtain mixed dispersion liquid, 0.5-0.8 g cyanuric acids three are added thereto
Poly cyanamid, 0.2-0.4 g atomized copper powders, 0.1-0.3 g germanium sulfides, 0.06-0.1 g dipivaloylmethane ceriums, 0.05-0.08 g
Silane coupler, then heats to 110 DEG C, insulated and stirred 25-30 min are cooled to after room temperature reacting liquid filtering obtaining solid-state
Product, is washed to neutrality with water and ethanol, then is placed in 60-70 DEG C of vacuum drying chamber dry 18 h, obtains being applied to surpass
The carbon electrode material of level capacitor.
Preferably, the step（1）The iodine absorption value of middle acetylene carbon black is 105 g/Kg.
Preferably, the step（5）It is middle that 0.6 g melamine cyanurates, 0.3 g atomization copper are added into mixed dispersion liquid
Powder, 0.2 g germanium sulfides, 0.08 g dipivaloylmethane ceriums, 0.05 g silane couplers.
Preferably, the step（5）In silane coupler be selected from VTES, methacryloxy
Any one in propyl trimethoxy silicane, 3- glycydoxy trimethoxy silanes.
Prepared present invention also offers the carbon electrode material applied to ultracapacitor obtained by above-mentioned preparation technology
Application in ultracapacitor.
Compared with prior art, its advantage is the present invention：
（1）The carbon electrode material preparation technology applied to ultracapacitor of the present invention is by by acetylene carbon black and sulfuric acid, benzene second
Alkene sodium sulfonate carries out Hybrid Heating, warm, cooling, dilution, centrifuge, washing etc. obtains modified carbon black after sequence of operations
Compound, adds the lithium of phosphoric acid hydrogen two, nickel chloride and is reacted in reactor, and acid treatment is carried out after drying, then by itself and third
The reactant mixing through pyroreaction such as alkene nitrile powder, dimethyl sulfoxide (DMSO), tetraethyl orthosilicate, adds distilled water ultrasonic disperse, and
Add melamine cyanurate, atomized copper powder, germanium sulfide, dipivaloylmethane cerium, silane coupler and carry out pyroreaction, finally
Finished product is obtained by washing, vacuum drying.The carbon electrode material applied to ultracapacitor being prepared from, its electrical conductivity is high,
Specific capacitance is big, and cycle-index is more, with preferable application prospect.
（2）Carbon electrode material raw material applied to ultracapacitor of the invention is cheap, technique is simple, suitable for extensive work
Industryization is used, practical.
Embodiment
The technical scheme of invention is described in detail with reference to specific embodiment.
Embodiment 1
（1）It is 105 g/Kg acetylene carbon blacks sulfuric acid by liquid-solid ratio 8 and mass concentration 92% under the conditions of 0 DEG C by 15 g iodine absorption values
Mixing, adds 3 g sodium p styrene sulfonates, is heated with 8 DEG C/min speed, is warming up to insulation reaction after 110 DEG C and holds 2 h, with
Reaction mixture is cooled to room temperature afterwards, 600 mL distilled water are added into reaction mixture and are diluted, then according to 7000
Rpm rotating speed is centrifuged, and is separated except solution, then with 1000 mL absolute ethyl alcohols by the lower sediment thing being centrifugally separating to obtain
Washing 2 times, the sediment after washing is added distilled water is made into mixed liquor that liquid-solid ratio is 15 and to transfer to high pressure hydro-thermal anti-
Answer in kettle, it is 1.2, the h of hydro-thermal process 10 at 350 DEG C to keep its volumetric filling ratio, is cooled to after room temperature and washes hydrothermal product
Wash, suction filtration, until pH value is 7.0, it is to dry to constant weight in 75 DEG C of vacuum drying chamber to be then placed in temperature, obtains being modified carbon black
Compound；
（2）By step（1）Obtained modified carbon black compound is added in distilled water with 25 KHz frequency with the lithium of 2g phosphoric acid hydrogen two
The min of rate ultrasonic disperse 30, then adds the g of nickel chloride 0.08, stirs 30 min at room temperature with 3000 rpm, by the mixed of formation
Close liquid to be transferred in reactor, 50 min are reacted at 150 DEG C；After reaction terminates, reaction mixture is placed in 80 DEG C of baking ovens
It is dried overnight, obtains desciccate；
（3）With 2.0 mol/L hydrochloric acid to step（2）Desciccate carry out acid treatment, the liquid-solid ratio of hydrochloric acid and desciccate
Be 55 DEG C for 8, treatment temperature, processing time be 3 h, it is neutrality that suction filtration to pH value, which is then washed with deionized, after processing
Product to be put into temperature be to dry 24 h in 60 DEG C of vacuum drying chamber, obtain the first dry reagent contained；
（4）0.6 mg polyacrylonitrile powders are dissolved in appropriate dimethyl sulfoxide (DMSO), 100 mL concentration are added for 0.5 mol/L
Ammonia spirit, 3 min are stirred at 70 DEG C with 200 rpm speed, 0.5 mL tetraethyl orthosilicates are then slowly added into, then
100 DEG C are warming up in polytetrafluoroethylcontainer container, the citric acid solution that 10 ml concentration are 0.2 mol/L is added, is continuously heating to
150 DEG C and stir 8 h at this temperature, obtained product centrifuged according to 5000 rpm rotating speed, sediment spend from
Sub- water is washed, and the second dry reagent contained is obtained after being dried at 120 DEG C；
（5）By step（3）Obtained the first dry reagent contained and step（4）Obtained the second dry reagent contained mixing, adds and steams
In distilled water, 45 min are handled with 50 KHz frequency ultrasound and obtain mixed dispersion liquid, 0.6 g cyanuric acid melamines are added thereto
Amine, 0.3 g atomized copper powders, 0.2 g germanium sulfides, 0.08 g dipivaloylmethane ceriums, 0.05 g VTESs, so
After be warming up to 110 DEG C, the min of insulated and stirred 25 is cooled to after room temperature reacting liquid filtering obtaining solid product, with water and ethanol
Washed to neutrality, then be placed in 60 DEG C of vacuum drying chambers dry 18 h, obtain the carbon electrode material applied to ultracapacitor
Material.
The performance test results of the obtained carbon electrode material applied to ultracapacitor are as shown in table 1.
Embodiment 2
（1）It is 105 g/Kg acetylene carbon blacks sulfuric acid by liquid-solid ratio 10 and mass concentration 92% under the conditions of 0 DEG C by 15 g iodine absorption values
Mixing, adds 3 g sodium p styrene sulfonates, is heated with 9 DEG C/min speed, is warming up to insulation reaction after 110 DEG C and holds 2.5 h,
Reaction mixture is then cooled to room temperature, 600 mL distilled water are added into reaction mixture and are diluted, then according to
7500 rpm rotating speed is centrifuged, and is separated except solution, then the lower floor being centrifugally separating to obtain is sunk with 1000 mL absolute ethyl alcohols
Starch wash 2 times, by after washing sediment add distilled water be made into liquid-solid ratio be 15 mixed liquor and transfer to water under high pressure
In thermal response kettle, it is 1.2, the h of hydro-thermal process 12 at 350 DEG C to keep its volumetric filling ratio, is cooled to hydrothermal product after room temperature
Washing, suction filtration, until pH value is 7.1, is then placed in the vacuum drying chamber that temperature is 75 DEG C and dries to constant weight, obtain carbon modified
Black compound；
（2）By step（1）Obtained modified carbon black compound is added in distilled water with 25 KHz frequency with the lithium of 2g phosphoric acid hydrogen two
The min of rate ultrasonic disperse 30, then adds the g of nickel chloride 0.08, stirs 30 min at room temperature with 3000 rpm, by the mixed of formation
Close liquid to be transferred in reactor, 50 min are reacted at 150 DEG C；After reaction terminates, reaction mixture is placed in 80 DEG C of baking ovens
It is dried overnight, obtains desciccate；
（3）With 2.0 mol/L hydrochloric acid to step（2）Desciccate carry out acid treatment, the liquid-solid ratio of hydrochloric acid and desciccate
Be 55 DEG C for 9, treatment temperature, processing time be 4 h, it is neutrality that suction filtration to pH value, which is then washed with deionized, after processing
Product to be put into temperature be to dry 24 h in 60 DEG C of vacuum drying chamber, obtain the first dry reagent contained；
（4）0.6 mg polyacrylonitrile powders are dissolved in appropriate dimethyl sulfoxide (DMSO), 100 mL concentration are added for 0.5 mol/L
Ammonia spirit, 4 min are stirred at 70 DEG C with 200 rpm speed, 0.5 mL tetraethyl orthosilicates are then slowly added into, then
100 DEG C are warming up in polytetrafluoroethylcontainer container, the citric acid solution that 10 ml concentration are 0.2 mol/L is added, is continuously heating to
150 DEG C and stir 9 h at this temperature, obtained product centrifuged according to 5000 rpm rotating speed, sediment spend from
Sub- water is washed, and the second dry reagent contained is obtained after being dried at 120 DEG C；
（5）By step（3）Obtained the first dry reagent contained and step（4）Obtained the second dry reagent contained mixing, adds and steams
In distilled water, 45 min are handled with 50 KHz frequency ultrasound and obtain mixed dispersion liquid, 0.6 g cyanuric acid melamines are added thereto
Amine, 0.3 g atomized copper powders, 0.2 g germanium sulfides, 0.08 g dipivaloylmethane ceriums, 0.05 g methacryloxypropyls three
Methoxy silane, then heats to 110 DEG C, the min of insulated and stirred 28 is cooled to after room temperature reacting liquid filtering obtaining solid-state production
Thing, is washed to neutrality with water and ethanol, then is placed in 65 DEG C of vacuum drying chambers dry 18 h, obtains being applied to super capacitor
The carbon electrode material of device.
The performance test results of the obtained carbon electrode material applied to ultracapacitor are as shown in table 1.
Embodiment 3
（1）It is 105 g/Kg acetylene carbon blacks sulfuric acid by liquid-solid ratio 12 and mass concentration 92% under the conditions of 0 DEG C by 15 g iodine absorption values
Mixing, adds 3 g sodium p styrene sulfonates, is heated with 10 DEG C/min speed, is warming up to insulation reaction after 110 DEG C and holds 3 h,
Reaction mixture is then cooled to room temperature, 600 mL distilled water are added into reaction mixture and are diluted, then according to
8000 rpm rotating speed is centrifuged, and is separated except solution, then the lower floor being centrifugally separating to obtain is sunk with 1000 mL absolute ethyl alcohols
Starch wash 3 times, by after washing sediment add distilled water be made into liquid-solid ratio be 15 mixed liquor and transfer to water under high pressure
In thermal response kettle, it is 1.2, the h of hydro-thermal process 15 at 350 DEG C to keep its volumetric filling ratio, is cooled to hydrothermal product after room temperature
Washing, suction filtration, until pH value is 7.2, is then placed in the vacuum drying chamber that temperature is 75 DEG C and dries to constant weight, obtain carbon modified
Black compound；
（2）By step（1）Obtained modified carbon black compound is added in distilled water with 25 KHz frequency with the lithium of 2g phosphoric acid hydrogen two
The min of rate ultrasonic disperse 30, then adds the g of nickel chloride 0.08, stirs 30 min at room temperature with 3000 rpm, by the mixed of formation
Close liquid to be transferred in reactor, 50 min are reacted at 150 DEG C；After reaction terminates, reaction mixture is placed in 80 DEG C of baking ovens
It is dried overnight, obtains desciccate；
（3）With 2.0 mol/L hydrochloric acid to step（2）Desciccate carry out acid treatment, the liquid-solid ratio of hydrochloric acid and desciccate
Be 55 DEG C for 10, treatment temperature, processing time be 5 h, it is neutrality that suction filtration to pH value, which is then washed with deionized, after processing
Product to be put into temperature be to dry 24 h in 60 DEG C of vacuum drying chamber, obtain the first dry reagent contained；
（4）0.6 mg polyacrylonitrile powders are dissolved in appropriate dimethyl sulfoxide (DMSO), 100 mL concentration are added for 0.5 mol/L
Ammonia spirit, 5 min are stirred at 70 DEG C with 200 rpm speed, 0.5 mL tetraethyl orthosilicates are then slowly added into, then
100 DEG C are warming up in polytetrafluoroethylcontainer container, the citric acid solution that 10 ml concentration are 0.2 mol/L is added, is continuously heating to
150 DEG C and stir 10 h at this temperature, obtained product centrifuged according to 5000 rpm rotating speed, sediment spend from
Sub- water is washed, and the second dry reagent contained is obtained after being dried at 120 DEG C；
（5）By step（3）Obtained the first dry reagent contained and step（4）Obtained the second dry reagent contained mixing, adds and steams
In distilled water, 45 min are handled with 50 KHz frequency ultrasound and obtain mixed dispersion liquid, 0.6 g cyanuric acid melamines are added thereto
Amine, 0.3 g atomized copper powders, 0.2 g germanium sulfides, 0.08 g dipivaloylmethane ceriums, 0.05 g 3- glycydoxies
Trimethoxy silane, then heats to 110 DEG C, the min of insulated and stirred 30 is cooled to after room temperature reacting liquid filtering obtaining solid-state
Product, is washed to neutrality with water and ethanol, then is placed in 70 DEG C of vacuum drying chambers dry 18 h, obtains being applied to super electricity
The carbon electrode material of container.
The performance test results of the obtained carbon electrode material applied to ultracapacitor are as shown in table 1.
Comparative example 1
（1）It is 105 g/Kg acetylene carbon blacks sulfuric acid by liquid-solid ratio 8 and mass concentration 92% under the conditions of 0 DEG C by 15 g iodine absorption values
Mixing, adds 3 g sodium p styrene sulfonates, is heated with 8 DEG C/min speed, is warming up to insulation reaction after 110 DEG C and holds 2 h, with
Reaction mixture is cooled to room temperature afterwards, 600 mL distilled water are added into reaction mixture and are diluted, then according to 7000
Rpm rotating speed is centrifuged, and is separated except solution, then with 1000 mL absolute ethyl alcohols by the lower sediment thing being centrifugally separating to obtain
Washing 2 times, the sediment after washing is added distilled water is made into mixed liquor that liquid-solid ratio is 15 and to transfer to high pressure hydro-thermal anti-
Answer in kettle, it is 1.2, the h of hydro-thermal process 10 at 350 DEG C to keep its volumetric filling ratio, is cooled to after room temperature and washes hydrothermal product
Wash, suction filtration, until pH value is 7.0, it is to dry to constant weight in 75 DEG C of vacuum drying chamber to be then placed in temperature, obtains being modified carbon black
Compound；
（2）By step（1）Obtained modified carbon black compound is added in distilled water with 25 KHz frequency with the lithium of 2g phosphoric acid hydrogen two
The min of rate ultrasonic disperse 30, then adds the g of nickel chloride 0.08, stirs 30 min at room temperature with 3000 rpm, by the mixed of formation
Close liquid to be transferred in reactor, 50 min are reacted at 150 DEG C；After reaction terminates, reaction mixture is placed in 80 DEG C of baking ovens
It is dried overnight, obtains desciccate；
（3）With 2.0 mol/L hydrochloric acid to step（2）Desciccate carry out acid treatment, the liquid-solid ratio of hydrochloric acid and desciccate
Be 55 DEG C for 8, treatment temperature, processing time be 3 h, it is neutrality that suction filtration to pH value, which is then washed with deionized, after processing
Product to be put into temperature be to dry 24 h in 60 DEG C of vacuum drying chamber, obtain the first dry reagent contained；
（4）0.6 mg polyacrylonitrile powders are dissolved in appropriate dimethyl sulfoxide (DMSO), 100 mL concentration are added for 0.5 mol/L
Ammonia spirit, 3 min are stirred at 70 DEG C with 200 rpm speed, 0.5 mL tetraethyl orthosilicates are then slowly added into, then
100 DEG C are warming up in polytetrafluoroethylcontainer container, the citric acid solution that 10 ml concentration are 0.2 mol/L is added, is continuously heating to
150 DEG C and stir 8 h at this temperature, obtained product centrifuged according to 5000 rpm rotating speed, sediment spend from
Sub- water is washed, and the second dry reagent contained is obtained after being dried at 120 DEG C；
（5）By step（3）Obtained the first dry reagent contained and step（4）Obtained the second dry reagent contained mixing, adds and steams
In distilled water, 45 min are handled with 50 KHz frequency ultrasound and obtain mixed dispersion liquid, 1 g cyanuric acid melamines are added thereto
Amine, 0.1 g atomized copper powders, 0.4 g germanium sulfides, 0.05 g dipivaloylmethane ceriums, 0.05 g VTESs, so
After be warming up to 110 DEG C, the min of insulated and stirred 25 is cooled to after room temperature reacting liquid filtering obtaining solid product, with water and ethanol
Washed to neutrality, then be placed in 60 DEG C of vacuum drying chambers dry 18 h, obtain the carbon electrode material applied to ultracapacitor
Material.
The performance test results of the obtained carbon electrode material applied to ultracapacitor are as shown in table 1.
Comparative example 2
（1）It is 105 g/Kg acetylene carbon blacks sulfuric acid by liquid-solid ratio 10 and mass concentration 92% under the conditions of 0 DEG C by 15 g iodine absorption values
Mixing, adds 3 g sodium p styrene sulfonates, is heated with 9 DEG C/min speed, is warming up to insulation reaction after 110 DEG C and holds 2.5 h,
Reaction mixture is then cooled to room temperature, 600 mL distilled water are added into reaction mixture and are diluted, then according to
7500 rpm rotating speed is centrifuged, and is separated except solution, then the lower floor being centrifugally separating to obtain is sunk with 1000 mL absolute ethyl alcohols
Starch wash 2 times, by after washing sediment add distilled water be made into liquid-solid ratio be 15 mixed liquor and transfer to water under high pressure
In thermal response kettle, it is 1.2, the h of hydro-thermal process 12 at 350 DEG C to keep its volumetric filling ratio, is cooled to hydrothermal product after room temperature
Washing, suction filtration, until pH value is 7.1, is then placed in the vacuum drying chamber that temperature is 75 DEG C and dries to constant weight, obtain carbon modified
Black compound；
（2）By step（1）Obtained modified carbon black compound is mixed with appropriate distilled water, then adds the g of nickel chloride 0.08,
30 min are stirred with 3000 rpm at room temperature, the mixed liquor of formation is transferred in reactor, 50 min are reacted at 150 DEG C；
After reaction terminates, reaction mixture is placed in 80 DEG C of baking ovens and is dried overnight, desciccate is obtained；
（3）With 2.0 mol/L hydrochloric acid to step（2）Desciccate carry out acid treatment, the liquid-solid ratio of hydrochloric acid and desciccate
Be 55 DEG C for 9, treatment temperature, processing time be 4 h, it is neutrality that suction filtration to pH value, which is then washed with deionized, after processing
Product to be put into temperature be to dry 24 h in 60 DEG C of vacuum drying chamber, obtain the first dry reagent contained；
（4）0.6 mg polyacrylonitrile powders are dissolved in appropriate dimethyl sulfoxide (DMSO), 100 mL concentration are added for 0.5 mol/L
Ammonia spirit, 4 min are stirred at 70 DEG C with 200 rpm speed, 0.5 mL tetraethyl orthosilicates are then slowly added into, then
100 DEG C are warming up in polytetrafluoroethylcontainer container, the citric acid solution that 10 ml concentration are 0.2 mol/L is added, is continuously heating to
150 DEG C and stir 9 h at this temperature, obtained product centrifuged according to 5000 rpm rotating speed, sediment spend from
Sub- water is washed, and the second dry reagent contained is obtained after being dried at 120 DEG C；
（5）By step（3）Obtained the first dry reagent contained and step（4）Obtained the second dry reagent contained mixing, adds and steams
In distilled water, 45 min are handled with 50 KHz frequency ultrasound and obtain mixed dispersion liquid, 0.6 g cyanuric acid melamines are added thereto
Amine, 0.3 g atomized copper powders, 0.2 g germanium sulfides, 0.08 g dipivaloylmethane ceriums, 0.05 g methacryloxypropyls three
Methoxy silane, then heats to 110 DEG C, the min of insulated and stirred 28 is cooled to after room temperature reacting liquid filtering obtaining solid-state production
Thing, is washed to neutrality with water and ethanol, then is placed in 65 DEG C of vacuum drying chambers dry 18 h, obtains being applied to super capacitor
The carbon electrode material of device.
The performance test results of the obtained carbon electrode material applied to ultracapacitor are as shown in table 1.
Comparative example 3
（1）It is 105 g/Kg acetylene carbon blacks sulfuric acid by liquid-solid ratio 13 and mass concentration 92% under the conditions of 0 DEG C by 15 g iodine absorption values
Mixing, adds 3 g sodium p styrene sulfonates, is heated with 7 DEG C/min speed, is warming up to insulation reaction after 110 DEG C and holds 3 h, with
Reaction mixture is cooled to room temperature afterwards, 600 mL distilled water are added into reaction mixture and are diluted, then according to 8000
Rpm rotating speed is centrifuged, and is separated except solution, then with 1000 mL absolute ethyl alcohols by the lower sediment thing being centrifugally separating to obtain
Washing 3 times, the sediment after washing is added distilled water is made into mixed liquor that liquid-solid ratio is 15 and to transfer to high pressure hydro-thermal anti-
Answer in kettle, it is 1.2, the h of hydro-thermal process 15 at 320 DEG C to keep its volumetric filling ratio, is cooled to after room temperature and washes hydrothermal product
Wash, suction filtration, until pH value is 7.2, it is to dry to constant weight in 75 DEG C of vacuum drying chamber to be then placed in temperature, obtains being modified carbon black
Compound；
（2）By step（1）Obtained modified carbon black compound is added in distilled water with 25 KHz frequency with the lithium of 2g phosphoric acid hydrogen two
The min of rate ultrasonic disperse 30, then adds the g of nickel chloride 0.08, stirs 30 min at room temperature with 3000 rpm, by the mixed of formation
Close liquid to be transferred in reactor, 50 min are reacted at 200 DEG C；After reaction terminates, reaction mixture is placed in 80 DEG C of baking ovens
It is dried overnight, obtains desciccate；
（3）With 2.0 mol/L hydrochloric acid to step（2）Desciccate carry out acid treatment, the liquid-solid ratio of hydrochloric acid and desciccate
Be 55 DEG C for 10, treatment temperature, processing time be 5 h, it is neutrality that suction filtration to pH value, which is then washed with deionized, after processing
Product to be put into temperature be to dry 24 h in 60 DEG C of vacuum drying chamber, obtain the first dry reagent contained；
（4）0.6 mg polyacrylonitrile powders are dissolved in appropriate dimethyl sulfoxide (DMSO), 100 mL concentration are added for 0.5 mol/L
Ammonia spirit, 5 min are stirred at 70 DEG C with 200 rpm speed, 0.5 mL tetraethyl orthosilicates are then slowly added into, then
100 DEG C are warming up in polytetrafluoroethylcontainer container, the citric acid solution that 10 ml concentration are 0.2 mol/L is added, is continuously heating to
150 DEG C and stir 10 h at this temperature, obtained product centrifuged according to 5000 rpm rotating speed, sediment spend from
Sub- water is washed, and the second dry reagent contained is obtained after being dried at 120 DEG C；
（5）By step（3）Obtained the first dry reagent contained and step（4）Obtained the second dry reagent contained mixing, adds and steams
In distilled water, 45 min are handled with 50 KHz frequency ultrasound and obtain mixed dispersion liquid, 0.6 g cyanuric acid melamines are added thereto
Amine, 0.3 g atomized copper powders, 0.2 g germanium sulfides, 0.08 g dipivaloylmethane ceriums, 0.05 g 3- glycydoxies
Trimethoxy silane, then heats to 110 DEG C, the min of insulated and stirred 30 is cooled to after room temperature reacting liquid filtering obtaining solid-state
Product, is washed to neutrality with water and ethanol, then is placed in 70 DEG C of vacuum drying chambers dry 18 h, obtains being applied to super electricity
The carbon electrode material of container.
The performance test results of the obtained carbon electrode material applied to ultracapacitor are as shown in table 1.
Carbon electrode material made from embodiment 1-3 and comparative example 1-3 applied to ultracapacitor is subjected to electricity respectively
Conductance, specific capacitance, this several performance tests of cycle-index.
Table 1
| Electrical conductivity（s/cm） | Specific capacitance（F/g） | Cycle-index（It is secondary） | |
| Embodiment 1 | 40.9 | 428 | 6500 |
| Embodiment 2 | 39.6 | 417 | 6200 |
| Embodiment 3 | 38.7 | 405 | 6100 |
| Comparative example 1 | 20.4 | 312 | 5200 |
| Comparative example 2 | 12.6 | 257 | 3800 |
| Comparative example 3 | 19.8 | 307 | 5000 |
The carbon electrode material preparation technology applied to ultracapacitor of the present invention is by by acetylene carbon black and sulfuric acid, styrene sulphur
Sour sodium carries out Hybrid Heating, warm, cooling, dilution, centrifuges, obtains modified carbon black after the sequence of operations such as washing and be combined
Thing, adds the lithium of phosphoric acid hydrogen two, nickel chloride and is reacted in reactor, and acid treatment is carried out after drying, then by itself and acrylonitrile
The reactant mixing through pyroreaction such as powder, dimethyl sulfoxide (DMSO), tetraethyl orthosilicate, adds distilled water ultrasonic disperse, and add
Melamine cyanurate, atomized copper powder, germanium sulfide, dipivaloylmethane cerium, silane coupler carry out pyroreaction, finally by
Washing, vacuum drying obtain finished product.The carbon electrode material applied to ultracapacitor being prepared from, its electrical conductivity is high, than electricity
Rong great, cycle-index is more, with preferable application prospect.The carbon electrode material raw material applied to ultracapacitor of the present invention is honest and clean
Valency, technique are simple, are used suitable for heavy industrialization, practical.
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize this hair
Equivalent structure or equivalent flow conversion that bright description is made, or directly or indirectly it is used in other related technology necks
Domain, is included within the scope of the present invention.
Claims (5)
1. a kind of carbon electrode material preparation method applied to ultracapacitor, it is characterised in that comprise the following steps：
（1）15 g acetylene carbon blacks are mixed under the conditions of 0 DEG C by liquid-solid ratio 8-12 with the sulfuric acid of mass concentration 92%, g pairs of addition 3
SSS, is heated with 8-10 DEG C/min speed, is warming up to insulation reaction after 110 DEG C and holds 2-3 h, then will reaction
Mixed liquor is cooled to room temperature, and 600 mL distilled water are added into reaction mixture and are diluted, then according to 7000-8000 rpm
Rotating speed centrifuged, separate except solution, then washed the lower sediment thing being centrifugally separating to obtain with 1000 mL absolute ethyl alcohols
2-3 times, by after washing sediment add distilled water be made into liquid-solid ratio be 15 mixed liquor and transfer to high pressure hydro-thermal reaction
In kettle, it is 1.2, the hydro-thermal process 10-15 h at 350 DEG C to keep its volumetric filling ratio, is cooled to after room temperature and washes hydrothermal product
Wash, suction filtration, until pH value is 7.0-7.2, it is to dry to constant weight in 75 DEG C of vacuum drying chamber to be then placed in temperature, is modified
Carbon black compound；
（2）By step（1）Obtained modified carbon black compound is added in distilled water with 25 KHz frequency with the lithium of 2g phosphoric acid hydrogen two
The min of rate ultrasonic disperse 30, then adds the g of nickel chloride 0.08, stirs 30 min at room temperature with 3000 rpm, by the mixed of formation
Close liquid to be transferred in reactor, 50 min are reacted at 150 DEG C；After reaction terminates, reaction mixture is placed in 80 DEG C of baking ovens
It is dried overnight, obtains desciccate；
（3）With 2.0 mol/L hydrochloric acid to step（2）Desciccate carry out acid treatment, the liquid-solid ratio of hydrochloric acid and desciccate
Be 55 DEG C for 8-10, treatment temperature, processing time be 3-5 h, it is neutrality that suction filtration to pH value, which is then washed with deionized, will be located
Product after reason is put into the vacuum drying chamber that temperature is 60 DEG C and dries 24 h, obtains the first dry reagent contained；
（4）0.6 mg polyacrylonitrile powders are dissolved in appropriate dimethyl sulfoxide (DMSO), 100 mL concentration are added for 0.5 mol/L
Ammonia spirit, 3-5 min are stirred at 70 DEG C with 200 rpm speed, 0.5 mL tetraethyl orthosilicates are then slowly added into, so
100 DEG C are warming up in polytetrafluoroethylcontainer container afterwards, the citric acid solution that 10 ml concentration are 0.2 mol/L is added, continues to heat up
8-10 h are stirred to 150 DEG C and at this temperature, obtained product are centrifuged according to 5000 rpm rotating speed, sediment is used
Deionized water is washed, and the second dry reagent contained is obtained after being dried at 120 DEG C；
（5）By step（3）Obtained the first dry reagent contained and step（4）Obtained the second dry reagent contained mixing, adds and steams
In distilled water, 45 min are handled with 50 KHz frequency ultrasound and obtain mixed dispersion liquid, 0.5-0.8 g cyanuric acids three are added thereto
Poly cyanamid, 0.2-0.4 g atomized copper powders, 0.1-0.3 g germanium sulfides, 0.06-0.1 g dipivaloylmethane ceriums, 0.05-0.08 g
Silane coupler, then heats to 110 DEG C, insulated and stirred 25-30 min are cooled to after room temperature reacting liquid filtering obtaining solid-state
Product, is washed to neutrality with water and ethanol, then is placed in 60-70 DEG C of vacuum drying chamber dry 18 h, obtains being applied to surpass
The carbon electrode material of level capacitor.
2. the carbon electrode material preparation method according to claim 1 applied to ultracapacitor, it is characterised in that described
Step（1）The iodine absorption value of middle acetylene carbon black is 105 g/Kg.
3. the carbon electrode material preparation method according to claim 1 applied to ultracapacitor, it is characterised in that described
Step（5）It is middle that 0.6 g melamine cyanurates, 0.3 g atomized copper powders, 0.2 g germanium sulfides, 0.08 are added into mixed dispersion liquid
G dipivaloylmethane ceriums, 0.05 g silane couplers.
4. the carbon electrode material preparation method according to claim 1 applied to ultracapacitor, it is characterised in that described
Step（5）In silane coupler be selected from VTES, methacryloxypropyl trimethoxy silane, 3-
Any one in glycydoxy trimethoxy silane.
5. the carbon electrode material applied to ultracapacitor obtained according to any one of the claim 1-4 preparation technologies is in system
Application in standby ultracapacitor.
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| CN106981372A (en) * | 2017-04-14 | 2017-07-25 | 苏州海凌达电子科技有限公司 | A kind of carbon electrode material preparation method applied to ultracapacitor |
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