CN102103935A - Super capacitor - Google Patents
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- CN102103935A CN102103935A CN 200910189146 CN200910189146A CN102103935A CN 102103935 A CN102103935 A CN 102103935A CN 200910189146 CN200910189146 CN 200910189146 CN 200910189146 A CN200910189146 A CN 200910189146A CN 102103935 A CN102103935 A CN 102103935A
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Abstract
The present invention relates to a super capacitor comprising a first electrode, a second electrode, a diaphragm and electrolyte, wherein the second electrode and the first electrode are arranged at intervals; the diaphragm is arranged between the first electrode and the second electrode; the first electrode, the second electrode and the diaphragm are arranged in the electrolyte; and the first electrode has a carbon nanotube composite structure which is a self-supporting structure and comprises a carbon nanotube structure and nanometer level particles arranged on the surface of the carbon nanotube structure.
Description
Technical field
The present invention relates to a kind of ultracapacitor, relate in particular to a kind of ultracapacitor based on carbon nano-tube.
Background technology
Characteristics such as ultracapacitor (supercapacitor) belongs to double electric layer capacitor, has higher specific power and long cycle life, and operating temperature range is wide; Therefore, in fields such as mobile communication, information technology, electric automobile, Aero-Space and science and techniques of defence of crucial importance and wide application prospect is arranged all.
Existing ultracapacitor generally comprises two electrodes, barrier film and electrolyte, and these two electrodes and barrier film all are arranged in this electrolyte; These two electrodes include a collector body and are arranged on electrode material on this collector body.Wherein, the decisive factor that influences this capacity of super capacitor is an electrode material.Desirable electrode material should have that degree of crystallinity height, good conductivity, specific area are big, micropore is concentrated characteristics such as (require micropore greater than 2nm) within the specific limits.Existing electrode material for super capacitor mainly contains: activated carbon series and transition metal oxide series.The material conductivity of activated carbon series is relatively poor, and it can make the equivalent series resistance of capacitor bigger as electrode; And the specific area practical efficiency of this activated carbon series is no more than 30%, and electrolyte is difficult to fully contact with the electrode of this activated carbon series, therefore, adopts this activated carbon series material less as the capacity of the ultracapacitor of electrode.Though transition metal oxide has good effect as electrode material aspect the capacity that improves ultracapacitor, its cost is too high, can't promote the use of.
Carbon nano-tube (Carbon Nanotube, CNT) be the material with carbon element of the seamless tubular shaped graphite-structure of a kind of nanoscale, it is big that it has specific area, the degree of crystallinity height, good conductivity, the characteristics that the interior external diameter of carbon nano-tube can be controlled by synthesis technique, and its specific surface utilance can reach 100%, thereby can become a kind of desirable super capacitor material.Carbon nano-tube is seen in the earliest in the report of Chunming Niu etc. as the research of super capacitor material and (sees also High power electrochemical capacitorsbased on carbon nanotube electrodes, Apply Physics Letter, Chunming Niu et al., vol 70, p1480-1482 (1997)).After they made membrane electrode with pure multi-wall carbon nano-tube pipe powder, encapsulation made a ultracapacitor.Because this membrane electrode is to adopt carbon nanotube powder as feedstock production, and carbon nanotube powder is very easily reunited, this makes this membrane electrode can not give full play to the performance of carbon nano-tube, has influenced the performance of capacitor, has limited the raising of condenser capacity.
For this reason, people such as the Zhang Jianrong of Nanjing University are disclosed on March 16th, 2005, and the amorphous manganese dioxide of a kind of electrode material for super capacitor/multi-walled carbon nano-tubes compound is provided in the Chinese invention patent ublic specification of application of publication number for CN 1594212A.The diameter of the carbon nano-tube in this amorphous manganese dioxide/multi-walled carbon nano-tubes compound is the 20-40 nanometer, and length is 200 nanometers-5 micron, and amorphous manganese dioxide load is in carbon nano tube surface.This manganese dioxide/multi-walled carbon nano-tubes compound is as the electrode of ultracapacitor, though can be so that the ratio electric capacity of ultracapacitor is improved, but because this manganese dioxide/multi-walled carbon nano-tubes composite construction is Powdered, it needs metal current collector when being used as electrode.Yet therefore described metal current collector fair heavier make that the quality of described ultracapacitor is heavier, thereby make the total energy density of described ultracapacitor and overall power density reduce.
Summary of the invention
In view of this, necessaryly provide a kind of the have higher total energy density and the ultracapacitor of overall power density.
A kind of ultracapacitor, it comprises: one first electrode; One second electrode, this second electrode and the described first electrode gap setting; One barrier film, this barrier film are arranged between described first electrode and second electrode; An and electrolyte, described first electrode, second electrode and barrier film all are arranged in this electrolyte, wherein, described first electrode is a composite structure of carbon nano tube, this composite structure of carbon nano tube is a self supporting structure, and comprises a carbon nano tube structure and be arranged at the nano-scale particle on this carbon nano tube structure surface.
Compared with prior art, first electrode in the ultracapacitor provided by the invention is a composite structure of carbon nano tube, this composite structure of carbon nano tube has the characteristics of self-supporting, can be directly as the electrode of ultracapacitor, do not need metal current collector, therefore, make ultracapacitor have bigger total energy density and overall power density.
Description of drawings
Fig. 1 is the structural representation of the ultracapacitor that provides of first embodiment of the invention.
Fig. 2 is the electron microscope scanning photo of the composite structure of carbon nano tube that adopts in the first embodiment of the invention.
Fig. 3 is the vertical view of the composite structure of carbon nano tube that adopts in the first embodiment of the invention.
Fig. 4 is the transmission electron microscope photo of the single-root carbon nano-tube in the composite structure of carbon nano tube that adopts in the first embodiment of the invention.
Fig. 5 is the structural representation of the ultracapacitor that provides of second embodiment of the invention.
Fig. 6 is the vertical view of the composite structure of carbon nano tube that adopts in the second embodiment of the invention.
Fig. 7 is the single-root carbon nano-tube transmission electron microscope photo in the composite structure of carbon nano tube that adopts in the second embodiment of the invention.
Fig. 8 is under the sweep speed of 10 milli pressure/seconds, the voltage of the ultracapacitor that first embodiment of the invention, second embodiment and the 3rd embodiment provide-compare current curve diagram.
Fig. 9 is under the ratio electric current of 10 peace/grams, the charging and discharging curve figure of the ultracapacitor that first embodiment of the invention, second embodiment and the 3rd embodiment provide.
Figure 10 is under the ratio electric current of 30 peace/grams, the cycle-index of the ultracapacitor that first embodiment of the invention, second embodiment and the 3rd embodiment provide-specific capacitance curve chart.
The main element symbol description
Ultracapacitor 10,20
First electrode 101,201
Second electrode 102,202
Barrier film 105,205
Electrolyte 106,206
Shell 107,207
Composite structure of carbon nano tube 110,210
Carbon nano tube structure 112,212
Carbon nano-tube 1122,2122
Nanosize metal oxide particle 114,214
Embodiment
Below in conjunction with the accompanying drawings and the specific embodiments, ultracapacitor provided by the invention is described in further detail.
See also Fig. 1, first embodiment of the invention provides a kind of ultracapacitor 10, and this ultracapacitor is a flat structure, comprising: one first electrode, 101, one second electrode 102, one barrier films, 105, one electrolyte 106 and shells 107.Described electrolyte 106 is arranged in the described shell 107.Described first electrode 101, second electrode 102 and described barrier film 105 all are arranged in the described electrolyte 106.Described barrier film 105 is arranged between described first electrode 101 and second electrode 102, and is provided with at interval with described first electrode 101 and second electrode 102 respectively.
Described first electrode 101 is a composite structure of carbon nano tube, and this composite structure of carbon nano tube is stratiform or membrane structure, the nano-scale particle that it comprises a carbon nano tube structure and is arranged at this carbon nano tube structure surface.Particularly, the self supporting structure that described carbon nano tube structure is made up of some carbon nano-tube, described nano-scale particle is arranged at the surface of described some carbon nano-tube.Described composite structure of carbon nano tube comprises a plurality of micropores, these a plurality of micropores are by existing the gap to form between the some carbon nano-tube in the described carbon nano tube structure, the size of this micropore is not more than 10 microns, and these a plurality of micropores occupy most of volume of described carbon nano tube structure.The existence of described a plurality of micropores makes that the specific area of described composite structure of carbon nano tube is bigger, can promote the fast charging and discharging of this ultracapacitor 10, and then improves the specific capacitance of this ultracapacitor 10.
Described carbon nano tube structure is a self supporting structure, be carbon nano tube structure and do not need large-area carrier supported, and as long as the relative both sides power of providing support can be unsettled on the whole and keep oneself state, that is to say, in the time of on two supporters that this carbon nano tube structure is placed (or being fixed in) to keep at a certain distance away to be provided with, the carbon nano tube structure between two supporters can unsettled maintenance oneself state.Described self-supporting is mainly by existing the continuous Van der Waals force that passes through to join end to end and extend carbon nanotubes arranged and realize in the carbon nano tube structure.
Described carbon nano tube structure is a stratiform or membrane structure, and it comprises at least one carbon nano-tube film, at least one liner structure of carbon nano tube or its combination.When described carbon nano tube structure comprised a plurality of carbon nano-tube film, this carbon nano-tube film can be provided with or stacked setting by substantially parallel no gap coplane.When described carbon nano tube structure only comprised a liner structure of carbon nano tube, this liner structure of carbon nano tube can fold or be wound in a stratiform carbon nano tube structure.When described carbon nano tube structure comprised a plurality of liner structure of carbon nano tube, these a plurality of liner structure of carbon nano tube can be arranged in parallel, arranged in a crossed manner or be woven into a stratiform carbon nano tube structure.When described carbon nano tube structure comprises carbon nano-tube film and liner structure of carbon nano tube, liner structure of carbon nano tube can be arranged at least one surface of carbon nano-tube film.Because the carbon nano-tube in this carbon nano tube structure has good flexible, makes this carbon nano tube structure have good flexible, can bending fold become arbitrary shape and be difficult for breaking.
Described carbon nano-tube film is made up of some carbon nano-tube, and the bearing of trend of most of carbon nano-tube is basically parallel to the surface of this carbon nano-tube film in this carbon nano-tube film.Carbon nano-tube lack of alignment in the described carbon nano-tube film or arrangement in order.So-called lack of alignment is meant that the orientation of carbon nano-tube is random.The so-called arrangement in order is meant that the orientation of carbon nano-tube is regular.Particularly, when carbon nano tube structure comprised the carbon nano-tube of lack of alignment, carbon nano-tube was twined mutually or isotropism is arranged; When carbon nano tube structure comprised orderly carbon nanotubes arranged, carbon nano-tube was arranged of preferred orient along a direction or a plurality of direction.So-called " preferred orientation " is meant that the most of carbon nano-tube in the described carbon nano tube structure have bigger orientation probability on a direction or several direction; That is, the most of carbon nano-tube in this carbon nano tube structure axially extends along same direction or several direction substantially.Described carbon nano-tube film comprises carbon nano-tube membrane, carbon nano-tube laminate and carbon nano-tube waddingization film.
Carbon nano-tube in this carbon nano tube structure comprises one or more in Single Walled Carbon Nanotube, double-walled carbon nano-tube and the multi-walled carbon nano-tubes.The diameter of described Single Walled Carbon Nanotube is 0.5 nanometer～50 nanometers, and the diameter of double-walled carbon nano-tube is 1.0 nanometers～50 nanometers, and the diameter of multi-walled carbon nano-tubes is 1.5 nanometers～50 nanometers.The length of described carbon nano-tube is greater than 50 microns.Preferably, the length of this carbon nano-tube is preferably 200 microns～900 microns.
The self supporting structure that described carbon nano-tube membrane is made up of some carbon nano-tube.Described some carbon nano-tube are arranged of preferred orient along same direction.The whole bearing of trend of most of carbon nano-tube substantially in the same direction in this carbon nano-tube membrane.And the whole bearing of trend of described most of carbon nano-tube is basically parallel to the surface of carbon nano-tube membrane.Further, most carbon nano-tube are to join end to end by Van der Waals force in the described carbon nano-tube membrane.Particularly, each carbon nano-tube joins end to end by Van der Waals force with carbon nano-tube adjacent on bearing of trend in most of carbon nano-tube of extending substantially in the same direction in the described carbon nano-tube membrane.Certainly, have the carbon nano-tube of minority random alignment in the described carbon nano-tube membrane, these carbon nano-tube can not arranged the overall orientation of most of carbon nano-tube in the carbon nano-tube membrane and be constituted obviously influence.Described carbon nano-tube membrane does not need large-area carrier supported, and as long as the relative both sides power of providing support can be unsettled on the whole and keep self membranaceous state, when being about to this carbon nano-tube film and placing (or being fixed in) to keep at a certain distance away on two supporters that are provided with, the carbon nano-tube film between two supporters can the membranaceous state of unsettled maintenance self.
Particularly, most carbon nano-tube of extending substantially in the same direction in the described carbon nano-tube membrane, and nisi linearity, bending that can be suitable; Perhaps be not fully according to arranging on the bearing of trend, can be suitable depart from bearing of trend.Therefore, can not get rid of between the carbon nano-tube arranged side by side in most carbon nano-tube of extending substantially in the same direction of carbon nano-tube membrane and may have the part contact.
Particularly, described carbon nano-tube membrane comprise a plurality of continuously and the carbon nano-tube fragment that aligns.These a plurality of carbon nano-tube fragments join end to end by Van der Waals force.Each carbon nano-tube fragment comprises a plurality of carbon nano-tube that are parallel to each other, and these a plurality of carbon nano-tube that are parallel to each other are combined closely by Van der Waals force.This carbon nano-tube fragment has length, thickness, uniformity and shape arbitrarily.Carbon nano-tube in this carbon nano-tube membrane is arranged of preferred orient along same direction.
Form a plurality of micropores between the carbon nano-tube in this carbon nano-tube membrane, these a plurality of micropores occupy most of volume of this carbon nano-tube membrane, as, the volume of micropore can reach 70% of carbon nano-tube membrane volume.Described carbon nano-tube membrane can be by directly pulling acquisition from carbon nano pipe array.The thickness of single-layer carbon nano-tube membrane can be 0.5 nanometer-100 micron.Be appreciated that by a plurality of carbon nano-tube membranes are parallel and do not have that the gap coplane is laid or/and stacked laying, can prepare the carbon nano tube structure of different area and thickness.When carbon nano tube structure comprised the carbon nano-tube membrane of a plurality of stacked settings, the orientation of the carbon nano-tube in the adjacent carbon nano-tube membrane formed an angle α, 0 °≤α≤90 °.It is disclosed that structure of described carbon nano-tube membrane and preparation method thereof sees also on August 13rd, 2008, and publication number is the Chinese invention patent ublic specification of application of 101239712A.
Described carbon nano-tube laminate comprises equally distributed a plurality of carbon nano-tube, and these a plurality of carbon nano-tube are unordered, be arranged of preferred orient along same direction or different directions, axially the extending along same direction or different directions of this a plurality of carbon nano-tube.Carbon nano-tube in described carbon nano-tube laminate part mutually overlaps, and attracts each other by Van der Waals force, combines closely, thereby forms a self supporting structure.In addition, described carbon nano-tube laminate is thick more, helps it more and has the self-supporting function, during greater than 1 micron, just has good self-supporting function as the thickness of carbon nano-tube laminate.Described carbon nano-tube laminate can obtain by rolling a carbon nano pipe array.This carbon nano pipe array is formed on a substrate surface, the surface of the carbon nano-tube in the prepared carbon nano-tube laminate and the substrate of this carbon nano pipe array β that has angle, and wherein, β is more than or equal to 0 degree and smaller or equal to 15 degree (0 °≤β≤15 °).Preferably, the surface that axially is basically parallel to this carbon nano-tube laminate of the carbon nano-tube in the described carbon nano-tube laminate.According to the mode difference that rolls, the carbon nano-tube in this carbon nano-tube laminate has different spread patterns.The area and the thickness of described carbon nano-tube laminate are not limit, and can select according to actual needs.The area of described carbon nano-tube laminate and the size of carbon nano pipe array are basic identical.The height of described carbon nano-tube laminate thickness and carbon nano pipe array and the pressure that rolls are relevant, can be 1 micron～1 millimeter.It is disclosed that described carbon nano-tube laminate and preparation method thereof sees also on December 3rd, 2008, and publication number is the Chinese invention patent ublic specification of application of CN101314464A.
Described carbon nano-tube waddingization film comprises the carbon nano-tube of mutual winding, and this length of carbon nanotube can be greater than 10 centimetres.Attract each other, twine by Van der Waals force between the described carbon nano-tube, form network-like structure, to form the carbon nano-tube waddingization film of a self-supporting.In addition, described carbon nano-tube waddingization film is thick more, helps it more and has the self-supporting function, during greater than 1 micron, just has good self-supporting function as the thickness of carbon nano-tube waddingization film.Described carbon nano-tube waddingization film isotropism.Carbon nano-tube in the described carbon nano-tube waddingization film is evenly to distribute, and random arrangement forms a large amount of microcellular structures.The length, width and the thickness that are appreciated that described carbon nano-tube waddingization film are not limit, and can select according to actual needs.The thickness of described carbon nano-tube waddingization film is 1 micron～1 millimeter, is preferably 100 microns.It is disclosed that described carbon nano-tube waddingization film and preparation method thereof sees also on October 15th, 2008, and publication number is the Chinese invention patent ublic specification of application of CN101284662A.
Described liner structure of carbon nano tube comprises at least one carbon nano tube line, the carbon nano tube line that this carbon nano tube line can be a non-carbon nano tube line that reverses or reverses.
The described non-carbon nano tube line that reverses is made up of some carbon nano-tube, and the axially basic of these some carbon nano-tube extended along being parallel to this non-carbon nano tube line axial direction that reverses.The non-carbon nano tube line that reverses can obtain by the carbon nano-tube membrane is handled by organic solvent.Particularly, this carbon nano-tube membrane comprise a plurality of continuously and the carbon nano-tube fragment that aligns.These a plurality of carbon nano-tube fragments join end to end by Van der Waals force.Each carbon nano-tube fragment comprises a plurality of carbon nano-tube that are parallel to each other and combine closely by Van der Waals force.This carbon nano-tube fragment has length, thickness, uniformity and shape arbitrarily.This non-carbon nano-tube line length of reversing is not limit, and diameter is 0.5 nanometer-1 millimeter.Particularly, organic solvent can be soaked into the whole surface of described carbon nano-tube membrane, under the capillary effect that when volatile organic solvent volatilizees, produces, the a plurality of carbon nano-tube that are parallel to each other in the carbon nano-tube membrane are combined closely by Van der Waals force, thereby make the carbon nano-tube membrane be punctured into a non-carbon nano tube line that reverses.This organic solvent is a volatile organic solvent, as ethanol, methyl alcohol, acetone, dichloroethanes or chloroform, adopts ethanol in the present embodiment.Compare with the carbon nano-tube film of handling without organic solvent by the non-carbon nano tube line that reverses that organic solvent is handled, specific area reduces, and viscosity reduces.
The described carbon nano tube line that reverses is made up of some carbon nano-tube, the axial axial direction spiral extension around this carbon nano tube line that reverses of these some carbon nano-tube.This carbon nano tube line can adopt a mechanical force that acquisition is reversed at described carbon nano-tube membrane two ends in opposite direction.Further, can adopt a volatile organic solvent to handle the carbon nano tube line that this reverses.Under the capillary effect that produces when volatile organic solvent volatilizees, adjacent carbon nano-tube is combined closely by Van der Waals force in the carbon nano tube line that reverses after the processing, and the specific area of the carbon nano tube line that reverses is reduced, and density and intensity increase.
Described carbon nano tube line and preparation method thereof sees also bulletin on August 20th, 2008, and notification number is the Chinese invention patent specification of CN100411979C; And on June 17th, 2009 bulletin, notification number is the Chinese invention patent specification of CN100500556C.
When described liner structure of carbon nano tube comprised a plurality of carbon nano tube line, these a plurality of carbon nano tube lines be arranged in parallel and form a pencil structure or this a plurality of carbon nano tube lines reverse composition hank line structure mutually.In addition, have the gap between the adjacent carbons nanotube in the described carbon nano tube line, so this liner structure of carbon nano tube has a large amount of micropores, and the aperture of micropore is approximately less than 10 microns.
Described nano-scale particle is arranged at the surface of described some carbon nano-tube.Particularly, described nano-scale particle can the compartment of terrain be formed at the surface of each carbon nano-tube; The surface that also can be arranged at each carbon nano-tube continuously to be forming one deck, and is coated on the surface of carbon nano-tube.Described nano-scale particle can promote the fast charging and discharging of described ultracapacitor 10, and then improves the electric capacity of this ultracapacitor 10.Chemical reaction does not take place with described electrolyte 106 in described nano-scale particle; Preferably, this nano-scale particle is nanosize metal oxide particle, nano level metal particle or both compositions.Described nanosize metal oxide particle is manganese dioxide particle (MnO
2), cobaltosic oxide particle (Co
3O
4), nickel monoxide particle (NiO), ruthenium-oxide particle (RuO
2) and yttrium oxide particle (IrO
2) in one or more.Described nano level metal particle is one or more in copper particle, nickel particle, gold grain, silver-colored particle, palladium particle, ruthenium particle, platinum and the rhodium particle.The magnitude range of described nano-scale particle is 1 nanometer-100 nanometer; Preferably, the scope of described nano-scale particle is 1 nanometer-50 nanometer.The quality percentage composition of described nano-scale particle in described composite structure of carbon nano tube is greater than 0 and less than 100%, and preferably, the quality percentage composition of described nano level metal particle in described composite structure of carbon nano tube is greater than 50% and less than 70%.
See also Fig. 2 to Fig. 4, in the present embodiment, described first electrode 101 is a composite structure of carbon nano tube 110.Carbon nano tube structure that described composite structure of carbon nano tube 110 is made up of the 20 folded layer by layer carbon nano-tube membranes 112 that are provided with and the nanosize metal oxide particle 114 that is arranged at this carbon nano tube structure surface are formed.Each layer carbon nano-tube membrane 112 is made up of some carbon nano-tube 1122, and the carbon nano-tube 1122 in the adjacent carbon nano-tube membrane axially between angle be 90 °.These 20 about 500 nanometers of thickness of folding the carbon nano-tube membrane 112 that is provided with layer by layer, its superficial density is approximately 27 microgram/square centimeters, and its square resistance is 50 Europe.Described nanosize metal oxide particle 114 is MnO
2Particle, MnO
2Particle is spaced apart in the surface of each carbon nano-tube 1122, and the quality percentage composition in this composite structure of carbon nano tube 110 is approximately 62%; This MnO
2The size of particle is about 5 nanometers.Therefore, this composite structure of carbon nano tube 110 is one carbon nano-tube/MnO
2Composite construction.
The material of the material of described second electrode 102 and first electrode 101 can be identical, also can be other electrode material, as active carbon, transition metal oxide etc.In the present embodiment, the material of described second electrode 102 is identical with the material of first electrode 101, is composite structure of carbon nano tube 110.Because composite structure of carbon nano tube 110 has self-supporting, so it when being applied to this ultracapacitor 10 as electrode, does not need other collector body, himself just can be used as collector body.
Described barrier film 105 is glass fibre or polymer film, and it allows the electrolyte ion circulation in the described electrolyte 106 and stops described first electrode 101 and second electrode 102 to contact.
Described electrolyte 106 is the carbonic allyl ester solution of the sodium hydroxid aqueous solution, potassium hydroxide aqueous solution, aqueous sulfuric acid, aqueous solution of nitric acid, aqueous sodium persulfate solution, potassium sulfate solution, lithium perchlorate, the carbonic allyl ester solution of tetraethylammonium tetrafluoroborate, or the mixed liquor of above combination in any.In the present embodiment, described electrolyte 106 is the metabisulfite solution of 0.5 mol.
Described shell 107 is glass shell or stainless steel casing.In the present embodiment, described shell 107 is a glass.
The structure type that is appreciated that this ultracapacitor is not limit, and can also be Coin shape capacitor or around volume type solvent capacitor.
The ultracapacitor 10 that present embodiment is provided carries out the work electric performance test, see also Fig. 8-10, the result shows: the ultracapacitor 10 in the present embodiment has higher efficiency for charge-discharge and specific capacitance, stability, and good cycle charge discharge electrical property preferably.Wherein, this ultracapacitor 10 is under the situation of 10 peace/gram electric currents, and it discharged and recharged the time greater than 120 seconds; The average quality specific capacitance is approximately 508 method/grams, and the volumetric capacitance amount is approximately 800 method/cubic centimetres.After this ultracapacitor 10 was through 2500 circulations, the loss of its specific capacitance was no more than 4.5%.Through calculating, the energy density of this ultracapacitor 10 is approximately 30 watts hours/kilograms, and power density is approximately 110 kilowatts/kilogram.
See also Fig. 5, second embodiment of the invention provides a kind of ultracapacitor 20, and the structure of the ultracapacitor 10 that the structure of this ultracapacitor 20 and first embodiment provide is basic identical.This ultracapacitor 20 is plate ultracapacitor also, and it comprises: one first electrode, 201, one second electrode 202, one barrier films, 205, one electrolyte 206 and shells 207.Described ultracapacitor 20 is with the difference of described ultracapacitor 10: the material of described first electrode 201 and second electrode 202 is different with the material of first electrode 101 among first embodiment and second electrode 102, and described electrolyte 206 is the potassium hydroxide solution of 1 mol.
Described first electrode 201 and second electrode 202 are composite structure of carbon nano tube 210, this composite structure of carbon nano tube 210 specifically sees also Fig. 6 and Fig. 7, and carbon nano tube structure that described composite structure of carbon nano tube 210 is made up of 20 layers of carbon nano-tube membrane 212 and the nanosize metal oxide particle 214 that is arranged at this carbon nano tube structure surface are formed.Each carbon nano-tube membrane 212 is made up of some carbon nano-tube 2122.Carbon nano tube structure in the composite structure of carbon nano tube 110 among the concrete structure of described carbon nano tube structure and first embodiment is identical.Described nanosize metal oxide particle 214 is Co
3O
4Particle, Co
3O
4Particle is arranged at intervals at the surface of each carbon nano-tube 2122, and the quality percentage composition in this composite structure of carbon nano tube 210 is approximately 54%, this Co
3O
4The size of particle is about 10 nanometers.Therefore, this composite structure of carbon nano tube 210 is one carbon nano-tube/Co
3O
4Composite construction.
The ultracapacitor 20 that present embodiment is provided carries out the service behaviour test, sees also Fig. 8-10.This ultracapacitor 20 is under the situation of 10 peace/gram electric currents, and it discharged and recharged the time greater than 45 seconds; The higher 1100 method/grams that surpass of the moment specific capacitance of this ultracapacitor 20.After this ultracapacitor 20 was through 2500 circulations, the loss of its specific capacitance was no more than 4.5%; Therefore, this ultracapacitor 20 is stable relatively good.Through calculating: the average quality specific capacitance of this ultracapacitor 20 is approximately 302 method/grams, and the volumetric capacitance amount is approximately 470 method/cubic centimetres.
Third embodiment of the invention also provides a ultracapacitor, and the ultracapacitor 20 that this ultracapacitor and second embodiment provide is basic identical.Difference is, first electrode 201 in the ultracapacitor 20 of first electrode in the ultracapacitor that the 3rd embodiment provides and the material of second electrode and second embodiment and the material of second electrode 202 are different.First electrode among the 3rd embodiment and the material of second electrode are carbon nano-tube/NiO composite construction.This carbon nano-tube/NiO composite construction is similar to the composite structure of carbon nano tube 210 among second embodiment; Difference is that the nanosize metal oxide particle in this carbon nano-tube/NiO composite construction is different with the nanosize metal oxide particle 214 in the composite structure of carbon nano tube 210.Nanosize metal oxide particle in the present embodiment is the NiO particle, and the quality percentage composition of NiO particle in this carbon nano-tube/NiO composite construction is approximately 51%.The ultracapacitor that adopts this carbon nano-tube/NiO composite construction is carried out the service behaviour test, see also Fig. 8-10.The ultracapacitor that the 3rd embodiment provides is under the situation of 10 peace/gram electric currents, and it discharged and recharged the time greater than 30 seconds; Its, quality was than the higher 1500 method/grams that surpass of capacitance moment.After this ultracapacitor was through 2500 circulations, the loss of its specific capacitance also was no more than 4.5%, so its stability is relatively good.Through calculating: the average quality specific capacitance of the ultracapacitor that the 3rd embodiment provides is approximately 336 method/grams, and the volumetric capacitance amount is approximately 530 method/cubic centimetres.
The ultracapacitor that the embodiment of the invention provides has the following advantages: first, the electrode of described ultracapacitor is owing to adopt the composite structure of carbon nano tube with self-supporting function, so do not need other collector body, itself just can be used as collector body this composite structure of carbon nano tube, thereby has simplified the structure of ultracapacitor.And the quality of this composite structure of carbon nano tube is less than the quality of metal current collector, therefore adopts the ultracapacitor of this composite structure of carbon nano tube to have higher total energy density and overall power density, especially adopts carbon nano-tube/MnO
2The ultracapacitor of composite construction.Second, described composite structure of carbon nano tube comprises a large amount of micropores, the existence of these a large amount of micropores has increased the specific area of this composite structure of carbon nano tube, make described electrolyte fully contact with this composite structure of carbon nano tube, thereby can promote the ultracapacitor fast charging and discharging, and then improve the capacitance of ultracapacitor.The 3rd, after the ultracapacitor that the embodiment of the invention provides circulated through 2500 times, the loss of its specific capacitance also was no more than 4.5%, experiment showed, the stable relatively good of this ultracapacitor.
In addition, those skilled in the art can also do other and change in spirit of the present invention, and the variation that these are done according to spirit of the present invention all should be included in the present invention's scope required for protection.
Claims (13)
1. ultracapacitor, it comprises:
One first electrode;
One second electrode, this second electrode and the described first electrode gap setting;
One barrier film, this barrier film are arranged between described first electrode and second electrode; And
One electrolyte, described first electrode, second electrode and barrier film all are arranged in this electrolyte, it is characterized in that, described first electrode is a composite structure of carbon nano tube, this composite structure of carbon nano tube is a self supporting structure, and comprises a carbon nano tube structure and be arranged at the nano-scale particle on this carbon nano tube structure surface.
2. ultracapacitor as claimed in claim 1 is characterized in that described carbon nano tube structure is made up of some carbon nano-tube, and described nano-scale particle is arranged at the surface of these some carbon nano-tube.
3. ultracapacitor as claimed in claim 1 is characterized in that described composite structure of carbon nano tube has a plurality of micropores.
4. ultracapacitor as claimed in claim 1 is characterized in that, described nano-scale particle is nanosize metal oxide particle, nano level metal particle or its composition.
5. ultracapacitor as claimed in claim 4 is characterized in that, described nanosize metal oxide particle is a kind of or its arbitrary composition in manganese dioxide particle, cobaltosic oxide particle, nickel monoxide particle, ruthenium-oxide particle and the yttrium oxide particle.
6. ultracapacitor as claimed in claim 4 is characterized in that, described nano level metal particle is a kind of or its arbitrary composition in copper particle, nickel particle, gold grain, silver-colored particle, palladium particle, ruthenium particle, platinum and the rhodium particle.
7. ultracapacitor as claimed in claim 1 is characterized in that, described carbon nano tube structure is at least one carbon nano-tube film, at least one liner structure of carbon nano tube or its combination.
8. ultracapacitor as claimed in claim 7 is characterized in that described carbon nano tube structure comprises a plurality of carbon nano-tube films, and this substantially parallel no gap of a plurality of carbon nano-tube films coplane is provided with or stacked setting.
9. as claim 7 or 8 described ultracapacitors, it is characterized in that described carbon nano-tube film is made up of some carbon nano-tube, the bearing of trend of most of carbon nano-tube is parallel to the surface of this carbon nano-tube film in this carbon nano-tube film.
10. ultracapacitor as claimed in claim 9 is characterized in that, most of carbon nano-tube join end to end by Van der Waals force with adjacent carbon nano-tube on bearing of trend in the described carbon nano-tube film.
11. ultracapacitor as claimed in claim 9 is characterized in that, described carbon nano-tube film comprises equally distributed a plurality of carbon nano-tube, and these a plurality of carbon nano-tube are unordered, be arranged of preferred orient along same direction or different directions.
12. ultracapacitor as claimed in claim 9 is characterized in that, described carbon nano-tube film comprises the carbon nano-tube of twining mutually by Van der Waals force.
13. ultracapacitor as claimed in claim 7, it is characterized in that, described liner structure of carbon nano tube comprises at least one carbon nano tube line, this at least one carbon nano tube line is made up of some carbon nano-tube, and the axially basic of these some carbon nano-tube extended or around the axial direction spiral extension of this carbon nano tube line along the axial direction that is parallel to this carbon nano tube line.
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| CN 200910189146 CN102103935A (en) | 2009-12-18 | 2009-12-18 | Super capacitor |
| US12/822,308 US8246860B2 (en) | 2009-10-23 | 2010-06-24 | Carbon nanotube composite, method for making the same, and electrochemical capacitor using the same |
| US12/826,950 US8246861B2 (en) | 2009-10-23 | 2010-06-30 | Carbon nanotube composite, method for making the same, and electrochemical capacitor using the same |
| US12/826,963 US8810995B2 (en) | 2009-10-23 | 2010-06-30 | Carbon nanotube composite, method for making the same, and electrochemical capacitor using the same |
| JP2010229678A JP5528982B2 (en) | 2009-12-18 | 2010-10-12 | Electric double layer capacitor |
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| CN 200910189146 CN102103935A (en) | 2009-12-18 | 2009-12-18 | Super capacitor |
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| JP2011129883A (en) | 2011-06-30 |
| JP5528982B2 (en) | 2014-06-25 |
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