CN105261487A - Preparation method for nuclear shell porous nano carbon material of super-capacitor electrode - Google Patents
Preparation method for nuclear shell porous nano carbon material of super-capacitor electrode Download PDFInfo
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Abstract
The invention discloses a preparation method for a nuclear shell porous nano carbon material of a super-capacitor electrode, and the method comprises the steps: the preparation of carbon source solution; the preparation of carbon nano tube dispersion liquid; the wrapping of a carbon nano tube; carbonization; and the forming of holes. The wrapping of the carbon nano tube is carried out in following steps that the carbon source solution and the carbon nano tube dispersion liquid are mixed uniformly and is stirred for 6-10 hours under the temperature from 60 DEG C to 180 DEG C; the surface of the carbon nano tube is uniformly wrapped by a carbon source wrapping layer, and then is washed and dried, thereby obtaining the wrapped cabin nano tube which takes the carbon nano tube as a core part and takes a carbon source as an external wrapping layer. The material prepared through the method is good in conductivity, is large in specific surface area, is abundant in hole structure, is short in ion diffusion distance, and facilitates the obtaining of large specific surface area, low resistance, high rate capability and long circulating service life after the material is used as an electrode material.
Description
Technical field
The present invention relates to a kind of preparation method of capacitance electrode material, especially for the preparation method of the nucleocapsid porous nano material with carbon element of electrode of super capacitor.
Background technology
Ultracapacitor (Supercapacitors, ultracapacitor), have another name called electrochemical capacitor (ElectrochemicalCapacitors), double electric layer capacitor (ElectricalDouble-LayerCapacitor), gold electric capacity, farad capacitor are a kind of electrochemical elements being carried out energy storage by polarized electrolytic matter grown up from the 1970s and 1980s in last century.It is different from traditional chemical power source, be a kind of between traditional capacitor and battery, there is the power supply of property, mainly rely on electric double layer and Redox pseudocapacitance charge storage electric energy.But chemical reaction does not occur in the process of its energy storage, this thermal energy storage process is reversible, also just because of this ultracapacitor can repeated charge hundreds thousand of time.Its general principle is the same with the double electric layer capacitor of other kind, is all the capacity utilizing the double electrical layers of active carbon porous electrode and electrolyte composition to obtain super large.Outstanding advantages is that power density is high, the discharge and recharge time is short, have extended cycle life, operating temperature range is wide, is the one that in the double electric layer capacitor having dropped into volume production in the world, capacity is maximum.
Ultracapacitor, owing to having high power density and long circulation life, all has wide practical use in various fields such as communications and transportation, wind power generation, electronic products.Mainly its energy density is lower to limit its factor applied at present.Active carbon is current topmost commercial electrode material, and it has, and specific area is large, pore structure is enriched, and the material extensively advantage such as inexpensive, thus in height ratio capacity electrode material, has obvious advantage.But because active carbon is graininess, and carbon atom mostly is sp3 form, therefore its conductivity is low, needs to add the conductive agents such as carbon black in actual applications and assist.In addition, the particle size of active carbon is usually at several microns to tens microns, and it is long that ion diffuses into active carbon inner distance completely, is subject to dynamics restriction.To sum up, active carbon is when for electrode material, and internal resistance is large, and high rate performance is not good.
Carbon nano-tube is the cellular one-dimentional structure formed by sp2 carbon due to it, has good conductivity, high mechanical strength and huge draw ratio and surface area, is widely used in the composite strengthening fields such as macromolecule, is also used as catalyst carrier simultaneously.Replace the conventional conductive agent such as carbon black with carbon nano-tube, it is extremely promising thinking that auxiliary activity charcoal is used in electrode material.But because carbon nano-tube caliber is thin, Van der Waals force is large, very easily form tube bank and be difficult to dispersion, when carbon nano-tube is mixed with active carbon, be difficult to mix, the conductivity of carbon nano-tube cannot obtain good performance.
Summary of the invention
For solving the problem, the preparation method of the nucleocapsid porous nano material with carbon element for electrode of super capacitor disclosed by the invention, its nucleocapsid porous nano material with carbon element prepared has good conductivity, specific area is large, pore structure enrich and ion diffuse apart from short advantage, be conducive to height ratio capacity, low internal resistance, the acquisition of high rate capability and long circulation life.
The preparation method of the nucleocapsid porous nano material with carbon element for electrode of super capacitor disclosed by the invention, comprises the preparation of carbon source solution; The preparation of carbon nano tube dispersion liquid; Carbon nano-tube is coated; Carbonization; Pore-creating;
Wherein carbon nano-tube is coated for carbon source solution and carbon nano tube dispersion liquid to be mixed, 6-10 hour is stirred at 60-180 DEG C, at the even coated carbon source coating layer of carbon nano tube surface, obtain taking carbon nano-tube as core through washing (can with ethanol diafiltration repeatedly), drying again, carbon source is the enveloped carbon nanometer tube of external coating.Carbon source solution, with arbitrary for carbon source in polyvinyl alcohol, polyethylene, polypropylene, nylon, be dissolved in dimethylbenzene or Glycerol solvents and obtain; In carbon source solution, carbon source concentration is 0.001-0.3mol/L.Carbon nano tube dispersion liquid is for obtain carbon nanotube dispersed in dimethylbenzene or Glycerol solvents; In carbon nano tube dispersion liquid, the mass percent of carbon nano-tube is 0.01%-3%.
The one of the preparation method of the nucleocapsid porous nano material with carbon element for electrode of super capacitor disclosed by the invention is improved, carbonization be by enveloped carbon nanometer tube in 0.1-1mol/L oxidizing acid, through 50-120 DEG C after oxidation processes 3-6 hour, carbon source coating layer is carbonized into agraphitic carbon shell, obtain the carbon nano-tube that agraphitic carbon shell is coated, wherein the concentration of oxidizing acid solution is with acid radical anion densimeter.
The one of the preparation method of the nucleocapsid porous nano material with carbon element for electrode of super capacitor disclosed by the invention is improved, pore-creating is after carbon nano-tube coated for agraphitic carbon shell being mixed with alkali, in 500-800 DEG C of process pore-creating in 3-6 hour, (neutralize with hydrochloric acid through cooling, acid neutralization again, hydrochloric acid belongs to volatile acid and is convenient to remove, and not easily with the formation bonding of nucleocapsid porous nano carbon material surface), wash, drying.
The one of the preparation method of the nucleocapsid porous nano material with carbon element for electrode of super capacitor disclosed by the invention is improved, and in carbon nano-tube encapsulation steps, drying is vacuum freeze drying, and drying time is 24-48h.
The one of the preparation method of the nucleocapsid porous nano material with carbon element for electrode of super capacitor disclosed by the invention is improved, and in carburising step, oxidizing acid is arbitrary in sulfuric acid, nitric acid.
The one of the preparation method of the nucleocapsid porous nano material with carbon element for electrode of super capacitor disclosed by the invention is improved, and the carbon nano-tube that in pore-creating step, agraphitic carbon shell is coated and the mixed proportion of alkali are (mass ratio) 1:(1-10).
The one of the preparation method of the nucleocapsid porous nano material with carbon element for electrode of super capacitor disclosed by the invention is improved, and in pore-creating step, alkali is at least one in NaOH, potassium hydroxide or calcium hydroxide.
The one of the preparation method of the nucleocapsid porous nano material with carbon element for electrode of super capacitor disclosed by the invention is improved, and in pore-creating step, drying is dry 12-24 hour at 20-110 DEG C.
The nucleocapsid porous nano material with carbon element being applied to electrode of super capacitor disclosed by the invention, nucleocapsid porous nano material with carbon element is take carbon nano-tube as core, and being uniformly coated with nanometer porous carbon-coating at core skin, described core is single-layer carbon nano-tube or multilayer carbon nanotube.
The one being applied to the nucleocapsid porous nano material with carbon element of electrode of super capacitor disclosed by the invention is improved, and the specific area of nucleocapsid porous nano material with carbon element is 300-2500m
2/ g.
The one being applied to the nucleocapsid porous nano material with carbon element of electrode of super capacitor disclosed by the invention is improved, and the number of plies of the carbon nano-tube of core is 1-20 layer.
The one being applied to the nucleocapsid porous nano material with carbon element of electrode of super capacitor disclosed by the invention is improved, and the specific area of carbon nano-tube is 150-1300m
2/ g.
The one being applied to the nucleocapsid porous nano material with carbon element of electrode of super capacitor disclosed by the invention is improved, and the aperture of nanometer porous carbon-coating is 1-50nm.
The one being applied to the nucleocapsid porous nano material with carbon element of electrode of super capacitor disclosed by the invention is improved, and the thickness of nanometer porous carbon-coating is 0.05-1 μm.
The one being applied to the nucleocapsid porous nano material with carbon element of electrode of super capacitor disclosed by the invention is improved, and the specific area of nanometer porous carbon-coating is 300-2500m
2/ g.
The ultracapacitor of application nucleocapsid porous nano material with carbon element disclosed by the invention, comprise positive pole, negative pole, electrolyte and barrier film, wherein negative or positive electrode surface-coated has slurry, pulp bales is containing nucleocapsid porous nano material with carbon element, described nucleocapsid porous nano material with carbon element is take carbon nano-tube as core, and being uniformly coated with nanometer porous carbon-coating at core skin, described core is the carbon nano-tube of multiple-level stack.
The one of the ultracapacitor of application nucleocapsid porous nano material with carbon element disclosed by the invention is improved, nucleocapsid porous nano material with carbon element specific capacity is in the electrolytic solution 120-250F/g (constant current charge-discharge current density is 0.5A/g), or 70-180F/g (constant current charge-discharge current density is 5A/g).
The one of the ultracapacitor of application nucleocapsid porous nano material with carbon element disclosed by the invention is improved, and the equivalent series resistance of super capacitor is 0.1-0.5 Ω.
The one of the ultracapacitor of application nucleocapsid porous nano material with carbon element disclosed by the invention is improved, and the specific area of nucleocapsid porous nano material with carbon element is 300-2500m
2/ g.
The one of the ultracapacitor of application nucleocapsid porous nano material with carbon element disclosed by the invention is improved, and the number of plies of the carbon nano-tube of core is 1-20 layer.
The one of the ultracapacitor of application nucleocapsid porous nano material with carbon element disclosed by the invention is improved, and the specific area of carbon nano-tube is 150-1300m
2/ g.
The one of the ultracapacitor of application nucleocapsid porous nano material with carbon element disclosed by the invention is improved, and the aperture of nanometer porous carbon-coating is 1-50nm.
The one of the ultracapacitor of application nucleocapsid porous nano material with carbon element disclosed by the invention is improved, and the thickness of nanometer porous carbon-coating is 0.05-1 μm.
The one of the ultracapacitor of application nucleocapsid porous nano material with carbon element disclosed by the invention is improved, and the specific area of nanometer porous carbon-coating is 300-2500m
2/ g.
The preparation method of the ultracapacitor of application nucleocapsid porous nano material with carbon element disclosed by the invention, comprise the steps: that negative pole, cellulosic separator, positive pole and cellulosic separator load in shell after being assembled into battery core according to Z-type lamination process, and encapsulation obtains after pouring into electrolyte, in the coating slurry of wherein positive pole or negative pole, include nucleocapsid porous nano material with carbon element.
Compared with the prior art this invention, has following usefulness:
(1) compared to the physical mixed of active carbon and carbon nano-tube, in this nucleocapsid porous nano material with carbon element, amorphous carbon layer is completely coated by carbon pipe, overcomes the Van der Waals force between tube and tube, makes carbon nanotube dispersed complete; Meanwhile, carbon nano-tube also contacts completely with active carbon, more contributes to electronics and is effectively transported on active carbon.This material specific surface area is large, and pore structure is abundant and conductivity is high, is conducive to low internal resistance, improves specific capacity, and effectively can improve high rate performance.
(2) this nucleocapsid structure due to the thickness of shell thin, ion is short to the distance entering porous carbon structure internal layer completely from electrolyte main body, is conducive to the fast transport of ion under large charging and discharging currents, is conducive to the raising of high rate performance.
(3) ultracapacitor of application nucleocapsid porous nano material with carbon element disclosed by the invention, long service life, under 0-2.7V voltage, circulate more than 5000 times rear specific capacity decline 1%-5%.
Embodiment
Below in conjunction with embodiment, illustrate the present invention further, following embodiment should be understood and be only not used in for illustration of the present invention and limit the scope of the invention.
Nucleocapsid porous nano material with carbon element embodiment 1
In the present embodiment, nucleocapsid porous nano material with carbon element is be core with carbon nano-tube, and (thickness is 0.05 μm, and aperture is 50nm, and specific area is 300m to be uniformly coated with nanometer porous carbon-coating at core skin
2/ g), core is that (specific area is 250m for the carbon nano-tube of 1 layer
2/ g), the specific area of nucleocapsid porous nano material with carbon element is 300m
2/ g.
Nucleocapsid porous nano material with carbon element embodiment 2
In the present embodiment, nucleocapsid porous nano material with carbon element is be core with carbon nano-tube, and (thickness is 0.1 μm, and aperture is 40nm, and specific area is 500m to be uniformly coated with nanometer porous carbon-coating at core skin
2/ g), core is that (specific area is 150m to 2 layers of stacking carbon nano-tube
2/ g), the specific area of nucleocapsid porous nano material with carbon element is 500m
2/ g.
Nucleocapsid porous nano material with carbon element embodiment 3
In the present embodiment, nucleocapsid porous nano material with carbon element is be core with carbon nano-tube, and (thickness is 0.3 μm, and aperture is 35nm, and specific area is 700m to be uniformly coated with nanometer porous carbon-coating at core skin
2/ g), core is that (specific area is 400m to 3 layers of stacking carbon nano-tube
2/ g), the specific area of nucleocapsid porous nano material with carbon element is 800m
2/ g.
Nucleocapsid porous nano material with carbon element embodiment 4
In the present embodiment, nucleocapsid porous nano material with carbon element is be core with carbon nano-tube, and (thickness is 1 μm, and aperture is 1nm, and specific area is 2500m to be uniformly coated with nanometer porous carbon-coating at core skin
2/ g), core is that (specific area is 1000m to 20 layers of stacking carbon nano-tube
2/ g), the specific area of nucleocapsid porous nano material with carbon element is 2500m
2/ g.
Nucleocapsid porous nano material with carbon element embodiment 5
In the present embodiment, nucleocapsid porous nano material with carbon element is be core with carbon nano-tube, and (thickness is 0.5 μm, and aperture is 20nm, and specific area is 1500m to be uniformly coated with nanometer porous carbon-coating at core skin
2/ g), core is that (specific area is 800m to 10 layers of stacking carbon nano-tube
2/ g), the specific area of nucleocapsid porous nano material with carbon element is 1300m
2/ g.
Nucleocapsid porous nano material with carbon element embodiment 6
In the present embodiment, nucleocapsid porous nano material with carbon element is be core with carbon nano-tube, and (thickness is 0.6 μm, and aperture is 25nm, and specific area is 2000m to be uniformly coated with nanometer porous carbon-coating at core skin
2/ g), core is that (specific area is 1100m to 13 layers of stacking carbon nano-tube
2/ g), the specific area of nucleocapsid porous nano material with carbon element is 1500m
2/ g.
Nucleocapsid porous nano material with carbon element embodiment 7
In the present embodiment, nucleocapsid porous nano material with carbon element is be core with carbon nano-tube, and (thickness is 0.08 μm, and aperture is 7nm, and specific area is 800m to be uniformly coated with nanometer porous carbon-coating at core skin
2/ g), core is that (specific area is 1300m to 17 layers of stacking carbon nano-tube
2/ g), the specific area of nucleocapsid porous nano material with carbon element is 1800m
2/ g.
Nucleocapsid porous nano material with carbon element embodiment 8
In the present embodiment, nucleocapsid porous nano material with carbon element is be core with carbon nano-tube, and (thickness is 0.15 μm, and aperture is 13nm, and specific area is 2200m to be uniformly coated with nanometer porous carbon-coating at core skin
2/ g), core is that (specific area is 800m to 15 layers of stacking carbon nano-tube
2/ g), the specific area of nucleocapsid porous nano material with carbon element is 1600m
2/ g.
Nucleocapsid porous nano material with carbon element embodiment 9
In the present embodiment, nucleocapsid porous nano material with carbon element is be core with carbon nano-tube, and (thickness is 0.33 μm, and aperture is 19nm, and specific area is 1600m to be uniformly coated with nanometer porous carbon-coating at core skin
2/ g), core is that (specific area is 700m to 12 layers of stacking carbon nano-tube
2/ g), the specific area of nucleocapsid porous nano material with carbon element is 1350m
2/ g.
Nucleocapsid porous nano material with carbon element embodiment 10
In the present embodiment, nucleocapsid porous nano material with carbon element is be core with carbon nano-tube, and (thickness is 0.68 μm, and aperture is 25nm, and specific area is 1200m to be uniformly coated with nanometer porous carbon-coating at core skin
2/ g), core is that (specific area is 600m to 16 layers of stacking carbon nano-tube
2/ g), the specific area of nucleocapsid porous nano material with carbon element is 2000m
2/ g.
Nucleocapsid porous nano material with carbon element embodiment 11
In the present embodiment, nucleocapsid porous nano material with carbon element is be core with carbon nano-tube, and (thickness is 0.84 μm, and aperture is 36nm, and specific area is 1750m to be uniformly coated with nanometer porous carbon-coating at core skin
2/ g), core is that (specific area is 1250m to 19 layers of stacking carbon nano-tube
2/ g), the specific area of nucleocapsid porous nano material with carbon element is 2300m
2/ g.
Include, without being limited to nucleocapsid porous nano material with carbon element cited by above nucleocapsid porous nano material with carbon element embodiment all to be prepared by the technical scheme cited by the preparation embodiment that includes, without being limited to following nucleocapsid porous nano material with carbon element, and do not exceed scope of the presently claimed invention.
The preparation embodiment 1 of nucleocapsid porous nano material with carbon element
Be dissolved in by polyvinyl alcohol in dimethylbenzene, forming concentration is the solution of 0.3mol/L.Be 1300m by specific area
2the Single Walled Carbon Nanotube of/g is scattered in dimethylbenzene by ultrasonic disperse and forms the dispersion liquid that concentration is 0.3wt%.
By above-mentioned two kinds of solution mixing, at 60 DEG C, stir 10 hours, make polyvinyl alcohol evenly coated in carbon nano tube surface.Afterwards by filter product is leached, with ethanol diafiltration repeatedly, use freeze dryer dry under vacuum, drying time 24h, acquisition carbon nano-tube is axle, and polyvinyl alcohol is the nucleocapsid structure of shell.
Product is placed in the sulfuric acid solution of 1mol/L, in 120 DEG C of process 6 hours, completes the carbonisation of polyvinyl alcohol.Rear diafiltration, drying, acquisition carbon nano-tube is axle, and agraphitic carbon is the pure carbon nucleocapsid structure of shell.
This pure carbon nucleocapsid structure is mixed (mass ratio) with the ratio of 1:1 with KOH, after within 6 hours, carry out pore-creating process in 500 DEG C of process.After cooling, neutralize with hydrochloric acid, and use deionized water diafiltration, drying 12 hours at 110 DEG C.After testing, the layer thickness of the nanometer porous carbon-coating that this step obtains is 0.05 μm, and the diameter of porous is distributed as 1-50nm.
The specific area of this nucleocapsid porous nano material with carbon element is 2500m
2/ g.The specific capacity of this material in organic electrolyte is 250F/g (constant current charge-discharge current density is 0.5A/g), or 180F/g (constant current charge-discharge current density is 5A/g).
The preparation embodiment 2 of nucleocapsid porous nano material with carbon element
Be dissolved in by polyvinyl alcohol in dimethylbenzene, forming concentration is the solution of 0.001mol/L.Be 1300m by specific area
2the Single Walled Carbon Nanotube of/g is scattered in dimethylbenzene by ultrasonic disperse and forms the dispersion liquid that concentration is 0.01wt%.
By above-mentioned two kinds of solution mixing, at 80 DEG C, stir 9.5 hours, make polyvinyl alcohol evenly coated in carbon nano tube surface.Afterwards by filter product is leached, with ethanol diafiltration repeatedly, use freeze dryer dry under vacuum, drying time 27h, acquisition carbon nano-tube is axle, and polyvinyl alcohol is the nucleocapsid structure of shell.
Product is placed in the sulfuric acid solution of 0.1mol/L, in 77 DEG C of process 4.6 hours, completes the carbonisation of polyvinyl alcohol.Rear diafiltration, drying, acquisition carbon nano-tube is axle, and agraphitic carbon is the pure carbon nucleocapsid structure of shell.
This pure carbon nucleocapsid structure is mixed (mass ratio) with the ratio of 1:2 with KOH, after within 6.8 hours, carry out pore-creating process in 570 DEG C of process.After cooling, neutralize with hydrochloric acid, and use deionized water diafiltration, drying 13 hours at 100 DEG C.After testing, the layer thickness of the nanometer porous carbon-coating that this step obtains is 0.05 μm, and the diameter of porous is distributed as 1-50nm.
The specific area of this nucleocapsid porous nano material with carbon element is 2500m
2/ g.The specific capacity of this material in organic electrolyte is 250F/g (constant current charge-discharge current density is 0.5A/g), or 180F/g (constant current charge-discharge current density is 5A/g).
The preparation embodiment 3 of nucleocapsid porous nano material with carbon element
Be dissolved in by polyvinyl alcohol in dimethylbenzene, forming concentration is the solution of 0.008mol/L.Be 1300m by specific area
2the Single Walled Carbon Nanotube of/g is scattered in dimethylbenzene by ultrasonic disperse and forms the dispersion liquid that concentration is 0.08wt%.
By above-mentioned two kinds of solution mixing, at 73 DEG C, stir 9 hours, make polyvinyl alcohol evenly coated in carbon nano tube surface.Afterwards by filter product is leached, with ethanol diafiltration repeatedly, use freeze dryer dry under vacuum, drying time 32h, acquisition carbon nano-tube is axle, and polyvinyl alcohol is the nucleocapsid structure of shell.
Product is placed in the sulfuric acid solution of 0.3mol/L, in 110 DEG C of process 5.5 hours, completes the carbonisation of polyvinyl alcohol.Rear diafiltration, drying, acquisition carbon nano-tube is axle, and agraphitic carbon is the pure carbon nucleocapsid structure of shell.
This pure carbon nucleocapsid structure is mixed (mass ratio) with the ratio of 1:3 with KOH, after within 5.5 hours, carry out pore-creating process in 520 DEG C of process.After cooling, neutralize with hydrochloric acid, and use deionized water diafiltration, drying 14 hours at 90 DEG C.After testing, the layer thickness of the nanometer porous carbon-coating that this step obtains is 1 μm, and the diameter of porous is distributed as 1-50nm.
The specific area of this nucleocapsid porous nano material with carbon element is 300m
2/ g.The specific capacity of this material in organic electrolyte is 120F/g (constant current charge-discharge current density is 0.5A/g), or 70F/g (constant current charge-discharge current density is 5A/g).
The preparation embodiment 4 of nucleocapsid porous nano material with carbon element
Be dissolved in by polyvinyl alcohol in dimethylbenzene, forming concentration is the solution of 0.01mol/L.Be 1300m by specific area
2the Single Walled Carbon Nanotube of/g is scattered in dimethylbenzene by ultrasonic disperse and forms the dispersion liquid that concentration is 1.01wt%.
By above-mentioned two kinds of solution mixing, at 95 DEG C, stir 8.5 hours, make polyvinyl alcohol evenly coated in carbon nano tube surface.Afterwards by filter product is leached, with ethanol diafiltration repeatedly, use freeze dryer dry under vacuum, drying time 35h, acquisition carbon nano-tube is axle, and polyvinyl alcohol is the nucleocapsid structure of shell.
Product is placed in the sulfuric acid solution of 0.6mol/L, in 108 DEG C of process 6.2 hours, completes the carbonisation of polyvinyl alcohol.Rear diafiltration, drying, acquisition carbon nano-tube is axle, and agraphitic carbon is the pure carbon nucleocapsid structure of shell.
This pure carbon nucleocapsid structure is mixed (mass ratio) with the ratio of 1:4 with KOH, after within 5 hours, carry out pore-creating process in 680 DEG C of process.After cooling, neutralize with hydrochloric acid, and use deionized water diafiltration, drying 15 hours at 80 DEG C.After testing, the layer thickness of the nanometer porous carbon-coating that this step obtains is 0.1 μm, and the diameter of porous is distributed as 1-50nm.
The specific area of this nucleocapsid porous nano material with carbon element is 2000m
2/ g.The specific capacity of this material in organic electrolyte is 220F/g (constant current charge-discharge current density is 0.5A/g), or 150F/g (constant current charge-discharge current density is 5A/g).
The preparation embodiment 5 of nucleocapsid porous nano material with carbon element
Be dissolved in by polyvinyl alcohol in dimethylbenzene, forming concentration is the solution of 0.05mol/L.Be 1300m by specific area
2the Single Walled Carbon Nanotube of/g is scattered in dimethylbenzene by ultrasonic disperse and forms the dispersion liquid that concentration is 3wt%.
By above-mentioned two kinds of solution mixing, at 104 DEG C, stir 8 hours, make polyvinyl alcohol evenly coated in carbon nano tube surface.Afterwards by filter product is leached, with ethanol diafiltration repeatedly, use freeze dryer dry under vacuum, drying time 40h, acquisition carbon nano-tube is axle, and polyvinyl alcohol is the nucleocapsid structure of shell.
Product is placed in the sulfuric acid solution of 0.5mol/L, in 66 DEG C of process 5.5 hours, completes the carbonisation of polyvinyl alcohol.Rear diafiltration, drying, acquisition carbon nano-tube is axle, and agraphitic carbon is the pure carbon nucleocapsid structure of shell.
This pure carbon nucleocapsid structure is mixed (mass ratio) with the ratio of 1:5 with KOH, after within 5.2 hours, carry out pore-creating process in 640 DEG C of process.After cooling, neutralize with hydrochloric acid, and use deionized water diafiltration, drying 16 hours at 70 DEG C.After testing, the layer thickness of the nanometer porous carbon-coating that this step obtains is 0.2 μm, and the diameter of porous is distributed as 1-50nm.
The specific area of this nucleocapsid porous nano material with carbon element is 1200m
2/ g.The specific capacity of this material in organic electrolyte is 200F/g (constant current charge-discharge current density is 0.5A/g), or 130F/g (constant current charge-discharge current density is 5A/g).
The preparation embodiment 6 of nucleocapsid porous nano material with carbon element
Be dissolved in by polyvinyl alcohol in dimethylbenzene, forming concentration is the solution of 0.08mol/L.Be 1300m by specific area
2the Single Walled Carbon Nanotube of/g is scattered in dimethylbenzene by ultrasonic disperse and forms the dispersion liquid that concentration is 0.8wt%.
By above-mentioned two kinds of solution mixing, at 113 DEG C, stir 7.5 hours, make polyvinyl alcohol evenly coated in carbon nano tube surface.Afterwards by filter product is leached, with ethanol diafiltration repeatedly, use freeze dryer dry under vacuum, drying time 43h, acquisition carbon nano-tube is axle, and polyvinyl alcohol is the nucleocapsid structure of shell.
Product is placed in the sulfuric acid solution of 0.9mol/L, in 98 DEG C of process 3.6 hours, completes the carbonisation of polyvinyl alcohol.Rear diafiltration, drying, acquisition carbon nano-tube is axle, and agraphitic carbon is the pure carbon nucleocapsid structure of shell.
This pure carbon nucleocapsid structure is mixed (mass ratio) with the ratio of 1:6 with KOH, after within 3.4 hours, carry out pore-creating process in 770 DEG C of process.After cooling, neutralize with hydrochloric acid, and use deionized water diafiltration, drying 17 hours at 60 DEG C.After testing, the layer thickness of the nanometer porous carbon-coating that this step obtains is 0.5 μm, and the diameter of porous is distributed as 1-50nm.
The specific area of this nucleocapsid porous nano material with carbon element is 2000m
2/ g.The specific capacity of this material in organic electrolyte is 220F/g (constant current charge-discharge current density is 0.5A/g), or 160F/g (constant current charge-discharge current density is 5A/g).
The preparation embodiment 7 of nucleocapsid porous nano material with carbon element
Be dissolved in by polyvinyl alcohol in dimethylbenzene, forming concentration is the solution of 0.1mol/L.Be 1300m by specific area
2the Single Walled Carbon Nanotube of/g is scattered in dimethylbenzene by ultrasonic disperse and forms the dispersion liquid that concentration is 2.1wt%.
By above-mentioned two kinds of solution mixing, at 125 DEG C, stir 7 hours, make polyvinyl alcohol evenly coated in carbon nano tube surface.Afterwards by filter product is leached, with ethanol diafiltration repeatedly, use freeze dryer dry under vacuum, drying time 45h, acquisition carbon nano-tube is axle, and polyvinyl alcohol is the nucleocapsid structure of shell.
Product is placed in the sulfuric acid solution of 0.78mol/L, in 100 DEG C of process 3 hours, completes the carbonisation of polyvinyl alcohol.Rear diafiltration, drying, acquisition carbon nano-tube is axle, and agraphitic carbon is the pure carbon nucleocapsid structure of shell.
This pure carbon nucleocapsid structure is mixed (mass ratio) with the ratio of 1:7 with KOH, after within 4.4 hours, carry out pore-creating process in 750 DEG C of process.After cooling, neutralize with hydrochloric acid, and use deionized water diafiltration, drying 18 hours at 50 DEG C.After testing, the layer thickness of the nanometer porous carbon-coating that this step obtains is 0.5 μm, and the diameter of porous is distributed as 1-50nm.
The specific area of this nucleocapsid porous nano material with carbon element is 800m
2/ g.The specific capacity of this material in organic electrolyte is 140F/g (constant current charge-discharge current density is 0.5A/g), or 110F/g (constant current charge-discharge current density is 5A/g).
The preparation embodiment 8 of nucleocapsid porous nano material with carbon element
Be dissolved in by polyvinyl alcohol in dimethylbenzene, forming concentration is the solution of 0.17mol/L.Be 1300m by specific area
2the Single Walled Carbon Nanotube of/g is scattered in dimethylbenzene by ultrasonic disperse and forms the dispersion liquid that concentration is 1.17wt%.
By above-mentioned two kinds of solution mixing, at 145 DEG C, stir 6.5 hours, make polyvinyl alcohol evenly coated in carbon nano tube surface.Afterwards by filter product is leached, with ethanol diafiltration repeatedly, use freeze dryer dry under vacuum, drying time 48h, acquisition carbon nano-tube is axle, and polyvinyl alcohol is the nucleocapsid structure of shell.
Product is placed in the sulfuric acid solution of 0.45mol/L, in 80 DEG C of process 5 hours, completes the carbonisation of polyvinyl alcohol.Rear diafiltration, drying, acquisition carbon nano-tube is axle, and agraphitic carbon is the pure carbon nucleocapsid structure of shell.
This pure carbon nucleocapsid structure is mixed (mass ratio) with the ratio of 1:8 with KOH, after within 4.8 hours, carry out pore-creating process in 600 DEG C of process.After cooling, neutralize with hydrochloric acid, and use deionized water diafiltration, drying 21 hours at 40 DEG C.After testing, the layer thickness of the nanometer porous carbon-coating that this step obtains is 0.05 μm, and the diameter of porous is distributed as 1-50nm.
The specific area of this nucleocapsid porous nano material with carbon element is 2500m
2/ g.The specific capacity of this material in organic electrolyte is 250F/g (constant current charge-discharge current density is 0.5A/g), or 180F/g (constant current charge-discharge current density is 5A/g).
The preparation embodiment 9 of nucleocapsid porous nano material with carbon element
Be dissolved in by polyvinyl alcohol in dimethylbenzene, forming concentration is the solution of 0.2mol/L.Be 1300m by specific area
2the Single Walled Carbon Nanotube of/g is scattered in dimethylbenzene by ultrasonic disperse and forms the dispersion liquid that concentration is 2.3wt%.
By above-mentioned two kinds of solution mixing, at 167 DEG C, stir 6 hours, make polyvinyl alcohol evenly coated in carbon nano tube surface.Afterwards by filter product is leached, with ethanol diafiltration repeatedly, use freeze dryer dry under vacuum, drying time 33h, acquisition carbon nano-tube is axle, and polyvinyl alcohol is the nucleocapsid structure of shell.
Product is placed in the sulfuric acid solution of 0.36mol/L, in 70 DEG C of process 3 hours, completes the carbonisation of polyvinyl alcohol.Rear diafiltration, drying, acquisition carbon nano-tube is axle, and agraphitic carbon is the pure carbon nucleocapsid structure of shell.
This pure carbon nucleocapsid structure is mixed (mass ratio) with the ratio of 1:9 with KOH, after within 4.5 hours, carry out pore-creating process in 700 DEG C of process.After cooling, neutralize with hydrochloric acid, and use deionized water diafiltration, drying 23 hours at 30 DEG C.After testing, the layer thickness of the nanometer porous carbon-coating that this step obtains is 0.05 μm, and the diameter of porous is distributed as 1-50nm.
The specific area of this nucleocapsid porous nano material with carbon element is 2500m
2/ g.The specific capacity of this material in organic electrolyte is 250F/g (constant current charge-discharge current density is 0.5A/g), or 180F/g (constant current charge-discharge current density is 5A/g).
The preparation embodiment 10 of nucleocapsid porous nano material with carbon element
Be dissolved in by polyvinyl alcohol in dimethylbenzene, forming concentration is the solution of 0.26mol/L.Be 1300m by specific area
2the Single Walled Carbon Nanotube of/g is scattered in dimethylbenzene by ultrasonic disperse and forms the dispersion liquid that concentration is 2.72wt%.
By above-mentioned two kinds of solution mixing, at 180 DEG C, stir 7.3 hours, make polyvinyl alcohol evenly coated in carbon nano tube surface.Afterwards by filter product is leached, with ethanol diafiltration repeatedly, use freeze dryer dry under vacuum, drying time 27h, acquisition carbon nano-tube is axle, and polyvinyl alcohol is the nucleocapsid structure of shell.
Product is placed in the sulfuric acid solution of 0.27mol/L, in 50 DEG C of process 4 hours, completes the carbonisation of polyvinyl alcohol.Rear diafiltration, drying, acquisition carbon nano-tube is axle, and agraphitic carbon is the pure carbon nucleocapsid structure of shell.
This pure carbon nucleocapsid structure is mixed (mass ratio) with the ratio of 1:10 with KOH, after within 3 hours, carry out pore-creating process in 800 DEG C of process.After cooling, neutralize with hydrochloric acid, and use deionized water diafiltration, within dry 24 hours at 20 DEG C, the layer thickness of the nanometer porous carbon-coating that this step obtains is 0.2 μm, and the diameter of porous is distributed as 1-50nm after testing.
The specific area of this nucleocapsid porous nano material with carbon element is 500m
2/ g.The specific capacity of this material in organic electrolyte is 130F/g (constant current charge-discharge current density is 0.5A/g), or 80F/g (constant current charge-discharge current density is 5A/g).
Distinguish with above-described embodiment, in carbon nano tube dispersion liquid, solvent can also be glycerine, carbon source solution can also be arbitrary in the glycerite of the glycerite of polyvinyl alcohol, poly xylene solution, poly glycerite, polyacrylic xylene solution, polyacrylic glycerite, the xylene solution of nylon, nylon, when carbonization, oxidizing acid can also be nitric acid, when pore-creating, alkali can also be arbitrary for what include, without being limited in following scheme: NaOH, calcium hydroxide, potassium hydroxide and NaOH mixture (mass ratio 1:2, 1:1, 1:3, 1:2.5, 1:2.7, 1:4, 1:5, 1:6, 1:7 and other arbitrarily than mixture), potassium hydroxide and calcium hydroxide mixture (mass ratio 1:2, 1:1, 1:3, 1:2.5, 1:2.7, 1:4, 1:5, 1:6, 1:7 and other arbitrarily than mixture), NaOH and calcium hydroxide mixture (mass ratio 1:2, 1:1, 1:3, 1:2.5, 1:2.7, 1:4, 1:5, 1:6, 1:7 and other arbitrarily than mixture) and NaOH, potassium hydroxide and calcium hydroxide three mixture (mass ratio 1:1:2, 0.5:1:1, 1:3:1, 1:1:2.5, 1:2.7:1, 1:1:4, 5:1:1, 1:6:1, 1:7:0.1 and other arbitrarily than mixture).
The embodiment 1 of the ultracapacitor of application nucleocapsid porous nano material with carbon element
The ultracapacitor of the present embodiment comprises positive pole, negative pole, electrolyte and barrier film, wherein negative or positive electrode surface-coated has slurry, pulp bales is containing nucleocapsid porous nano material with carbon element, and wherein nucleocapsid porous nano material with carbon element adopts nucleocapsid porous nano material with carbon element embodiment 1.Through assembling, encapsulate the capacitor obtained, its equivalent series resistance is 0.5 Ω after testing; Under 0-2.7V voltage, the specific capacity after 5000 times that circulates declines 5%.
The embodiment 2 of the ultracapacitor of application nucleocapsid porous nano material with carbon element
The ultracapacitor of the present embodiment comprises positive pole, negative pole, electrolyte and barrier film, wherein negative or positive electrode surface-coated has slurry, pulp bales is containing nucleocapsid porous nano material with carbon element, and wherein nucleocapsid porous nano material with carbon element adopts nucleocapsid porous nano material with carbon element embodiment 2.Through assembling, encapsulate the capacitor obtained, its equivalent series resistance is 0.48 Ω after testing; Under 0-2.7V voltage, the specific capacity after 8000 times that circulates declines 5%.
The embodiment 3 of the ultracapacitor of application nucleocapsid porous nano material with carbon element
The ultracapacitor of the present embodiment comprises positive pole, negative pole, electrolyte and barrier film, wherein negative or positive electrode surface-coated has slurry, pulp bales is containing nucleocapsid porous nano material with carbon element, and wherein nucleocapsid porous nano material with carbon element adopts nucleocapsid porous nano material with carbon element embodiment 3.Through assembling, encapsulate the capacitor obtained, its equivalent series resistance is 0.4 Ω after testing; Under 0-2.7V voltage, the specific capacity after 14000 times that circulates declines 5%.
The embodiment 4 of the ultracapacitor of application nucleocapsid porous nano material with carbon element
The ultracapacitor of the present embodiment comprises positive pole, negative pole, electrolyte and barrier film, wherein negative or positive electrode surface-coated has slurry, pulp bales is containing nucleocapsid porous nano material with carbon element, and wherein nucleocapsid porous nano material with carbon element adopts nucleocapsid porous nano material with carbon element embodiment 4.Through assembling, encapsulate the capacitor obtained, its equivalent series resistance is 0.1 Ω after testing; Under 0-2.7V voltage, the specific capacity after 22000 times that circulates declines 5%.
The embodiment 5 of the ultracapacitor of application nucleocapsid porous nano material with carbon element
The ultracapacitor of the present embodiment comprises positive pole, negative pole, electrolyte and barrier film, wherein negative or positive electrode surface-coated has slurry, pulp bales is containing nucleocapsid porous nano material with carbon element, and wherein nucleocapsid porous nano material with carbon element adopts nucleocapsid porous nano material with carbon element embodiment 5.Through assembling, encapsulate the capacitor obtained, its equivalent series resistance is 0.2 Ω after testing; Under 0-2.7V voltage, the specific capacity after 20000 times that circulates declines 5%.
The embodiment 6 of the ultracapacitor of application nucleocapsid porous nano material with carbon element
The ultracapacitor of the present embodiment comprises positive pole, negative pole, electrolyte and barrier film, wherein negative or positive electrode surface-coated has slurry, pulp bales is containing nucleocapsid porous nano material with carbon element, and wherein nucleocapsid porous nano material with carbon element adopts nucleocapsid porous nano material with carbon element embodiment 6.Through assembling, encapsulate the capacitor obtained, its equivalent series resistance is 0.4 Ω after testing; Under 0-2.7V voltage, the specific capacity after 12000 times that circulates declines 5%.
The embodiment 7 of the ultracapacitor of application nucleocapsid porous nano material with carbon element
The ultracapacitor of the present embodiment comprises positive pole, negative pole, electrolyte and barrier film, wherein negative or positive electrode surface-coated has slurry, pulp bales is containing nucleocapsid porous nano material with carbon element, and wherein nucleocapsid porous nano material with carbon element adopts nucleocapsid porous nano material with carbon element embodiment 7.Through assembling, encapsulate the capacitor obtained, its equivalent series resistance is 0.35 Ω after testing; Under 0-2.7V voltage, the specific capacity after 15000 times that circulates declines 5%.
The embodiment 8 of the ultracapacitor of application nucleocapsid porous nano material with carbon element
The ultracapacitor of the present embodiment comprises positive pole, negative pole, electrolyte and barrier film, wherein negative or positive electrode surface-coated has slurry, pulp bales is containing nucleocapsid porous nano material with carbon element, and wherein nucleocapsid porous nano material with carbon element adopts nucleocapsid porous nano material with carbon element embodiment 8.Through assembling, encapsulate the capacitor obtained, its equivalent series resistance is 0.45 Ω after testing; Under 0-2.7V voltage, the specific capacity after 10000 times that circulates declines 5%.
The embodiment 9 of the ultracapacitor of application nucleocapsid porous nano material with carbon element
The ultracapacitor of the present embodiment comprises positive pole, negative pole, electrolyte and barrier film, wherein negative or positive electrode surface-coated has slurry, pulp bales is containing nucleocapsid porous nano material with carbon element, and wherein nucleocapsid porous nano material with carbon element adopts nucleocapsid porous nano material with carbon element embodiment 9.Through assembling, encapsulate the capacitor obtained, its equivalent series resistance is 0.25 Ω after testing; Under 0-2.7V voltage, the specific capacity after 5500 times that circulates declines 5%.
The embodiment 10 of the ultracapacitor of application nucleocapsid porous nano material with carbon element
The ultracapacitor of the present embodiment comprises positive pole, negative pole, electrolyte and barrier film, wherein negative or positive electrode surface-coated has slurry, pulp bales is containing nucleocapsid porous nano material with carbon element, and wherein nucleocapsid porous nano material with carbon element adopts nucleocapsid porous nano material with carbon element embodiment 10.Through assembling, encapsulate the capacitor obtained, its equivalent series resistance is 0.33 Ω after testing; Under 0-2.7V voltage, the specific capacity after 8000 times that circulates declines 5%.
The embodiment 11 of the ultracapacitor of application nucleocapsid porous nano material with carbon element
The ultracapacitor of the present embodiment comprises positive pole, negative pole, electrolyte and barrier film, wherein negative or positive electrode surface-coated has slurry, pulp bales is containing nucleocapsid porous nano material with carbon element, and wherein nucleocapsid porous nano material with carbon element adopts nucleocapsid porous nano material with carbon element embodiment 11.Through assembling, encapsulate the capacitor obtained, its equivalent series resistance is 0.42 Ω after testing; Under 0-2.7V voltage, the specific capacity after 7000 times that circulates declines 5%.
In view of the present invention program's embodiment is numerous, each embodiment experimental data is huge numerous, be not suitable for particularize explanation herein, but the content of the required checking of each embodiment is all close with the final conclusion obtained, so do not illustrate one by one the checking content of each embodiment herein, only enumerate above-mentioned part and the excellent part of the present patent application is representatively described, and not as the restriction to application claims scope.
The technical scope midrange non-limit part that this place embodiment is protected application claims and in embodiment technical scheme to the new technical scheme that the equal replacement of single or multiple technical characteristic is formed, equally all in the scope of protection of present invention; Simultaneously in all embodiments enumerated or do not enumerate of the present invention program, parameters in the same embodiment only represents an example (i.e. a kind of feasible scheme) of its technical scheme, and between parameters, there is not strict cooperation and qualified relation, wherein each parameter can be replaced, except special declaration mutually when stating ask without prejudice to axiom and the present invention.
Technological means disclosed in the present invention program is not limited only to the technological means disclosed in above-mentioned technological means, also comprises the technical scheme be made up of above technical characteristic combination in any.The above is the specific embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (8)
1. for the preparation method of the nucleocapsid porous nano material with carbon element of electrode of super capacitor, it is characterized in that: comprise the preparation of carbon source solution, the preparation of carbon nano tube dispersion liquid; Carbon nano-tube is coated; Carbonization; Pore-creating;
Wherein carbon nano-tube is coated for carbon source solution and carbon nano tube dispersion liquid to be mixed, 6-10 hour is stirred at 60-180 DEG C, at the even coated carbon source coating layer of carbon nano tube surface, then obtain taking carbon nano-tube as core through washing, drying, carbon source is the enveloped carbon nanometer tube of external coating.
2. the preparation method of the nucleocapsid porous nano material with carbon element for electrode of super capacitor according to claim 1, it is characterized in that: described carbonization for by enveloped carbon nanometer tube in 0.1-1mol/L oxidizing acid, through 50-120 DEG C after oxidation processes 3-6 hour, carbon source coating layer is carbonized into agraphitic carbon shell, obtain the carbon nano-tube that agraphitic carbon shell is coated, wherein the concentration of oxidizing acid solution is with acid radical anion densimeter.
3. the preparation method of the nucleocapsid porous nano material with carbon element for electrode of super capacitor according to claim 1, it is characterized in that: described pore-creating is after carbon nano-tube coated for agraphitic carbon shell being mixed with alkali, pore-creating in 3-6 hour is processed at 500-800 DEG C, then through cooling, acid neutralization, washing, drying.
4. the preparation method of the nucleocapsid porous nano material with carbon element for electrode of super capacitor according to claim 1, is characterized in that: dry in described carbon nano-tube encapsulation steps is vacuum freeze drying, and drying time is 24-48h.
5. the preparation method of the nucleocapsid porous nano material with carbon element for electrode of super capacitor according to claim 2, is characterized in that: in described carburising step, oxidizing acid is arbitrary in sulfuric acid, nitric acid.
6. the preparation method of the nucleocapsid porous nano material with carbon element for electrode of super capacitor according to claim 3, is characterized in that: the carbon nano-tube that in described pore-creating step, agraphitic carbon shell is coated and the mixed proportion of alkali are (mass ratio) 1:(1-10).
7. the preparation method of the nucleocapsid porous nano material with carbon element for electrode of super capacitor according to claim 3 or 6, is characterized in that: in described pore-creating step, alkali is at least one in NaOH, potassium hydroxide or calcium hydroxide.
8. the preparation method of the nucleocapsid porous nano material with carbon element for electrode of super capacitor according to claim 3, is characterized in that: dry in described pore-creating step is dry 12-24 hour at 20-110 DEG C.
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