CN1770344A - Super capacitor and manufacturing method thereof - Google Patents
Super capacitor and manufacturing method thereof Download PDFInfo
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- CN1770344A CN1770344A CN 200410009700 CN200410009700A CN1770344A CN 1770344 A CN1770344 A CN 1770344A CN 200410009700 CN200410009700 CN 200410009700 CN 200410009700 A CN200410009700 A CN 200410009700A CN 1770344 A CN1770344 A CN 1770344A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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
This invention relates to one super capacity for energy storage and its process method, wherein, the capacitor comprises positive electrode, negative electrode, catalyze liquid, film, collector film and sealed shell. The porous carbon electrode is added with proportion of metal oxidation nanometer tube of non-active substance. The catalyze liquid is of organic catalyze liquid. The positive and negative electrodes adopt porous isolation film. The super capacitor adopts metal oxidation nanometer tube to form three-dimensional network skeleton structure in the base part to greatly improve the utility rate of the active substance. The invention adopts high catalyze liquid organic to improve its energy intensity and power property with large prospect.
Description
Technical field
The present invention relates to a kind of ultracapacitor and manufacture method thereof, relate in particular to the new oxide nanotube compound porous carbon type ultracapacitor and the manufacture method thereof that are used for the energy storage.
Technical background
Ultracapacitor is a kind of novel energy device that occurs in recent years, it is a kind of a kind of novel energy device between rechargeable battery and capacitor, have the dual-use function of electric capacity and battery concurrently, its power density is far above common batteries (10 times～100 times), energy density is far above conventional physical electric capacity (＞100 times), compare with battery with ordinary capacitor, it is little that ultracapacitor has a volume, capacity is big, charging rate is fast, have extended cycle life, the discharge power height, working temperature wide (40 ℃～85 ℃), good reliability and advantage such as with low cost, therefore probably develop into a kind of novel from now on, efficiently, practical energy accumulating device, thereby at the energy, communication, power electronics, all there is very wide application prospect in fields such as national defence, as: portable instrument equipment, the data accumulating storage system, electric car power supply, aspects such as emergent back-up source.
Active carbon because have porous, big specific area, porosity height, chemical stability is good, with low cost and characteristics such as long service life, electrode material as double electric layer capacitor, can obtain high energy density and power density, therefore at present mostly with active carbon as polarizing electrode.But active carbon itself exists capacity density and the lower shortcoming of conductivity, has limited ultracapacitor in many application that require the high-energy-density field, and the capacity density that therefore improves electrode material becomes one of present urgency key issue to be solved.
In order further to improve the performance of carbon-based electrode material, by surface modification and various novel preparation process the carbon-based electrode material is carried out a large amount of research work, mainly comprised active carbon, activated carbon fiber, carbon gel, CNT (carbon nano-tube), vitreous carbon, activated carbon fiber, high-density graphite and the resulting foam of pyrolyzed-polymer matrix etc.
Present research for active carbon obtains the specific area maximum and can reach 3000m
2More than/the g, but its capacity density do not present simply with the increase of specific area and increases progressively, and this and its porosity and pore-size distribution are closely related, wherein in micropore (2nm～50nm) shared ratio is one of key factor of its amount of capacity of decision.But in fact micropore in the active carbon (＜2nm) proportion is bigger, because electrolyte can not soak into wherein, thereby this a part of micropore can not form electric double layer and storage power, so the existence of this a part of micropore is for not contribution of the capacity density that improves material.For example for present common specific area＞2000m
2The active carbon electrode material of/g, the utilance of its specific surface usually＜30%, its capacity density is general＜210F/g, is generally＜100F/g.Therefore controlling pore-size distribution increasing specific surface area utilance is a kind of important channel of improving carbon-based electrode material capacitances such as active carbon.
A kind of electrode material for super capacitor is disclosed among the Chinese patent CN1357899A, this material is made up of carbon nano-tube and metal oxide, because high conductivity, high-specific surface area, the high microporosity of carbon nano-tube, with compound high energy density and the power density of obtaining of metal oxide, but carbon nano-tube costs an arm and a leg, and has the too high problem of production cost.
A kind of ultracapacitor that utilizes the activated carbon fiber of high-specific surface area as the self-supporting electrode is proposed in the U.S. Pat 6198623, though having the micropore prosperity, this electrode material is easy to the advantage that electrolyte soaks into, but because main electric double layer capacitance and a small amount of pseudo capacitance storage power of relying on, its micropore utilance still is limited on certain level, therefore still has the lower shortcoming of energy density.
A kind of automobile-used ultracapacitor is disclosed among the Chinese patent CN1431670, it mainly adopts carbon cloth and nickel oxide respectively as negative pole and positive pole, electrolyte adopts the alkali type aqueous solution such as potassium hydroxide, therefore exists operating voltage to hang down and shortcomings such as energy density is lower.
At carbon-based materials such as above employing carbon nano-tube, carbon fibers is that the ultracapacitor of electrode exists the low lower and more high key issue that needs to be resolved hurrily of cost of energy density that causes of effective drainage porosity, the novel ultracapacitor of developing low-cost high capacity density, and the widespread commercial application that is implemented in renewable energy resources field and dynamical system has crucial realistic meaning.
Summary of the invention
The objective of the invention is to overcome the low and more high shortcoming of production cost of ultracapacitor energy density in the prior art, a kind of novel ultracapacitor and manufacture method thereof that is used for the energy field of storage is provided.The present invention has that technology is simple, with low cost to be easy to commercial advantages of application.
Ultracapacitor of the present invention is made up of positive pole, negative pole, electrolyte, barrier film, collector body film and package casing.In the hole that electrolyte is adsorbed in the hole of positive pole, negative pole and barrier film and package casing inside is not occupied by electrode and barrier film; Anodal and negative pole lays respectively at the surface of collector body film; Separated by the porous insulation barrier film between the active material face of positive pole and negative pole; Draw positive and negative terminals from anodal and negative pole one side respectively; Constitute the ultracapacitor monomer by the shell encapsulation again.
Its feature of ultracapacitor monomer of the present invention comprises:
(1) anodal and negative pole all adopts metal oxide nanotubes-porous carbon composite material, conductive agent and binding agent to form.Its component and content are: metal oxide nanotubes 0.5mass%～20mass%, porous carbon 65mass%～95mass%, conductive agent 0.1mass%～30mass%, binding agent 3.0mass%～10mass%;
(2) electrolyte adopts organic electrolyte, and wherein organic solvent is two or more in ethylene carbonate, propene carbonate, methyl ethyl carbonate fat, sulfolane, methyl-sulfoxide, dimethyl carbonate, carbonic acid diethyl ester, dimethylacetylamide, nitroethylene etc. and the derivative thereof; Electrolyte is lithium hexafluoro phosphate, LiBF4, tetrafluoro boric acid tetraethyl amine, tetramethyl tetrafluoro boric acid amine, tetrapropyl tetrafluoro boric acid amine, tetrabutyl tetrafluoro boric acid amine, trimethyl ethyl tetrafluoro boric acid amine, diethyl-dimethyl tetrafluoro boric acid amine, N-ethyl-N-crassitude tetrafluoro boric acid amine; In ammonium hexafluorophosphate class such as tetraethyl hexafluorophosphoric acid amine, tetramethyl hexafluorophosphoric acid amine, tetrapropyl hexafluorophosphoric acid amine, tetrabutyl hexafluorophosphoric acid amine, trimethyl ethyl hexafluorophosphoric acid amine, triethyl group methyl hexafluorophosphoric acid amine, the diethyl-dimethyl hexafluorophosphoric acid amine etc. one or more; Concentration of electrolyte is 0.5mol/L～3.0mol/L;
(3) the porous insulation barrier film is the penetrating film of a kind of ion, is mainly a kind of in polypropylene porous membrane, polyethylene porous membrane, glass fibre porous membrane and the polytetrafluoroethylporous porous film etc., and thickness is 8 μ m～200 μ m;
(4) the collector body film is a kind of in aluminium film, Copper Foil, nickel foam film, stainless steel film, the punching nickel film etc.
Metal oxide nanotubes in the above-mentioned negative or positive electrode is Al
2O
3, ZrO
2, TiO
2In the composition of one or more arbitrary proportions, its pore diameter range is 1nm～50nm; Conductive agent is the composition of one or more arbitrary proportions in acetylene black, graphite, carbon nano-fiber, the nano metal, and wherein nano metal is the composition of one or more arbitrary proportions among Al, Ni, Co, Tl, Cu, the Fe.
Porous carbon is the composition of one or more arbitrary proportions in the porous carbon materials such as active carbon, activated carbon fiber and carbon aerogels described in the above-mentioned negative or positive electrode, and its density is 0.5g/cm
3～1.6g/cm
3, further preferable range is 0.7g/cm
3～1.2g/cm
3Specific area is 100m
2/ g～4000m
2/ g, the specific area of micro content＜5%; The molal quantity of the active group on surface and the ratio of its carbon molal quantity are 0.1%～2.5%;
Above-mentioned binding agent is the group and the thing of polytetrafluoroethylene or poly-inclined to one side tetrafluoroethene and N-methyl pyrrolidone, and its portfolio ratio is (1～15): 100.
The manufacture method of ultracapacitor of the present invention comprises following processing step:
(1) according to mass ratio (65～95): (0.5～20): (0.1～30): (3.0～10) are weighing porous carbon, metal oxide nanotubes, conductive agent and binding agent respectively, and place the vacuum ball grinder that fills agate ball, material ball ratio is 1: (1～3), mixing of planetary ball mill, rotating speed is 150rpm～500rpm, 1 hour～72 hours ball milling time, be prepared into uniform and stable electrode slurry;
(2) with made slurry on the flow casting molding machine, be uniformly coated on the collector body film, then after isostatic cool pressing pressurization, make the electrode slice of required specification through vacuumize, section, wherein hydrostatic pressure is 100MPa～250MPa;
(3) made electrode slice and barrier film being placed concentration is the electrolyte of 0.5mol/L～3mol/L, under the vacuum condition, soaks 2 hours～24 hours;
(4) will contain the electrode slice and the barrier film of electrolyte again, after the repressed encapsulation, form the target ultracapacitor.
Ultracapacitor employing metal oxide nanotubes composite carbon sill is an electrode among the present invention, and adopting the penetrating film of ion of insulating properties is barrier film, and adopting organic electrolyte simultaneously is Working electrolyte.Ultracapacitor has higher operating voltage so on the one hand, on the other hand the three-dimensional network skeleton structure that in the matrix of porous carbon materials, constitutes of metal oxide nanotubes formed more in micropore diameter and large aperture, help the infiltration of electrolyte, improved the effective ratio area of active carbon and nano metal and nano active carbon fiber itself, form the little electric capacity of more electric double layer, thereby improve the capacity density of composite electrode, thus metal oxide composite carbon sill electrode select energy density and the power density that helps improving ultracapacitor for use.
The advantage that the present invention compared with prior art has is: prior art mostly is the carbon-based materials such as active carbon, activated carbon fiber and carbon nano-tube that utilize high-specific surface area and is electrode, pore-size distribution is difficult to control, effective drainage porosity is lower, and to adopt alkaline aqueous solutions such as potassium hydroxide be Working electrolyte more, therefore (0.5V～1.2V) and cost finally cause the energy density of ultracapacitor and power density to be limited in a very limited level than problems such as height that the effective ratio area that can form electric capacity is lower, the monomer operating voltage is low.It is electrode that ultracapacitor of the present invention adopts metal oxide nanotubes composite carbon sill, utilize low-cost active carbon with high specific surface area, carbon aerogels, porous carbon materials such as nano active carbon fiber, its high-specific surface area and the low-cost advantage that is easy to get have been kept, introduce metal oxide nanotubes simultaneously, on the basis of the effective ratio area that improves the carbon-based electrode material, utilize the nanometer cooperative effect on nano carbon-base material surface and metal oxide nanotubes surface, the passage that transports of electrolyte ion is provided by metal oxide nanotubes, increased the sharp frequency of active material surface area greatly, adopt the organic electrolyte that has than high working voltage simultaneously, thereby can increase substantially the energy density and the power density of ultracapacitor; The present invention makes the simple easy operating of method technology of ultracapacitor, and with low cost being beneficial to realized the wide range of commercial application.
Description of drawings
Accompanying drawing is a ultracapacitor monomer structure schematic diagram.
Among the figure: 1 is positive terminal; 2 is negative terminal; 3 is positive plate; 4 is negative plate; 5 is the porous insulation barrier film; 6 is electrolyte; 7 is collector body; 8 is package casing.
Embodiment
Further specify the present invention below in conjunction with the drawings and specific embodiments.
As shown in drawings, ultracapacitor of the present invention comprises: positive pole 3, negative pole 4, electrolyte 6, barrier film 5, collector body film 7 and package casing 8 are formed.That electrolyte 6 is adsorbed on is anodal 3, in the hole of negative pole 4 and barrier film 5 and package casing 8 inside not by anodal 3 and the hole that occupies of negative pole 4 and barrier film 5 in; Positive pole 3 and negative pole 4 lay respectively at the surface of collector body film 7; Separated by porous insulation barrier film 5 between active material one side of anodal 3 negative poles 4; Draw positive terminal 1 and negative terminal 2 from positive pole 3 and negative pole 4 one sides respectively; Again by the shell encapsulation 8 ultracapacitor monomers that constitute.
Ultracapacitor manufacture method embodiment of the present invention is as follows:
Embodiment 1
At first according to mass ratio 65: 20: 12: 3 weighing porous carbons (mass ratio is 1: 1 the active carbon and the composition of carbon fiber), TiO respectively
2(pore diameter range is 1nm～50nm), conductive agent (mass ratio be 1: 1 nano metal Ni and the composition of Co) and binding agent (mass ratio is 15: 100 the polytetrafluoroethylene and the composition of N-methyl pyrrolidone) to nanotube, and place the vacuum ball grinder that fills agate ball, material ball ratio is 1: 3, mixing of planetary ball mill, rotating speed is 150rpm, 72 hours ball milling time, be prepared into uniform and stable electrode slurry; Again with made slurry on the flow casting molding machine, be uniformly coated on collector body aluminium film surface, then after isostatic cool pressing pressurization, make the electrode slice of required specification through vacuumize, section, wherein hydrostatic pressure is 100MPa; Again made electrode slice and barrier film being placed concentration is in the electrolyte (electrolyte is a lithium hexafluoro phosphate, and organic solvent is that mass ratio is 1: 1 the ethylene carbonate and the composition of propene carbonate) of 0.5mol/L, under the vacuum condition, soaks 2 hours; The electrode slice and the polypropylene porous septum that will contain electrolyte then after the repressed encapsulation, are formed the target ultracapacitor.
Embodiment 2
At first according to mass ratio 95: 0.5: 0.1: 3.4 weighing porous carbons (mass ratio is 1: 1 the active carbon and the composition of carbon fiber), ZrO respectively
2(pore diameter range is 1nm～20nm), conductive agent (mass ratio is 1: 1 acetylene black and the composition of nano metal Ni) and binding agent (mass ratio is 15: 100 the polytetrafluoroethylene and the composition of N-methyl pyrrolidone) to nanotube, and place the vacuum ball grinder that fills agate ball, material ball ratio is 1: 3, mixing of planetary ball mill, rotating speed is 200rpm, 1 hour ball milling time, be prepared into uniform and stable electrode slurry; Again with made slurry on the flow casting molding machine, be uniformly coated on collector body aluminium film surface, then after isostatic cool pressing pressurization, make the electrode slice of required specification through vacuumize, section, wherein hydrostatic pressure is 150MPa; Again made electrode slice and barrier film being placed concentration is in the electrolyte (electrolyte is a lithium hexafluoro phosphate, and organic solvent is that mass ratio is 1: 1 the ethylene carbonate and the composition of propene carbonate) of 1.5mol/L, under the vacuum condition, soaks 24 hours; The electrode slice and the polypropylene porous septum that will contain electrolyte then after the repressed encapsulation, are formed the target ultracapacitor.
Embodiment 3
At first according to mass ratio 85: 5: 5: 5 weighing porous carbons (mass ratio is 1: 1 the active carbon and the composition of carbon fiber), TiO respectively
2(pore diameter range is 1nm～50nm), conductive agent (mass ratio is 1: 1 acetylene black and the composition of nano metal Al) and binding agent (mass ratio is 10: 100 the polytetrafluoroethylene and the composition of N-methyl pyrrolidone) to nanotube, and place the vacuum ball grinder that fills agate ball, material ball ratio is 1: 2, mixing of planetary ball mill, rotating speed is 200rpm, 24 hours ball milling time, be prepared into uniform and stable electrode slurry; Again with made slurry on the flow casting molding machine, be uniformly coated on collector body nickel foam film surface, then after isostatic cool pressing pressurization, make the electrode slice of required specification through vacuumize, section, wherein hydrostatic pressure is 100MPa; Again made electrode slice and barrier film being placed concentration is in the electrolyte (electrolyte is a lithium hexafluoro phosphate, and organic solvent is that mass ratio is 1: 1 the ethylene carbonate and the composition of propene carbonate) of 1.0mol/L, under the vacuum condition, soaks 12 hours; The electrode slice and the polypropylene porous septum that will contain electrolyte then after the repressed encapsulation, are formed the target ultracapacitor.
Embodiment 4
At first according to mass ratio 80: 10: 5: 5 weighing porous carbons (mass ratio is 1: 1 the active carbon and the composition of carbon fiber), TiO respectively
2(pore diameter range is 1nm～50nm), conductive agent (mass ratio is 1: 1 acetylene black and the composition of nano metal Ni) and binding agent (mass ratio is 10: 100 the polytetrafluoroethylene and the composition of N-methyl pyrrolidone) to nanotube, and place the vacuum ball grinder that fills agate ball, material ball ratio is 1: 2, mixing of planetary ball mill, rotating speed is 200rpm, 48 hours ball milling time, be prepared into uniform and stable electrode slurry; Again with made slurry on the flow casting molding machine, be uniformly coated on collector body aluminium film surface, then after isostatic cool pressing pressurization, make the electrode slice of required specification through vacuumize, section, wherein hydrostatic pressure is 100MPa; Again made electrode slice and barrier film being placed concentration is in the electrolyte (electrolyte is a lithium hexafluoro phosphate, and organic solvent is that mass ratio is 1: 1 the ethylene carbonate and the composition of propene carbonate) of 1.0mol/L, under the vacuum condition, soaks 12 hours; The electrode slice and the polypropylene porous septum that will contain electrolyte then after the repressed encapsulation, are formed the target ultracapacitor.
Embodiment 5
At first according to mass ratio 75: 14.9: 0.1: 10 weighing porous carbons (mass ratio is 1: 1 the active carbon and the composition of carbon fiber), AlO respectively
2(pore diameter range is 1nm～50nm), conductive agent (mass ratio is 1: 0.01 acetylene black and the composition of nano metal Al) and binding agent (mass ratio is 8: 100 the polytetrafluoroethylene and the group and the thing of N-methyl pyrrolidone) to nanotube, and place the vacuum ball grinder that fills agate ball, material ball ratio is 1: 1, mixing of planetary ball mill, rotating speed is 200rpm, 60 hours ball milling time, be prepared into uniform and stable electrode slurry; Again with made slurry on the flow casting molding machine, be uniformly coated on the collector body copper foil surface, then after isostatic cool pressing pressurization, make the electrode slice of required specification through vacuumize, section, wherein hydrostatic pressure is 200MPa; Made electrode slice and barrier film being placed concentration is that (electrolyte is a lithium hexafluoro phosphate for the electrolyte of 1.0mol/L again, organic solvent is that mass ratio is the composition of 1: 1: 1 ethylene carbonate, propene carbonate and methyl ethyl carbonate fat) in, under the vacuum condition, soaked 12 hours; The electrode slice and the polypropylene porous septum that will contain electrolyte then after the repressed encapsulation, are formed the target ultracapacitor.
Embodiment 6
At first according to mass ratio 75: 14.9: 0.1: 10 respectively weighing porous carbons (mass ratio is 1: 1 the active carbon and the composition of carbon fiber), (mass ratio is 1: 1: 1 TiO to metal oxide nanotubes
2Nanotube, ZrO
2Nanotube and Al
2O
3The composition of nanotube, pore diameter range is 1nm～50nm), conductive agent (mass ratio is 0.1: 1 acetylene black and the composition of nano metal Ni) and binding agent (mass ratio is 10: 100 the polytetrafluoroethylene and the composition of N-methyl pyrrolidone), and place the vacuum ball grinder that fills agate ball, material ball ratio is 1: 1, mixing of planetary ball mill, rotating speed is 500rpm, 1 hour ball milling time, is prepared into uniform and stable electrode slurry; Again with made slurry on the flow casting molding machine, be uniformly coated on collector body punching nickel film surface, then after isostatic cool pressing pressurization, make the electrode slice of required specification through vacuumize, section, wherein hydrostatic pressure is 200MPa; Made electrode slice and barrier film being placed concentration is that (electrolyte is a lithium hexafluoro phosphate for the electrolyte of 3.0mol/L again, organic solvent is that mass ratio is the composition of 1: 1: 1 ethylene carbonate, propene carbonate and methyl ethyl carbonate fat) in, under the vacuum condition, soaked 12 hours; The electrode slice and the polyethylene porous septum that will contain electrolyte then after the repressed encapsulation, are formed the target ultracapacitor.
Embodiment 7
At first according to mass ratio 65: 0.5: 30: 9.5 respectively weighing porous carbons (mass ratio is 1: 1 the active carbon and the composition of carbon fiber), (mass ratio is 1: 1 ZrO to metal oxide nanotubes
2Nanotube and Al
2O
3The composition of nanotube, pore diameter range is 1nm～50nm), conductive agent (mass ratio is 1: 1 acetylene black and the composition of nano metal Ni) and binding agent (mass ratio is 10: 100 the polytetrafluoroethylene and the composition of N-methyl pyrrolidone), and place the vacuum ball grinder that fills agate ball, material ball ratio is 1: 2, mixing of planetary ball mill, rotating speed is 260rpm, 6 hours ball milling time, is prepared into uniform and stable electrode slurry; Again with made slurry on the flow casting molding machine, be uniformly coated on collector body aluminium film surface, then after isostatic cool pressing pressurization, make the electrode slice of required specification through vacuumize, section, wherein hydrostatic pressure is 150MPa; Made electrode slice and barrier film being placed concentration is that (electrolyte is a lithium hexafluoro phosphate for the electrolyte of 1.0mol/L again, organic solvent is that mass ratio is the composition of 1: 1: 1 ethylene carbonate, propene carbonate and methyl ethyl carbonate fat) in, under the vacuum condition, soaked 24 hours; The electrode slice and the polypropylene porous septum that will contain electrolyte then after the repressed encapsulation, are formed the target ultracapacitor.
Embodiment 8
At first according to mass ratio 65: 0.5: 30: 9.5 respectively weighing porous carbons (mass ratio is 1: 1 the active carbon and the composition of carbon fiber), (mass ratio is 1: 1: 1 TiO to metal oxide nanotubes
2Nanotube, ZrO
2Nanotube and Al
2O
3The composition of nanotube, pore diameter range is 1nm～50nm), conductive agent (mass ratio is 0.3: 1 the acetylene black and the composition of graphite) and binding agent (mass ratio is 10: 100 the polytetrafluoroethylene and the composition of N-methyl pyrrolidone), and place the vacuum ball grinder that fills agate ball, material ball ratio is 1: 2, mixing of planetary ball mill, rotating speed is 500rpm, 2 hours ball milling time, is prepared into uniform and stable electrode slurry; Again with made slurry on the flow casting molding machine, be uniformly coated on collector body nickel foam film surface, then after isostatic cool pressing pressurization, make the electrode slice of required specification through vacuumize, section, wherein hydrostatic pressure is 250MPa; Made electrode slice and barrier film being placed concentration is that (electrolyte is a lithium hexafluoro phosphate for the electrolyte of 3.0mol/L again, organic solvent is that mass ratio is the composition of 1: 1: 1 ethylene carbonate, propene carbonate and methyl ethyl carbonate fat) in, under the vacuum condition, soaked 24 hours; The electrode slice and the polyethylene porous septum that will contain electrolyte then after the repressed encapsulation, are formed the target ultracapacitor.
Embodiment 9
At first according to mass ratio 75: 10: 10: 5 respectively the weighing activated carbon, (mass ratio is 1: 1: 1 TiO to metal oxide nanotubes
2Nanotube, ZrO
2Nanotube and Al
2O
3The composition of nanotube, pore diameter range is 1nm～50nm), conductive agent (mass ratio is 0.3: 1 the acetylene black and the composition of graphite) and binding agent (mass ratio is 10: 100 the polytetrafluoroethylene and the group and the thing of N-methyl pyrrolidone), and place the vacuum ball grinder that fills agate ball, material ball ratio is 1: 2, mixing of planetary ball mill, rotating speed is 230rpm, 40 hours ball milling time, is prepared into uniform and stable electrode slurry; Again with made slurry on the flow casting molding machine, be uniformly coated on collector body punching nickel film surface, then after isostatic cool pressing pressurization, make the electrode slice of required specification through vacuumize, section, wherein hydrostatic pressure is 160MPa; Made electrode slice and barrier film being placed concentration is that (electrolyte is a hexafluorophosphoric acid amine for the electrolyte of 1.0mol/L again, organic solvent is that mass ratio is the composition of 1: 1: 1 ethylene carbonate, propene carbonate and methyl ethyl carbonate fat) in, under the vacuum condition, soaked 24 hours; The electrode slice and the glass fibre porous septum that will contain electrolyte then after the repressed encapsulation, are formed the target ultracapacitor.
Embodiment 10
At first according to mass ratio 80: 10: 7: 3 respectively the weighing activated carbon, (mass ratio is 1: 1: 1 TiO to metal oxide nanotubes
2Nanotube, ZrO
2Nanotube and Al
2O
3The composition of nanotube, pore diameter range is 1nm～50nm), conductive agent (mass ratio is 0.3: 1 the acetylene black and the composition of graphite) and binding agent (mass ratio is 10: 100 the polytetrafluoroethylene and the composition of N-methyl pyrrolidone), and place the vacuum ball grinder that fills agate ball, material ball ratio is 1: 2, mixing of planetary ball mill, rotating speed is 240rpm, 40 hours ball milling time, is prepared into uniform and stable electrode slurry; Again with made slurry on the flow casting molding machine, be uniformly coated on collector body copper film surface, then after isostatic cool pressing pressurization, make the electrode slice of required specification through vacuumize, section, wherein hydrostatic pressure is 160MPa; Made electrode slice and barrier film being placed concentration is that (electrolyte is that mass ratio is 1: 1 tetrafluoro boric acid amine and a hexafluorophosphoric acid amine for the electrolyte of 1.0mol/L again, organic solvent is that mass ratio is the composition of 1: 1: 1 ethylene carbonate, propene carbonate and methyl ethyl carbonate fat) in, under the vacuum condition, soaked 24 hours; The electrode slice and the glass fibre porous septum that will contain electrolyte then after the repressed encapsulation, are formed the target ultracapacitor.
Embodiment 11
At first according to mass ratio 80: 5: 5: 10 respectively the weighing activated carbon fibers, (mass ratio is 1: 1 TiO to metal oxide nanotubes
2Nanotube and ZrO
2The composition of nanotube, pore diameter range is 1nm～50nm), conductive agent (mass ratio is the composition of 0.3: 1: 1 acetylene black, graphite and nano metal Ni) and binding agent (mass ratio is 5: 100 the poly-inclined to one side tetrafluoroethene and the composition of N-methyl pyrrolidone), and place the vacuum ball grinder that fills agate ball, material ball ratio is 1: 2, mixing of planetary ball mill, rotating speed is 220rpm, 30 hours ball milling time, is prepared into uniform and stable electrode slurry; Again with made slurry on the flow casting molding machine, be uniformly coated on collector body aluminium film surface, then after isostatic cool pressing pressurization, make the electrode slice of required specification through vacuumize, section, wherein hydrostatic pressure is 160MPa; Made electrode slice and barrier film being placed concentration is that (electrolyte is that mass ratio is 1: 1 tetrafluoro boric acid amine and a hexafluorophosphoric acid amine for the electrolyte of 1.0mol/L again, organic solvent is that mass ratio is the composition of 1: 1: 1 ethylene carbonate, propene carbonate and methyl ethyl carbonate fat) in, under the vacuum condition, soaked 24 hours; The electrode slice and the glass fibre porous septum that will contain electrolyte then after the repressed encapsulation, are formed the target ultracapacitor.
Embodiment 12
At first according to mass ratio 75: 20: 2: 3 respectively the weighing activated carbon fibers, (mass ratio is 1: 1 TiO to metal oxide nanotubes
2Nanotube and ZrO
2The composition of nanotube, pore diameter range is 1nm～50nm), conductive agent (mass ratio is the composition of 1: 1: 1 acetylene black, graphite and nano metal Ni) and binding agent (mass ratio is 5: 100 the poly-inclined to one side tetrafluoroethene and the composition of N-methyl pyrrolidone), and place the vacuum ball grinder that fills agate ball, material ball ratio is 1: 2, mixing of planetary ball mill, rotating speed is 220rpm, 30 hours ball milling time, is prepared into uniform and stable electrode slurry; Again with made slurry on the flow casting molding machine, be uniformly coated on collector body nickel foam film surface, then after isostatic cool pressing pressurization, make the electrode slice of required specification through vacuumize, section, wherein hydrostatic pressure is 160MPa; Made electrode slice and barrier film being placed concentration is that (electrolyte is that mass ratio is 1: 1 tetrafluoro boric acid amine and a hexafluorophosphoric acid amine for the electrolyte of 1.0mol/L again, organic solvent is that mass ratio is 1: 1 the ethylene carbonate and the composition of propene carbonate) in, under the vacuum condition, soaked 24 hours; The electrode slice and the glass fibre porous septum that will contain electrolyte then after the repressed encapsulation, are formed the target ultracapacitor.
Embodiment 13
At first according to mass ratio 85: 8: 2: 5 respectively the weighing activated carbon fibers, (mass ratio is 1: 0.1: 0.5 Al to metal oxide nanotubes
2O
3Nanotube, TiO
2Nanotube and ZrO
2The composition of nanotube, the composition of 0.6 acetylene black, graphite, nano metal Ni and nano metal Cu) and binding agent (mass ratio is 5: 100 the poly-inclined to one side tetrafluoroethene and the composition of N-methyl pyrrolidone) pore diameter range is that (mass ratio is 1: 1: 1: for 1nm～50nm), conductive agent, and place the vacuum ball grinder that fills agate ball, material ball ratio is 1: 2, mixing of planetary ball mill, rotating speed is 220rpm, 30 hours ball milling time, be prepared into uniform and stable electrode slurry; Again with made slurry on the flow casting molding machine, be uniformly coated on collector body aluminium film surface, then after isostatic cool pressing pressurization, make the electrode slice of required specification through vacuumize, section, wherein hydrostatic pressure is 160MPa; Made electrode slice and barrier film being placed concentration is that (electrolyte is that mass ratio is 1: 1 tetrafluoro boric acid amine and a hexafluorophosphoric acid amine for the electrolyte of 1.0mol/L again, organic solvent is that mass ratio is 1: 1 the ethylene carbonate and the composition of propene carbonate) in, under the vacuum condition, soaked 24 hours; The electrode slice and the polytetrafluoroethylstephanoporate stephanoporate barrier film that will contain electrolyte then after the repressed encapsulation, are formed the target ultracapacitor.
Embodiment 14
At first according to mass ratio 84: 3: 8: 5 respectively the weighing activated carbon fibers, (mass ratio is 1: 0.1: 0.5 Al to metal oxide nanotubes
2O
3Nanotube, TiO
2Nanotube and ZrO
2The composition of nanotube, the composition of 0.6 acetylene black, graphite, nano metal Ni and nano metal Cu) and binding agent (mass ratio is 5: 100 the poly-inclined to one side tetrafluoroethene and the composition of N-methyl pyrrolidone) pore diameter range is that (mass ratio is 1: 1: 1: for 1nm～50nm), conductive agent, and place the vacuum ball grinder that fills agate ball, material ball ratio is 1: 2, mixing of planetary ball mill, rotating speed is 270rpm, 24 hours ball milling time, be prepared into uniform and stable electrode slurry; Again with made slurry on the flow casting molding machine, be uniformly coated on collector body aluminium film surface, then after isostatic cool pressing pressurization, make the electrode slice of required specification through vacuumize, section, wherein hydrostatic pressure is 180MPa; Made electrode slice and barrier film being placed concentration is that (electrolyte is that mass ratio is 1: 1 the diethyl-dimethyl tetrafluoro boric acid amine and the composition of tetrabutyl hexafluorophosphoric acid amine for the electrolyte of 1.0mol/L again, organic solvent is that mass ratio is the composition of 1: 1 ethylene carbonate and propene carbonate) in, under the vacuum condition, soaked 24 hours; The electrode slice and the polytetrafluoroethylstephanoporate stephanoporate barrier film that will contain electrolyte then after the repressed encapsulation, are formed the target ultracapacitor.
Embodiment 15
At first according to mass ratio 75: 10: 10: 5 respectively the weighing activated carbon, (mass ratio is 1: 1: 1 TiO to metal oxide nanotubes
2Nanotube, ZrO
2Nanotube and Al
2O
3The composition of nanotube, pore diameter range is 1nm～50nm), conductive agent (mass ratio is 0.3: 1 the acetylene black and the composition of graphite) and binding agent (mass ratio is 10: 100 the polytetrafluoroethylene and the composition of N-methyl pyrrolidone), and place the vacuum ball grinder that fills agate ball, material ball ratio is 1: 2, mixing of planetary ball mill, rotating speed is 230rpm, 40 hours ball milling time, is prepared into uniform and stable electrode slurry; Again with made slurry on the flow casting molding machine, be uniformly coated on the collector body copper foil surface, then after isostatic cool pressing pressurization, make the electrode slice of required specification through vacuumize, section, wherein hydrostatic pressure is 160MPa; Made electrode slice and barrier film being placed concentration is that (electrolyte is that mass ratio is 1: 1: 1: the composition of 1: 1: 1 diethyl-dimethyl tetrafluoro boric acid amine, N-ethyl-N-crassitude tetrafluoro boric acid amine, tetraethyl hexafluorophosphoric acid amine, tetramethyl hexafluorophosphoric acid amine, tetrapropyl hexafluorophosphoric acid amine and tetrabutyl hexafluorophosphoric acid amine) for the electrolyte of 1.0mol/L again, organic solvent is that mass ratio is the composition of 1: 1: 1 ethylene carbonate, propene carbonate and methyl-sulfoxide) in, under the vacuum condition, soaked 24 hours; The electrode slice and the glass fibre porous septum that will contain electrolyte then after the repressed encapsulation, are formed the target ultracapacitor.
Embodiment 16
At first according to mass ratio 69: 20: 8: 3 respectively the weighing activated carbon, (mass ratio is 1: 0.5: 1 TiO to metal oxide nanotubes
2Nanotube, ZrO
2Nanotube and Al
2O
3The composition of nanotube, pore diameter range is 1nm～50nm), conductive agent (mass ratio be 2: 1: 1 nano metal Ni, Tl and the composition of Co) and binding agent (mass ratio is 10: 100 the polytetrafluoroethylene and the composition of N-methyl pyrrolidone), and place the vacuum ball grinder that fills agate ball, material ball ratio is 1: 1, mixing of planetary ball mill, rotating speed is 250rpm, 24 hours ball milling time, is prepared into uniform and stable electrode slurry; Again with made slurry on the flow casting molding machine, be uniformly coated on collector body stainless steel film surface, then after isostatic cool pressing pressurization, make the electrode slice of required specification through vacuumize, section, wherein hydrostatic pressure is 160MPa; Again made electrode slice and barrier film being placed concentration is the electrolyte (electrolyte is that mass ratio is 1: 1: 1 diethyl-dimethyl tetrafluoro boric acid amine, tetraethyl hexafluorophosphoric acid amine and a tetramethyl hexafluorophosphoric acid amine) of 1.0mol/L, organic solvent is that mass ratio is the composition of 1: 1: 1 ethylene carbonate, propene carbonate and methyl-sulfoxide) in, under the vacuum condition, soaked 24 hours; The electrode slice and the glass fibre porous septum that will contain electrolyte then after the repressed encapsulation, are formed the target ultracapacitor.
Embodiment 17
At first according to mass ratio 96.4: 0.5: 0.1: 3 porous carbon (mass ratio is the composition of 1: 1: 1 active carbon, carbon fiber and carbon aerogels), AlO
2(pore diameter range is 1nm～50nm), conductive agent (mass ratio is 1: 0.01 acetylene black and the composition of nano metal Al) and binding agent (mass ratio is 8: 100 the polytetrafluoroethylene and the composition of N-methyl pyrrolidone) to nanotube, and place the vacuum ball grinder that fills agate ball, material ball ratio is 1: 1, mixing of planetary ball mill, rotating speed is 200rpm, 10 hours ball milling time, be prepared into uniform and stable electrode slurry; Again with made slurry on the flow casting molding machine, be uniformly coated on collector body aluminium film surface, then after isostatic cool pressing pressurization, make the electrode slice of required specification through vacuumize, section, wherein hydrostatic pressure is 200MPa; Again made electrode slice and barrier film being placed concentration is the electrolyte (electrolyte is that mass ratio is 1: 1: 1 diethyl-dimethyl tetrafluoro boric acid amine, tetraethyl hexafluorophosphoric acid amine and a tetramethyl hexafluorophosphoric acid amine) of 1.0mol/L, organic solvent is that mass ratio is the composition of 1: 1: 1 ethylene carbonate, propene carbonate and methyl-sulfoxide) in, under the vacuum condition, soaked 12 hours; The electrode slice and the polypropylene porous septum that will contain electrolyte then after the repressed encapsulation, are formed the target ultracapacitor.
Embodiment 18
At first according to mass ratio 65: 20: 12: 3 weighing porous carbons (mass ratio is the composition of 0.1: 1: 1 active carbon, carbon fiber and carbon aerogels), TiO respectively
2(pore diameter range is 1nm～50nm), conductive agent (mass ratio is 1: 1 nano metal Ni and the composition of nano metal Al) and binding agent (mass ratio is 15: 100 the polytetrafluoroethylene and the composition of N-methyl pyrrolidone) to nanotube, and place the vacuum ball grinder that fills agate ball, material ball ratio is 1: 3, mixing of planetary ball mill, rotating speed is 150rpm, 72 hours ball milling time, be prepared into uniform and stable electrode slurry; Again with made slurry on the flow casting molding machine, be uniformly coated on collector body aluminium film surface, then after isostatic cool pressing pressurization, make the electrode slice of required specification through vacuumize, section, wherein hydrostatic pressure is 100MPa; Again made electrode slice and barrier film being placed concentration is the electrolyte (electrolyte is that mass ratio is 1: 0.5: 1 diethyl-dimethyl tetrafluoro boric acid amine, tetraethyl hexafluorophosphoric acid amine and a tetramethyl hexafluorophosphoric acid amine) of 0.5mol/L, organic solvent is that mass ratio is the composition of 0.3: 1: 1 ethylene carbonate, methyl ethyl carbonate fat and methyl-sulfoxide) in, under the vacuum condition, soaked 2 hours; The electrode slice and the polypropylene porous septum that will contain electrolyte then after the repressed encapsulation, are formed the target ultracapacitor.
Embodiment 19
At first according to mass ratio 80: 10: 5: 5 weighing carbon aerogels, TiO respectively
2(pore diameter range is 1nm～50nm), conductive agent (mass ratio is 1: 1 acetylene black and the composition of nano metal Al) and binding agent (mass ratio is 8: 100 the polytetrafluoroethylene and the group and the thing of N-methyl pyrrolidone) to nanotube, and place the vacuum ball grinder that fills agate ball, material ball ratio is 1: 2, mixing of planetary ball mill, rotating speed is 100rpm, 24 hours ball milling time, be prepared into uniform and stable electrode slurry; Again with made slurry on the flow casting molding machine, be uniformly coated on collector body Thin Stainless Steel surface, then after isostatic cool pressing pressurization, make the electrode slice of required specification through vacuumize, section, wherein hydrostatic pressure is 100MPa; Made electrode slice and barrier film being placed concentration is that (electrolyte is a tetrafluoro boric acid amine for the electrolyte of 1.0mol/L again, organic solvent is that mass ratio is the composition of 1: 1: 1 sulfolane, dimethylacetylamide and nitroethylene) in, under the vacuum condition, soaked 12 hours; The electrode slice and the polypropylene porous septum that will contain electrolyte then after the repressed encapsulation, are formed the target ultracapacitor.
Embodiment 20
At first according to mass ratio 75: 14.9: 0.1: 10 respectively weighing porous carbons (mass ratio is 1: 1 the active carbon and the composition of carbon fiber), (mass ratio is 1: 1: 1 TiO to metal oxide nanotubes
2Nanotube, ZrO
2Nanotube and Al
2O
3The composition of nanotube, pore diameter range is 1nm～50nm), conductive agent (mass ratio is 1: 1 acetylene black and the composition of nano metal Ni) and binding agent (mass ratio is 10: 100 the polytetrafluoroethylene and the group and the thing of N-methyl pyrrolidone), and place the vacuum ball grinder that fills agate ball, material ball ratio is 1: 2, mixing of planetary ball mill, rotating speed is 200rpm, 48 hours ball milling time, is prepared into uniform and stable electrode slurry; Again with made slurry on the flow casting molding machine, be uniformly coated on collector body aluminium film surface, then after isostatic cool pressing pressurization, make the electrode slice of required specification through vacuumize, section, wherein hydrostatic pressure is 250MPa; Again made electrode slice and barrier film being placed concentration is in the electrolyte (electrolyte is a tetrafluoro boric acid amine, and organic solvent is that mass ratio is 1: 1 the sulfolane and the composition of nitroethylene) of 1.0mol/L, under the vacuum condition, soaks 24 hours; The electrode slice and the polyethylene porous septum that will contain electrolyte then after the repressed encapsulation, are formed the target ultracapacitor.
Claims (5)
1, a kind of ultracapacitor, comprise: in the hole that anodal [3], negative pole [4], electrolyte [6], barrier film [5], collector body film [7] and package casing [8], electrolyte [6] are adsorbed in the hole of positive pole [3], negative pole [4] and barrier film [5] and package casing [8] inside is not occupied by positive pole [3] and negative pole [4] and barrier film [5]; Anodal [3] and negative pole [4] lay respectively at the surface of collector body film [7]; Separated by porous insulation barrier film [5] between active material one side of anodal [3] and negative pole [4]; Draw positive terminal [1] and negative terminal [2] from anodal [3] and negative pole [4] one sides respectively; Constitute the ultracapacitor monomer by shell encapsulation [8] again, it is characterized in that:
(1) anodal [3] and negative pole [4] all adopt metal oxide nanotubes-porous carbon composite material, conductive agent and binding agent to form; Its component and content are: metal oxide nanotubes 0.5mass%～20mass%, porous carbon 65mass%～95mass%, conductive agent 0.1mass%～30mass%, binding agent 3.0mass%～10mass%;
(2) electrolyte [6] adopts organic electrolyte, and wherein electrolyte is lithium hexafluoro phosphate, LiBF4, tetrafluoro boric acid tetraethyl amine, tetramethyl tetrafluoro boric acid amine, tetrapropyl tetrafluoro boric acid amine, tetrabutyl tetrafluoro boric acid amine, trimethyl ethyl tetrafluoro boric acid amine, diethyl-dimethyl tetrafluoro boric acid amine, N-ethyl-N-crassitude tetrafluoro boric acid amine; The composition of one or more arbitrary proportions in ammonium hexafluorophosphate class such as tetraethyl hexafluorophosphoric acid amine, tetramethyl hexafluorophosphoric acid amine, tetrapropyl hexafluorophosphoric acid amine, tetrabutyl hexafluorophosphoric acid amine, trimethyl ethyl hexafluorophosphoric acid amine, triethyl group methyl hexafluorophosphoric acid amine, the diethyl-dimethyl hexafluorophosphoric acid amine etc.; Organic solvent is the composition of two or more arbitrary proportion in ethylene carbonate, propene carbonate, methyl ethyl carbonate fat, sulfolane, methyl-sulfoxide, dimethyl carbonate, carbonic acid diethyl ester, dimethylacetylamide, nitroethylene etc. and the derivative thereof; Concentration of electrolyte is 0.5mol/L～3.0mol/L;
(3) barrier film [5] is the porous insulation barrier film, is mainly a kind of in polypropylene porous membrane, polyethylene porous membrane, glass fibre porous membrane and the polytetrafluoroethylporous porous film etc., and thickness is 8 μ m～200 μ m;
(4) the collector body film is a kind of in aluminium film, Copper Foil, nickel foam film, stainless steel film, the punching nickel film etc.
2, ultracapacitor according to claim 1 is characterized in that: the metal oxide nanotubes in described positive pole [3] or the negative pole [4] is Al
2O
3, ZrO
2, TiO
2In the composition of one or more arbitrary proportions, its pore diameter range is 1nm～50nm; Conductive agent is the composition of one or more arbitrary proportions in acetylene black, graphite, carbon nano-fiber, the nano metal fiber, and wherein nano metal is the composition of one or more arbitrary proportions among Al, Ni, Co, Tl, Cu, the Fe.
3, ultracapacitor according to claim 1 and 2, it is characterized in that: porous carbon is the composition of one or more arbitrary proportions in the porous carbon materials such as active carbon, activated carbon fiber and carbon aerogels described in described positive pole [3] or the negative pole [4], and its density is 0.5g/cm
3～1.6g/cm
3, further preferable range is 0.7g/cm
3～1.2g/cm
3Specific area is 100m
2/ g～4000m
2/ g, the specific area of micro content＜5%; The molal quantity of the active group on surface and the ratio of its carbon molal quantity are 0.1%～2.5%.
4, according to any one described ultracapacitor of claim 1 to 3, it is characterized in that: described binding agent is the composition of polytetrafluoroethylene or poly-inclined to one side tetrafluoroethene and N-methyl pyrrolidone, and its portfolio ratio is (1～15): 100.
5, the manufacture method of the described ultracapacitor of claim 1 is characterized in that described method comprises following processing step:
(1) according to mass ratio (65～95): (0.5～20): (0.1～30): (3.0～10) are weighing porous carbon, metal oxide nanotubes, conductive agent and binding agent respectively, and place the vacuum ball grinder that fills agate ball, material ball ratio is 1: (1～3), mixing of planetary ball mill, rotating speed is 150rpm～500rpm, 1 hour～72 hours ball milling time, be prepared into uniform and stable electrode slurry;
(2) with made slurry on the flow casting molding machine, be uniformly coated on the collector body film, then after isostatic cool pressing pressurization, make the electrode slice of required specification through vacuumize, section, wherein hydrostatic pressure is 100MPa～250MPa;
(3) made electrode slice and barrier film being placed concentration is the electrolyte of 0.5mol/L～3mol/L, under the vacuum condition, soaks 2 hours～24 hours;
(4) will contain the electrode slice and the barrier film of electrolyte again, after repressed, the shell encapsulation, form the target ultracapacitor.
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