CN106847532A - A kind of preparation method of the high performance material for ultracapacitor - Google Patents
A kind of preparation method of the high performance material for ultracapacitor Download PDFInfo
- Publication number
- CN106847532A CN106847532A CN201710224122.2A CN201710224122A CN106847532A CN 106847532 A CN106847532 A CN 106847532A CN 201710224122 A CN201710224122 A CN 201710224122A CN 106847532 A CN106847532 A CN 106847532A
- Authority
- CN
- China
- Prior art keywords
- ultracapacitor
- high performance
- performance material
- liquid
- distilled water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
-
- 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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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
-
- 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 a kind of preparation method of the high performance material for ultracapacitor, the technique is by by acetylene carbon black and sulfuric acid, SSS carries out Hybrid Heating, it is warm, modified carbon black compound is obtained after the sequence of operations such as cooling, add the lithium of phosphoric acid hydrogen two, nickel chloride is reacted in reactor, by it, composition mixes through the reactant of pyroreaction with acrylonitrile powder etc. after acid treatment, add distilled water ultrasonic disperse, and add dibutyl sebacate, nano magnesia, bismuth trioxide, coconut monoethanolamide, silane coupler carries out pyroreaction, finally by washing, vacuum drying obtains finished product.The high performance material for ultracapacitor being prepared from, its specific capacity is big, good cycling stability, energy density are high, electric conductivity is good, with preferable application prospect.Application of the high performance material in ultracapacitor is prepared as being used for ultracapacitor obtained in the preparation technology is also disclosed simultaneously.
Description
Technical field
The present invention relates to this technical field of capacitor material, a kind of high-performance for ultracapacitor is related specifically to
The preparation method of material.
Background technology
Ultracapacitor is the energy storage device between traditional capacitor and battery, is widely used in stand-by power supply, just
The fields such as formula portable power source, hybrid vehicle power supply are taken, is had a good application prospect.Its both have capacitor high power and
Can with fast charging and discharging the characteristics of, and the energy stores characteristic with electrochemical cell.From overall structure, ultracapacitor
Mainly it is made up of positive and negative electrode, electrolyte, barrier film, lead and encapsulating material.Ultracapacitor is divided into double electricity according to energy storage mechnism
Layer capacitor and Faradic pseudo-capacitor, energy stores and the conversion of double layer capacitor are based on double electrode layer theory, using electricity
Pole/electrolyte interface separation of charge forms electric double layer to realize a kind of new type of energy storage device of energy stores.Ultracapacitor
Performance depends primarily on the electrode material on positive and negative electrode piece.According to the difference for storing and converting electric energy mechanism, ultracapacitor
It is broadly divided into fake capacitance ultracapacitor and double electric layers supercapacitor.Fake capacitance ultracapacitor is by electro-chemical activity thing
There is faraday's redox reaction between electrode surface and electrolyte to carry out the storage and conversion of energy, electrode used therein in matter
Material is main based on the larger metal oxide of specific capacitance and conducting polymer, thus fake capacitance ultracapacitor is with higher
Energy density, but electrode material electric conductivity is poor, causes the high rate performance and cyclical stability of ultracapacitor poor.Double electricity
Layer ultracapacitor stores electric charge by being enriched with ion on electrode, and electrode is mainly using activated carbon, the carbon that specific surface area is big
The carbon materials such as nanotube, carbon aerogels, Graphene, the high rate performance and cycle performance of ultracapacitor is preferable.But, electric double layer
General its specific capacitance value of electrode active material that ultracapacitor is used is relatively low, and electric conductivity is poor, causes super capacitor
The energy density of device is relatively low, limits its development.
The content of the invention
In order to solve the above technical problems, the present invention provides a kind of preparation side of high performance material for ultracapacitor
Method, the technique carries out Hybrid Heating, warm, cooling, dilution, centrifugation by by acetylene carbon black and sulfuric acid, SSS
Modified carbon black compound is obtained after the sequence of operations such as separation, washing, the lithium of phosphoric acid hydrogen two, nickel chloride is added and is entered in reactor
Row reaction, acid treatment is carried out after drying, then by it with acrylonitrile powder, dimethyl sulfoxide (DMSO), tetraethyl orthosilicate etc. through pyroreaction
Reactant mixing, add distilled water ultrasonic disperse, and add dibutyl sebacate, nano magnesia, bismuth trioxide, coconut oil
Sour single ethanol amide, silane coupler carry out pyroreaction, and finished product is obtained finally by washing, vacuum drying.It is prepared from
For the high performance material of ultracapacitor, its specific capacity is big, good cycling stability, energy density are high, electric conductivity is good, has
Preferable application prospect.Also disclose simultaneously and prepared as the high performance material for being used for ultracapacitor obtained in the preparation technology
Application in ultracapacitor.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of preparation method of high performance material for ultracapacitor, comprises the following steps：
（1）15 g acetylene carbon blacks are mixed by liquid-solid ratio 8-12 under the conditions of 0 DEG C with the sulfuric acid of mass concentration 92%, addition 3 g pairs
SSS, is heated with the speed of 8-10 DEG C/min, and insulation reaction holds 2-3 h after being warming up to 110 DEG C, then will reaction
Mixed liquor is cooled to room temperature, to adding 600 mL distilled water to be diluted in reaction mixture, then according to 7000-8000 rpm
Rotating speed be centrifuged, separate removal solution, then washed with the lower sediment thing that 1000 mL absolute ethyl alcohols will be centrifugally separating to obtain
2-3 times, distilled water is added to be made into the mixed liquor that liquid-solid ratio is 15 and transfer to high pressure hydro-thermal reaction the sediment after washing
In kettle, keep its volumetric filling ratio for 1.2, the hydro-thermal process 10-15 h at 350 DEG C, wash hydrothermal product after being cooled to room temperature
Wash, suction filtration, until pH value is 7.0-7.2, be then placed in drying to constant weight in the vacuum drying chamber that temperature is 75 DEG C, be modified
Carbon black compound；
（2）By step（1）The modified carbon black compound for obtaining is added in distilled water with the frequency of 25 KHz with the lithium of 2g phosphoric acid hydrogen two
The min of rate ultrasonic disperse 30, is subsequently adding the g of nickel chloride 0.08, stirs 30 min with 3000 rpm at room temperature, mixed by what is formed
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 the hydrochloric acid of 2.0 mol/L to step（2）Desciccate carry out acid treatment, the liquid-solid ratio of hydrochloric acid and desciccate
For 8-10, treatment temperature be 55 DEG C, process time be 3-5 h, be then washed with deionized suction filtration to pH value for neutrality, will locate
Product after reason dries 24 h in being put into the vacuum drying chamber that temperature is 60 DEG C, obtains the first dry reagent contained；
（4）0.6 mg polyacrylonitrile powders are dissolved in appropriate dimethyl sulfoxide (DMSO), 100 mL concentration is added for 0.5 mol/L
Ammonia spirit, 3-5 min are stirred at 70 DEG C with the speed of 200 rpm, be then slowly added into 0.5 mL tetraethyl orthosilicates, 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, continue to heat up
8-10 h are stirred to 150 DEG C and at this temperature, the product that will be obtained is centrifuged according to the rotating speed of 5000 rpm, 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）The first dry reagent contained and step for obtaining（4）The the second dry reagent contained mixing for obtaining, adds and steams
In distilled water, 45 min are processed with the frequency ultrasound of 50 KHz and obtains mixed dispersion liquid, be added to 0.5-0.8 g decanedioic acid two
Butyl ester, 0.2-0.4 g nano magnesias, 0.1-0.3 g bismuth trioxides, 0.06-0.1 g coconut monoethanolamides, 0.05-
0.08 g silane couplers, then heat to 110 DEG C, and insulated and stirred 25-30 min obtain reacting liquid filtering after being cooled to room temperature
To solid product, washed to neutrality with water and ethanol, then be placed in 60-70 DEG C of vacuum drying chamber dry 18 h, used
In the high performance material of ultracapacitor.
Preferably, the step（1）The iodine absorption value of middle acetylene carbon black is 105 g/Kg.
Preferably, the step（5）It is middle to 0.6 g dibutyl sebacates are added in mixed dispersion liquid, 0.3 g is nano oxidized
Magnesium, 0.2 g bismuth trioxides, 0.08 g coconut monoethanolamides, 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.
It is super in preparation present invention also offers the high performance material for ultracapacitor obtained by above-mentioned preparation technology
Application in level capacitor.
Compared with prior art, its advantage is the present invention：
（1）High performance material preparation technology for ultracapacitor of the invention is by by acetylene carbon black and sulfuric acid, styrene
Sodium sulfonate carries out obtaining modified carbon black after the sequence of operations such as Hybrid Heating, warm, cooling, dilution, centrifugation, washing answering
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 propylene
Nitrile powder, dimethyl sulfoxide (DMSO), tetraethyl orthosilicate etc. mix through the reactant of pyroreaction, add distilled water ultrasonic disperse, and add
Plus dibutyl sebacate, nano magnesia, bismuth trioxide, coconut monoethanolamide, silane coupler carry out pyroreaction,
Finished product is obtained finally by washing, vacuum drying.The high performance material for ultracapacitor being prepared from, its specific capacity
Greatly, good cycling stability, energy density be high, electric conductivity is good, with preferable application prospect.
（2）High performance material raw material for ultracapacitor of the invention is cheap, process is simple, is suitable to large-scale industry
Change and use, it is practical.
Specific embodiment
The technical scheme invented is described in detail with reference to specific embodiment.
Embodiment 1
（1）By 15 g iodine absorption values be 105 g/Kg acetylene carbon blacks under the conditions of 0 DEG C by the sulfuric acid of liquid-solid ratio 8 and mass concentration 92%
Mixing, adds 3 g sodium p styrene sulfonates, is heated with the speed of 8 DEG C/min, and insulation reaction holds 2 h after being warming up to 110 DEG C, with
Reaction mixture is cooled to room temperature afterwards, to adding 600 mL distilled water to be diluted in reaction mixture, then according to 7000
The rotating speed of rpm is centrifuged, and separates removal solution, then the lower sediment thing that will be centrifugally separating to obtain with 1000 mL absolute ethyl alcohols
Washing 2 times, the sediment after washing adds 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, keep its volumetric filling ratio for 1.2, the h of hydro-thermal process 10 at 350 DEG C, wash hydrothermal product after being cooled to room temperature
Wash, suction filtration, until pH value is 7.0, be then placed in drying to constant weight in the vacuum drying chamber that temperature is 75 DEG C, obtain modified carbon black
Compound；
（2）By step（1）The modified carbon black compound for obtaining is added in distilled water with the frequency of 25 KHz with the lithium of 2g phosphoric acid hydrogen two
The min of rate ultrasonic disperse 30, is subsequently adding the g of nickel chloride 0.08, stirs 30 min with 3000 rpm at room temperature, mixed by what is formed
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 the hydrochloric acid of 2.0 mol/L to step（2）Desciccate carry out acid treatment, the liquid-solid ratio of hydrochloric acid and desciccate
For 8, treatment temperature be 55 DEG C, process time be 3 h, be then washed with deionized suction filtration to pH value for neutrality, after treatment
Product be put into 24 h dried in the vacuum drying chamber that temperature is 60 DEG C, obtain the first dry reagent contained；
（4）0.6 mg polyacrylonitrile powders are dissolved in appropriate dimethyl sulfoxide (DMSO), 100 mL concentration is added for 0.5 mol/L
Ammonia spirit, 3 min are stirred at 70 DEG C with the speed of 200 rpm, be then slowly added into 0.5 mL tetraethyl orthosilicates, then
100 DEG C are warming up in polytetrafluoroethylcontainer container, the citric acid solution for adding 10 ml concentration to be 0.2 mol/L is continuously heating to
150 DEG C and stir 8 h at this temperature, the product that will be obtained is centrifuged according to the rotating speed of 5000 rpm, 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）The first dry reagent contained and step for obtaining（4）The the second dry reagent contained mixing for obtaining, adds and steams
In distilled water, 45 min are processed with the frequency ultrasound of 50 KHz and obtains mixed dispersion liquid, be added to the fourth of 0.6 g decanedioic acid two
Ester, 0.3 g nano magnesias, 0.2 g bismuth trioxides, 0.08 g coconut monoethanolamides, the ethoxy of 0.05 g vinyl three
Base silane, then heats to 110 DEG C, and reacting liquid filtering is obtained solid product by the min of insulated and stirred 25 after being cooled to room temperature, uses
Water and ethanol are washed to neutrality, then are placed in 60 DEG C of vacuum drying chambers dry 18 h, obtain the height for ultracapacitor
Performance materials.
The performance test results of the obtained high performance material for ultracapacitor are as shown in table 1.
Embodiment 2
（1）By 15 g iodine absorption values be 105 g/Kg acetylene carbon blacks under the conditions of 0 DEG C by the sulfuric acid of liquid-solid ratio 10 and mass concentration 92%
Mixing, adds 3 g sodium p styrene sulfonates, is heated with the speed of 9 DEG C/min, and insulation reaction holds 2.5 h after being warming up to 110 DEG C,
Reaction mixture is then cooled to room temperature, to adding 600 mL distilled water to be diluted in reaction mixture, then according to
The rotating speed of 7500 rpm is centrifuged, and separates removal solution, then sunk with the lower floor that 1000 mL absolute ethyl alcohols will be centrifugally separating to obtain
Starch is washed 2 times, adds distilled water to be made into the mixed liquor that liquid-solid ratio is 15 and transfer to water under high pressure the sediment after washing
In thermal response kettle, its volumetric filling ratio is kept for 1.2, the h of hydro-thermal process 12 at 350 DEG C, be cooled to hydrothermal product after room temperature
Washing, suction filtration, until pH value is 7.1, are then placed in being dried to constant weight in the vacuum drying chamber that temperature is 75 DEG C, obtain carbon modified
Black compound；
（2）By step（1）The modified carbon black compound for obtaining is added in distilled water with the frequency of 25 KHz with the lithium of 2g phosphoric acid hydrogen two
The min of rate ultrasonic disperse 30, is subsequently adding the g of nickel chloride 0.08, stirs 30 min with 3000 rpm at room temperature, mixed by what is formed
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 the hydrochloric acid of 2.0 mol/L to step（2）Desciccate carry out acid treatment, the liquid-solid ratio of hydrochloric acid and desciccate
For 9, treatment temperature be 55 DEG C, process time be 4 h, be then washed with deionized suction filtration to pH value for neutrality, after treatment
Product be put into 24 h dried in the vacuum drying chamber that temperature is 60 DEG C, obtain the first dry reagent contained；
（4）0.6 mg polyacrylonitrile powders are dissolved in appropriate dimethyl sulfoxide (DMSO), 100 mL concentration is added for 0.5 mol/L
Ammonia spirit, 4 min are stirred at 70 DEG C with the speed of 200 rpm, be then slowly added into 0.5 mL tetraethyl orthosilicates, then
100 DEG C are warming up in polytetrafluoroethylcontainer container, the citric acid solution for adding 10 ml concentration to be 0.2 mol/L is continuously heating to
150 DEG C and stir 9 h at this temperature, the product that will be obtained is centrifuged according to the rotating speed of 5000 rpm, 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）The first dry reagent contained and step for obtaining（4）The the second dry reagent contained mixing for obtaining, adds and steams
In distilled water, 45 min are processed with the frequency ultrasound of 50 KHz and obtains mixed dispersion liquid, be added to the fourth of 0.6 g decanedioic acid two
Ester, 0.3 g nano magnesias, 0.2 g bismuth trioxides, 0.08 g coconut monoethanolamides, 0.05 g methacryloxypropyls
Base propyl trimethoxy silicane, then heats to 110 DEG C, and the min of insulated and stirred 28 obtains reacting liquid filtering after being cooled to room temperature
To solid product, washed to neutrality with water and ethanol, then be placed in 65 DEG C of vacuum drying chambers dry 18 h, obtained for surpassing
The high performance material of level capacitor.
The performance test results of the obtained high performance material for ultracapacitor are as shown in table 1.
Embodiment 3
（1）By 15 g iodine absorption values be 105 g/Kg acetylene carbon blacks under the conditions of 0 DEG C by the sulfuric acid of liquid-solid ratio 12 and mass concentration 92%
Mixing, adds 3 g sodium p styrene sulfonates, is heated with the speed of 10 DEG C/min, and insulation reaction holds 3 h after being warming up to 110 DEG C,
Reaction mixture is then cooled to room temperature, to adding 600 mL distilled water to be diluted in reaction mixture, then according to
The rotating speed of 8000 rpm is centrifuged, and separates removal solution, then sunk with the lower floor that 1000 mL absolute ethyl alcohols will be centrifugally separating to obtain
Starch is washed 3 times, adds distilled water to be made into the mixed liquor that liquid-solid ratio is 15 and transfer to water under high pressure the sediment after washing
In thermal response kettle, its volumetric filling ratio is kept for 1.2, the h of hydro-thermal process 15 at 350 DEG C, be cooled to hydrothermal product after room temperature
Washing, suction filtration, until pH value is 7.2, are then placed in being dried to constant weight in the vacuum drying chamber that temperature is 75 DEG C, obtain carbon modified
Black compound；
（2）By step（1）The modified carbon black compound for obtaining is added in distilled water with the frequency of 25 KHz with the lithium of 2g phosphoric acid hydrogen two
The min of rate ultrasonic disperse 30, is subsequently adding the g of nickel chloride 0.08, stirs 30 min with 3000 rpm at room temperature, mixed by what is formed
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 the hydrochloric acid of 2.0 mol/L to step（2）Desciccate carry out acid treatment, the liquid-solid ratio of hydrochloric acid and desciccate
For 10, treatment temperature be 55 DEG C, process time be 5 h, be then washed with deionized suction filtration to pH value for neutrality, after treatment
Product be put into 24 h dried in the vacuum drying chamber that temperature is 60 DEG C, obtain the first dry reagent contained；
（4）0.6 mg polyacrylonitrile powders are dissolved in appropriate dimethyl sulfoxide (DMSO), 100 mL concentration is added for 0.5 mol/L
Ammonia spirit, 5 min are stirred at 70 DEG C with the speed of 200 rpm, be then slowly added into 0.5 mL tetraethyl orthosilicates, then
100 DEG C are warming up in polytetrafluoroethylcontainer container, the citric acid solution for adding 10 ml concentration to be 0.2 mol/L is continuously heating to
150 DEG C and stir 10 h at this temperature, the product that will be obtained is centrifuged according to the rotating speed of 5000 rpm, 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）The first dry reagent contained and step for obtaining（4）The the second dry reagent contained mixing for obtaining, adds and steams
In distilled water, 45 min are processed with the frequency ultrasound of 50 KHz and obtains mixed dispersion liquid, be added to the fourth of 0.6 g decanedioic acid two
Ester, 0.3 g nano magnesias, 0.2 g bismuth trioxides, 0.08 g coconut monoethanolamides, 0.05 g 3- glycidol ethers
Epoxide propyl trimethoxy silicane, then heats to 110 DEG C, the min of insulated and stirred 30, is cooled to reacting liquid filtering after room temperature
Obtain solid product, washed to neutrality with water and ethanol, then be placed in 70 DEG C of vacuum drying chambers dry 18 h, obtain for
The high performance material of ultracapacitor.
The performance test results of the obtained high performance material for ultracapacitor are as shown in table 1.
Comparative example 1
（1）By 15 g iodine absorption values be 105 g/Kg acetylene carbon blacks under the conditions of 0 DEG C by the sulfuric acid of liquid-solid ratio 8 and mass concentration 92%
Mixing, adds 3 g sodium p styrene sulfonates, is heated with the speed of 8 DEG C/min, and insulation reaction holds 2 h after being warming up to 110 DEG C, with
Reaction mixture is cooled to room temperature afterwards, to adding 600 mL distilled water to be diluted in reaction mixture, then according to 7000
The rotating speed of rpm is centrifuged, and separates removal solution, then the lower sediment thing that will be centrifugally separating to obtain with 1000 mL absolute ethyl alcohols
Washing 2 times, the sediment after washing adds 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, keep its volumetric filling ratio for 1.2, the h of hydro-thermal process 10 at 350 DEG C, wash hydrothermal product after being cooled to room temperature
Wash, suction filtration, until pH value is 7.0, be then placed in drying to constant weight in the vacuum drying chamber that temperature is 75 DEG C, obtain modified carbon black
Compound；
（2）By step（1）The modified carbon black compound for obtaining is added in distilled water with the frequency of 25 KHz with the lithium of 2g phosphoric acid hydrogen two
The min of rate ultrasonic disperse 30, is subsequently adding the g of nickel chloride 0.08, stirs 30 min with 3000 rpm at room temperature, mixed by what is formed
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 the hydrochloric acid of 2.0 mol/L to step（2）Desciccate carry out acid treatment, the liquid-solid ratio of hydrochloric acid and desciccate
For 8, treatment temperature be 55 DEG C, process time be 3 h, be then washed with deionized suction filtration to pH value for neutrality, after treatment
Product be put into 24 h dried in the vacuum drying chamber that temperature is 60 DEG C, obtain the first dry reagent contained；
（4）0.6 mg polyacrylonitrile powders are dissolved in appropriate dimethyl sulfoxide (DMSO), 100 mL concentration is added for 0.5 mol/L
Ammonia spirit, 3 min are stirred at 70 DEG C with the speed of 200 rpm, be then slowly added into 0.5 mL tetraethyl orthosilicates, then
100 DEG C are warming up in polytetrafluoroethylcontainer container, the citric acid solution for adding 10 ml concentration to be 0.2 mol/L is continuously heating to
150 DEG C and stir 8 h at this temperature, the product that will be obtained is centrifuged according to the rotating speed of 5000 rpm, 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）The first dry reagent contained and step for obtaining（4）The the second dry reagent contained mixing for obtaining, adds and steams
In distilled water, 45 min are processed with the frequency ultrasound of 50 KHz and obtains mixed dispersion liquid, be added to the fourth of 0.4 g decanedioic acid two
Ester, 0.6 g nano magnesias, 0.5 g bismuth trioxides, 0.05 g coconut monoethanolamides, the ethoxy of 0.05 g vinyl three
Base silane, then heats to 110 DEG C, and reacting liquid filtering is obtained solid product by the min of insulated and stirred 25 after being cooled to room temperature, uses
Water and ethanol are washed to neutrality, then are placed in 60 DEG C of vacuum drying chambers dry 18 h, obtain the height for ultracapacitor
Performance materials.
The performance test results of the obtained high performance material for ultracapacitor are as shown in table 1.
Comparative example 2
（1）By 15 g iodine absorption values be 105 g/Kg acetylene carbon blacks under the conditions of 0 DEG C by the sulfuric acid of liquid-solid ratio 10 and mass concentration 92%
Mixing, adds 3 g sodium p styrene sulfonates, is heated with the speed of 9 DEG C/min, and insulation reaction holds 2.5 h after being warming up to 110 DEG C,
Reaction mixture is then cooled to room temperature, to adding 600 mL distilled water to be diluted in reaction mixture, then according to
The rotating speed of 7500 rpm is centrifuged, and separates removal solution, then sunk with the lower floor that 1000 mL absolute ethyl alcohols will be centrifugally separating to obtain
Starch is washed 2 times, adds distilled water to be made into the mixed liquor that liquid-solid ratio is 15 and transfer to water under high pressure the sediment after washing
In thermal response kettle, its volumetric filling ratio is kept for 1.2, the h of hydro-thermal process 12 at 350 DEG C, be cooled to hydrothermal product after room temperature
Washing, suction filtration, until pH value is 7.1, are then placed in being dried to constant weight in the vacuum drying chamber that temperature is 75 DEG C, obtain carbon modified
Black compound；
（2）By step（1）The modified carbon black compound for obtaining mixes with appropriate distilled water, is subsequently adding 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, obtain desciccate；
（3）With the hydrochloric acid of 2.0 mol/L to step（2）Desciccate carry out acid treatment, the liquid-solid ratio of hydrochloric acid and desciccate
For 9, treatment temperature be 55 DEG C, process time be 4 h, be then washed with deionized suction filtration to pH value for neutrality, after treatment
Product be put into 24 h dried in the vacuum drying chamber that temperature is 60 DEG C, obtain the first dry reagent contained；
（4）0.6 mg polyacrylonitrile powders are dissolved in appropriate dimethyl sulfoxide (DMSO), 100 mL concentration is added for 0.5 mol/L
Ammonia spirit, 4 min are stirred at 70 DEG C with the speed of 200 rpm, be then slowly added into 0.5 mL tetraethyl orthosilicates, then
100 DEG C are warming up in polytetrafluoroethylcontainer container, the citric acid solution for adding 10 ml concentration to be 0.2 mol/L is continuously heating to
150 DEG C and stir 9 h at this temperature, the product that will be obtained is centrifuged according to the rotating speed of 5000 rpm, 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）The first dry reagent contained and step for obtaining（4）The the second dry reagent contained mixing for obtaining, adds and steams
In distilled water, 45 min are processed with the frequency ultrasound of 50 KHz and obtains mixed dispersion liquid, be added to the fourth of 0.6 g decanedioic acid two
Ester, 0.3 g nano magnesias, 0.2 g bismuth trioxides, 0.08 g coconut monoethanolamides, 0.05 g methacryloxypropyls
Base propyl trimethoxy silicane, then heats to 110 DEG C, and the min of insulated and stirred 28 obtains reacting liquid filtering after being cooled to room temperature
To solid product, washed to neutrality with water and ethanol, then be placed in 65 DEG C of vacuum drying chambers dry 18 h, obtained for surpassing
The high performance material of level capacitor.
The performance test results of the obtained high performance material for ultracapacitor are as shown in table 1.
Comparative example 3
（1）By 15 g iodine absorption values be 105 g/Kg acetylene carbon blacks under the conditions of 0 DEG C by the sulfuric acid of liquid-solid ratio 7 and mass concentration 92%
Mixing, adds 3 g sodium p styrene sulfonates, is heated with the speed of 15 DEG C/min, and insulation reaction holds 1.5 after being warming up to 110 DEG C
H, is then cooled to room temperature by reaction mixture, to adding 600 mL distilled water to be diluted in reaction mixture, then according to
The rotating speed of 8000 rpm is centrifuged, and separates removal solution, then sunk with the lower floor that 1000 mL absolute ethyl alcohols will be centrifugally separating to obtain
Starch is washed 3 times, adds distilled water to be made into the mixed liquor that liquid-solid ratio is 15 and transfer to water under high pressure the sediment after washing
In thermal response kettle, its volumetric filling ratio is kept for 1.2, the h of hydro-thermal process 15 at 350 DEG C, be cooled to hydrothermal product after room temperature
Washing, suction filtration, until pH value is 7.2, are then placed in being dried to constant weight in the vacuum drying chamber that temperature is 75 DEG C, obtain carbon modified
Black compound；
（2）By step（1）The modified carbon black compound for obtaining is added in distilled water with the frequency of 25 KHz with the lithium of 2g phosphoric acid hydrogen two
The min of rate ultrasonic disperse 20, is subsequently adding the g of nickel chloride 0.1, stirs 30 min with 3000 rpm at room temperature, mixed by what is formed
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 the hydrochloric acid of 2.0 mol/L to step（2）Desciccate carry out acid treatment, the liquid-solid ratio of hydrochloric acid and desciccate
For 10, treatment temperature be 55 DEG C, process time be 5 h, be then washed with deionized suction filtration to pH value for neutrality, after treatment
Product be put into 24 h dried in the vacuum drying chamber that temperature is 60 DEG C, obtain the first dry reagent contained；
（4）0.6 mg polyacrylonitrile powders are dissolved in appropriate dimethyl sulfoxide (DMSO), 100 mL concentration is added for 0.5 mol/L
Ammonia spirit, 5 min are stirred at 70 DEG C with the speed of 200 rpm, be then slowly added into 0.5 mL tetraethyl orthosilicates, then
100 DEG C are warming up in polytetrafluoroethylcontainer container, the citric acid solution for adding 10 ml concentration to be 0.2 mol/L is continuously heating to
150 DEG C and stir 10 h at this temperature, the product that will be obtained is centrifuged according to the rotating speed of 5000 rpm, 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）The first dry reagent contained and step for obtaining（4）The the second dry reagent contained mixing for obtaining, adds and steams
In distilled water, 45 min are processed with the frequency ultrasound of 50 KHz and obtains mixed dispersion liquid, be added to the fourth of 0.6 g decanedioic acid two
Ester, 0.3 g nano magnesias, 0.2 g bismuth trioxides, 0.08 g coconut monoethanolamides, 0.05 g 3- glycidol ethers
Epoxide propyl trimethoxy silicane, then heats to 110 DEG C, the min of insulated and stirred 30, is cooled to reacting liquid filtering after room temperature
Obtain solid product, washed to neutrality with water and ethanol, then be placed in 70 DEG C of vacuum drying chambers dry 18 h, obtain for
The high performance material of ultracapacitor.
The performance test results of the obtained high performance material for ultracapacitor are as shown in table 1.
The high performance material for being used for ultracapacitor obtained in embodiment 1-3 and comparative example 1-3 is carried out into specific capacity, is held
Amount retention rate, energy density, this several performance tests of discharge time and dielectric constant.
Table 1
| Specific capacitance（F/g, 1A/g） | Capacity retention rate（%, 5000 cyclic voltammetries） | Energy density（Wh/kg） | Discharge time s | Dielectric constant | |
| Embodiment 1 | 372 | 91.4 | 9.91 | 495 | 1055 |
| Embodiment 2 | 370 | 91.8 | 9.85 | 486 | 1046 |
| Embodiment 3 | 368 | 91.1 | 9.90 | 491 | 1070 |
| Comparative example 1 | 246 | 73.8 | 6.83 | 360 | 751 |
| Comparative example 2 | 234 | 72.9 | 7.09 | 351 | 745 |
| Comparative example 3 | 267 | 76.6 | 7.38 | 378 | 602 |
High performance material preparation technology for ultracapacitor of the invention is by by acetylene carbon black and sulfuric acid, styrene sulfonic acid
Sodium carries out obtaining modified carbon black after the sequence of operations such as Hybrid Heating, warm, cooling, dilution, centrifugation, washing being 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
Powder, dimethyl sulfoxide (DMSO), tetraethyl orthosilicate etc. mix through the reactant of pyroreaction, add distilled water ultrasonic disperse, and add
Dibutyl sebacate, nano magnesia, bismuth trioxide, coconut monoethanolamide, silane coupler carry out pyroreaction, most
Finished product is obtained by washing, vacuum drying afterwards.The high performance material for ultracapacitor being prepared from, its specific capacity is big,
Good cycling stability, energy density are high, electric conductivity is good, with preferable application prospect.It is of the invention for ultracapacitor
High performance material raw material is cheap, process is simple, be suitable to heavy industrialization utilization, it is practical.
Embodiments of the invention are the foregoing is only, the scope of the claims of the invention is not thereby limited, 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. the preparation method of a kind of high performance material for ultracapacitor, it is characterised in that comprise the following steps：
（1）15 g acetylene carbon blacks are mixed by liquid-solid ratio 8-12 under the conditions of 0 DEG C with the sulfuric acid of mass concentration 92%, addition 3 g pairs
SSS, is heated with the speed of 8-10 DEG C/min, and insulation reaction holds 2-3 h after being warming up to 110 DEG C, then will reaction
Mixed liquor is cooled to room temperature, to adding 600 mL distilled water to be diluted in reaction mixture, then according to 7000-8000 rpm
Rotating speed be centrifuged, separate removal solution, then washed with the lower sediment thing that 1000 mL absolute ethyl alcohols will be centrifugally separating to obtain
2-3 times, distilled water is added to be made into the mixed liquor that liquid-solid ratio is 15 and transfer to high pressure hydro-thermal reaction the sediment after washing
In kettle, keep its volumetric filling ratio for 1.2, the hydro-thermal process 10-15 h at 350 DEG C, wash hydrothermal product after being cooled to room temperature
Wash, suction filtration, until pH value is 7.0-7.2, be then placed in drying to constant weight in the vacuum drying chamber that temperature is 75 DEG C, be modified
Carbon black compound；
（2）By step（1）The modified carbon black compound for obtaining is added in distilled water with the frequency of 25 KHz with the lithium of 2g phosphoric acid hydrogen two
The min of rate ultrasonic disperse 30, is subsequently adding the g of nickel chloride 0.08, stirs 30 min with 3000 rpm at room temperature, mixed by what is formed
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 the hydrochloric acid of 2.0 mol/L to step（2）Desciccate carry out acid treatment, the liquid-solid ratio of hydrochloric acid and desciccate
For 8-10, treatment temperature be 55 DEG C, process time be 3-5 h, be then washed with deionized suction filtration to pH value for neutrality, will locate
Product after reason dries 24 h in being put into the vacuum drying chamber that temperature is 60 DEG C, obtains the first dry reagent contained；
（4）0.6 mg polyacrylonitrile powders are dissolved in appropriate dimethyl sulfoxide (DMSO), 100 mL concentration is added for 0.5 mol/L
Ammonia spirit, 3-5 min are stirred at 70 DEG C with the speed of 200 rpm, be then slowly added into 0.5 mL tetraethyl orthosilicates, 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, continue to heat up
8-10 h are stirred to 150 DEG C and at this temperature, the product that will be obtained is centrifuged according to the rotating speed of 5000 rpm, 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）The first dry reagent contained and step for obtaining（4）The the second dry reagent contained mixing for obtaining, adds and steams
In distilled water, 45 min are processed with the frequency ultrasound of 50 KHz and obtains mixed dispersion liquid, be added to 0.5-0.8 g decanedioic acid two
Butyl ester, 0.2-0.4 g nano magnesias, 0.1-0.3 g bismuth trioxides, 0.06-0.1 g coconut monoethanolamides, 0.05-
0.08 g silane couplers, then heat to 110 DEG C, and insulated and stirred 25-30 min obtain reacting liquid filtering after being cooled to room temperature
To solid product, washed to neutrality with water and ethanol, then be placed in 60-70 DEG C of vacuum drying chamber dry 18 h, used
In the high performance material of ultracapacitor.
2. the preparation method of the high performance material for ultracapacitor according to claim 1, it is characterised in that described
Step（1）The iodine absorption value of middle acetylene carbon black is 105 g/Kg.
3. the preparation method of the high performance material for ultracapacitor according to claim 1, it is characterised in that described
Step（5）It is middle to adding 0.6 g dibutyl sebacates in mixed dispersion liquid, 0.3 g nano magnesias, 0.2 g bismuth trioxides,
0.08 g coconut monoethanolamides, 0.05 g silane couplers.
4. the preparation method of the high performance material for ultracapacitor according to claim 1, 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. it is prepared by the high performance material for ultracapacitor that the preparation technology according to claim any one of 1-4 is obtained
Application in ultracapacitor.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710224122.2A CN106847532A (en) | 2017-04-07 | 2017-04-07 | A kind of preparation method of the high performance material for ultracapacitor |
| PCT/CN2017/098517 WO2018184341A1 (en) | 2017-04-07 | 2017-08-22 | Preparation method for high-performance material for use in supercapacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710224122.2A CN106847532A (en) | 2017-04-07 | 2017-04-07 | A kind of preparation method of the high performance material for ultracapacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106847532A true CN106847532A (en) | 2017-06-13 |
Family
ID=59148231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710224122.2A Pending CN106847532A (en) | 2017-04-07 | 2017-04-07 | A kind of preparation method of the high performance material for ultracapacitor |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN106847532A (en) |
| WO (1) | WO2018184341A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018184341A1 (en) * | 2017-04-07 | 2018-10-11 | 苏州海凌达电子科技有限公司 | Preparation method for high-performance material for use in supercapacitor |
| CN112645322A (en) * | 2020-11-30 | 2021-04-13 | 河南省大潮炭能科技有限公司 | Carbon soaking method for super capacitor |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110148530B (en) * | 2019-06-18 | 2021-05-25 | 合肥师范学院 | Preparation method of magnetic field induced nickel chloride/polyaniline supercapacitor electrode material |
| CN110739158B (en) * | 2019-09-23 | 2022-06-24 | 青岛大学 | Surface-modified oxygen-containing functional group-containing graphene for supercapacitor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009201405A (en) * | 2008-02-27 | 2009-09-10 | Kochi Univ | Method for producing glucose, and method for producing sulfonated active carbon |
| CN101786015A (en) * | 2010-03-31 | 2010-07-28 | 华南理工大学 | Hydrothermal preparation method of carbon-based solid sulfoacid |
| CN105903481A (en) * | 2016-04-27 | 2016-08-31 | 中国科学院合肥物质科学研究院 | Sulfonyl-functionalized carbon-based metal catalyst and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457832C (en) * | 2006-12-04 | 2009-02-04 | 浙江大学 | Method for preparing water-dispersive carbon black adopting surface graft modification method |
| US8614878B2 (en) * | 2008-01-17 | 2013-12-24 | Fraser W. SEYMOUR | Nanoscale intercalation materials on carbon powder, process for production, and use thereof |
| CN103663448B (en) * | 2012-09-19 | 2017-08-01 | 天津普兰纳米科技有限公司 | Preparation method, gained carbon material and its application of carbon material |
| CN104779064A (en) * | 2015-04-03 | 2015-07-15 | 安徽江威精密制造有限公司 | Electrode material capable of improving cycle performance of super capacitor and preparation method of electrode material |
| CN106847532A (en) * | 2017-04-07 | 2017-06-13 | 苏州海凌达电子科技有限公司 | A kind of preparation method of the high performance material for ultracapacitor |
-
2017
- 2017-04-07 CN CN201710224122.2A patent/CN106847532A/en active Pending
- 2017-08-22 WO PCT/CN2017/098517 patent/WO2018184341A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009201405A (en) * | 2008-02-27 | 2009-09-10 | Kochi Univ | Method for producing glucose, and method for producing sulfonated active carbon |
| CN101786015A (en) * | 2010-03-31 | 2010-07-28 | 华南理工大学 | Hydrothermal preparation method of carbon-based solid sulfoacid |
| CN105903481A (en) * | 2016-04-27 | 2016-08-31 | 中国科学院合肥物质科学研究院 | Sulfonyl-functionalized carbon-based metal catalyst and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| JIE SHENG等: "Synthesis of microporous carbon nanofibers with high specific surface using tetraethyl orthosilicate template for supercapacitors", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018184341A1 (en) * | 2017-04-07 | 2018-10-11 | 苏州海凌达电子科技有限公司 | Preparation method for high-performance material for use in supercapacitor |
| CN112645322A (en) * | 2020-11-30 | 2021-04-13 | 河南省大潮炭能科技有限公司 | Carbon soaking method for super capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018184341A1 (en) | 2018-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104973596B (en) | A kind of Heteroatom doping hollow ball graphene composite material and preparation method and application | |
| CN105720246B (en) | Graininess stannic oxide/two-dimensional nano carbonization titanium composite material and application | |
| CN106847532A (en) | A kind of preparation method of the high performance material for ultracapacitor | |
| CN105140046B (en) | A kind of nanometer of γ-MnO2The preparation method and applications of/graphene aerogel composite material | |
| CN104835963B (en) | Lithium ion battery composite anode material and preparation method thereof | |
| CN105645410B (en) | 3D network pore structure Supercapacitor carbons and preparation method thereof | |
| CN109485867A (en) | A kind of preparation method and applications of metal organic framework compound | |
| CN104176783B (en) | The preparations and applicatio method of the coated manganese dioxide nanowire of a kind of nitrogen carbon material | |
| CN108831757B (en) | A kind of preparation method of N and S codope graphene/carbon nano-tube aeroge | |
| CN108545712A (en) | A method of synthesizing multi-stage porous carbon material with salt template carbonization ZIF-8 | |
| CN107230558A (en) | A kind of Fe3O4The preparation method of/graphene composite material | |
| CN104993116B (en) | A kind of self assembly anode material for lithium-ion batteries V2O5Preparation method | |
| CN106683891A (en) | High-conductivity flexible graphite/mesoporous graphitized carbon composite membrane electrode preparation method | |
| CN104466110B (en) | Preparation method of high-performance lithium ion battery negative electrode material | |
| CN107086131A (en) | Water system Asymmetric Supercapacitor based on NiS/N rGO Yu N rGO | |
| CN109767928A (en) | The synthetic method and its application of Fluorin doped carbon coating silica nano particle@carbon nano tube compound material | |
| CN109400905A (en) | A kind of metal organic framework Mn-BTC and preparation method and application | |
| CN109659521A (en) | A kind of preparation method of high-performance sodium-ion battery vanadic anhydride/grapheme composite positive electrode material | |
| CN106571248A (en) | Preparation method for electrode material of Se-doped ZnO-SnO2 supercapacitor taking foamed nickel as substrate | |
| CN108597891A (en) | Composite material and preparation method and application are covered in a kind of double load double-contractings of silica@metal oxides/graphene aerogel | |
| CN105161690B (en) | The method that molybdenum disulfide charge and discharge cycles ability is improved by doped graphene and titanium dioxide | |
| CN107706003B (en) | A kind of hydro-thermal method prepares graphene/CaTi2O4(OH)2The method of composite granule and its product obtained | |
| CN110767465B (en) | Preparation method of supercapacitor based on two-dimensional niobium carbide nano composite material | |
| CN104124435B (en) | Multiple edge MoS2nanometer sheet/Graphene electrochemistry storage sodium combination electrode and preparation method | |
| CN109599271A (en) | A kind of electrode material Ni3V2O8And its synthetic method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170613 |