CN101923962A - Active carbon electrode and super capacitor containing same - Google Patents
Active carbon electrode and super capacitor containing same Download PDFInfo
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- CN101923962A CN101923962A CN2010101299050A CN201010129905A CN101923962A CN 101923962 A CN101923962 A CN 101923962A CN 2010101299050 A CN2010101299050 A CN 2010101299050A CN 201010129905 A CN201010129905 A CN 201010129905A CN 101923962 A CN101923962 A CN 101923962A
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Abstract
The invention discloses an active carbon electrode and a super capacitor containing the active carbon electrode. The invention also discloses methods for manufacturing the active carbon electrode and the super capacitor. The active carbon electrode comprises an aluminium foil substrate, a graphite electroconductive adhesive layer and an active carbon coating and is formed by superposition followed by roll-in processing. The graphite electroconductive adhesive layer comprises a bonding agent and a graphite material, the active carbon coating comprises an active carbon material, acetylene black and the bonding agent. Preferably, when acting as a positive electrode, the bonding agent is the mixture of polyvinylpyrrolidone and sodium carboxymethylcellulose; and when acting as a negative electrode, the bonding agent is the mixture of butadiene styrene rubber latex and sodium carboxymethylcellulose. The active carbon electrode features fine electric property and structural strength, and the capacitor equipped with the active carbon electrode features fine energy storage property and stability, thus being widely applied to fields such as industry, transportation, electronics, military science and the like.
Description
Technical field
The present invention relates to the ultracapacitor technical field, particularly comprise the ultracapacitor and the manufacture method thereof of activated carbon positive pole and activated carbon negative pole.
Background technology
Ultracapacitor is a kind of novel energy-storing device, integrates characteristics such as high-energy-density, high power density, long-life, and it also has advantages such as non-maintaining, high reliability in addition, is a kind of new electronic component that has both electric capacity and battery behavior.It mainly is divided into and is based upon " electric double layer type " ultracapacitor on the interfacial electric double layer basis and is based upon " pseudo-capacitance type " ultracapacitor on " pseudo capacitance " basis according to the difference of energy storage mechanism.The character of material with carbon element is the decisive factor of decision " electric double layer type " ultracapacitor performance.Specific area, pore-size distribution, electrochemical stability and conductivity etc. comprising material with carbon element.The material with carbon element that meets the demands through research has active carbon, carbon nano-fiber, CNT (carbon nano-tube) or the like, the United States Patent (USP) (US6955694) of relatively more typical patent of this respect such as U.S. MAXWELL company, the said firm in Chinese patents " multi-electrode double layer capacitor " (CA1408121A) with hermetic electrolyte seal, and the Chinese patent of Sino Power Star Co., Ltd. (SPSCAP) " active carbon fiber fabrics/spraying aluminium compound polar plate double electric layer capacitor and preparation method thereof " is (ZL03124290.1).The principle of " pseudo-capacitance " is that electrode material utilizes lithium ion or the storage of proton in the three-dimensional or accurate two-dimensional crystal lattice stereochemical structure of material to stay the purpose that reaches storage power, such electrode material comprises metal oxide, nitride, high molecular polymer or the like, comparatively typical patent such as Tsing-Hua University " based on composite super capacitor of cobalt oxide and ruthenium-oxide and preparation method thereof " (ZL200810111892.7).The core component of ultracapacitor is its electrode, and the key factor of restriction active carbon material bonding strength is an adhesive, and there is the not high problem of adhesion strength in the polytetrafluoroethylene that adopt as adhesive more in the traditional handicraft.The present invention proposes a kind of novel electrode, based on ultracapacitor of this novel electrode and preparation method thereof, the use of new type bonding agent can effectively improve pole strength, ultracapacitor based on above-mentioned novel electrode has characteristics such as energy storage density is big, discharge power is high, stable performance, has important use in traffic, the energy, space flight, green novel energy source and military domain.
Summary of the invention
In order to address the above problem, the invention provides a kind of active carbon electrode and with the ultracapacitor of described electrode as positive pole and/or negative pole.Specifically, the present invention finishes by following technical solution.
1. active carbon electrode, wherein, described active carbon electrode comprises aluminium foil substrate, graphite electroconductive adhesive layer and active carbon coating, and at superposition after rolling process handle and form.
2. according to technical scheme 1 described active carbon electrode, wherein, described graphite electroconductive adhesive layer comprises adhesive and graphite material; Described active carbon coating comprises active carbon material, acetylene black and described adhesive.
3. according to technical scheme 1 or 2 described active carbon electrodes, wherein, described active carbon electrode is as positive pole, and described adhesive is anodal adhesive, comprises polyvinylpyrrolidone and sodium carboxymethylcellulose.
4. according to technical scheme 3 described active carbon electrodes, wherein, in the gross mass of described graphite electroconductive adhesive layer, the mass ratio of described anodal adhesive is 10% to 20%; Preferably, in the gross mass of described anodal adhesive, the mass ratio of described polyvinylpyrrolidone is 20% to 50%; In addition preferably, the mass ratio between described polyvinylpyrrolidone and the sodium carboxymethylcellulose is 1: 3; In addition preferably, described graphite electroconductive adhesive layer is made by slurry, described slurry adopts following method preparation: deionized water is heated to 35 ℃ to 45 ℃, add described sodium carboxymethylcellulose and polyvinylpyrrolidone successively, stir then, add described graphite material again, after stirring, further adopt colloid mill to carry out milled processed.
5. according to technical scheme 4 described active carbon electrodes, wherein, the method that described graphite electroconductive adhesive layer adopts spraying or blade coating is attached to the surface of described aluminium foil matrix with described slurry, and the thickness of formed graphite electroconductive adhesive layer is 20 microns to 50 microns.
6. according to technical scheme 3 described active carbon electrodes, wherein, in the gross mass of described active carbon coating, the mass ratio of described anodal adhesive is 5% to 10%; Preferably, in the gross mass of described anodal adhesive, the mass ratio of described polyvinylpyrrolidone is 20% to 50%; In addition preferably, the mass ratio between described polyvinylpyrrolidone and the sodium carboxymethylcellulose is 1: 3; In addition preferably, the mass ratio of described active carbon material and acetylene black is 9: 1; In addition preferably, described active carbon coating is made by slurry, described slurry adopts following method preparation: deionized water is heated to 35 ℃ to 45 ℃, add described sodium carboxymethylcellulose and polyvinylpyrrolidone successively, stir then, add described acetylene black and active carbon material more successively, after stirring, further adopt colloid mill to carry out milled processed.
7. according to technical scheme 6 described active carbon electrodes, wherein, described active carbon coating adopts the method for blade coating that described slurry is attached to described graphite conductive adhesive laminar surface, and formed active carbon coating thickness is 100 microns to 200 microns.
8. according to technical scheme 1 or 2 described active carbon electrodes, wherein, described active carbon electrode is as negative pole, and described adhesive is the negative pole adhesive, comprises styrene butadiene rubber latex and sodium carboxymethylcellulose.
9. according to technical scheme 8 described active carbon electrodes, wherein, in the gross mass of described graphite electroconductive adhesive layer, the mass ratio of described negative pole adhesive is 10% to 20%; Preferably, in the gross mass of described negative pole adhesive, the mass ratio of described styrene butadiene rubber latex is 20% to 60%; In addition preferably, the mass ratio of described styrene butadiene rubber latex and sodium carboxymethylcellulose is 2: 3; In addition preferably, described graphite electroconductive adhesive layer is made by slurry, described slurry is prepared by following method: deionized water is heated to 55 ℃ to 65 ℃, add described sodium carboxymethylcellulose and styrene butadiene rubber latex successively, stir then, add described graphite material again, after stirring, further adopt colloid mill to carry out milled processed.
10. according to technical scheme 9 described active carbon electrodes, wherein, the method that described graphite electroconductive adhesive layer adopts spraying or blade coating is attached to the surface of described aluminium foil matrix with described slurry, and the thickness of formed graphite electroconductive adhesive layer is 20 microns to 50 microns.
11. according to technical scheme 8 described active carbon electrodes, wherein, in the gross mass of described active carbon coating, the mass ratio of described negative pole adhesive is 5% to 10%; Preferably, in the gross mass of described negative pole adhesive, the mass ratio of described styrene butadiene rubber latex is 20% to 50%; In addition preferably, the mass ratio between described styrene butadiene rubber latex and the sodium carboxymethylcellulose is 2: 3; In addition preferably, the mass ratio of described active carbon material and acetylene black is 9: 1; In addition preferably, described active carbon coating is made by slurry, described slurry adopts following method preparation: deionized water is heated to 55 ℃ to 65 ℃, add described sodium carboxymethylcellulose and styrene butadiene rubber latex successively, stir then, add described acetylene black and active carbon material more successively, after stirring, further adopt colloid mill to carry out milled processed.
12. according to technical scheme 11 described active carbon electrodes, wherein, the method that described active carbon coating adopts blade coating is attached to the surface of described graphite electroconductive adhesive layer with described slurry, the thickness of formed active carbon coating is 100 microns to 200 microns.
13. ultracapacitor, wherein, described ultracapacitor comprises positive pole, negative pole and shell, described positive pole and/or negative pole are technical scheme 1 or 2 described electrodes, described shell is stainless steel casing or aluminum shell, and described positive pole and negative pole superposition or coiling successively become electrode cores and are placed in the described shell, and described body seal has nonaqueous electrolyte; Preferably, described just very technical scheme 3 to 7 each described active carbon electrodes, described negative pole are technical scheme 8 to 12 each described active carbon electrodes.
The present invention proposes a kind of novel active carbon electrode, based on the manufacture method of ultracapacitor and the described active carbon electrode and the described ultracapacitor of described active carbon electrode.The structure of described ultracapacitor is after the anodal and activated carbon negative pole of activated carbon superposes successively or is wound as electrode cores, be sealed in for example stainless steel or interior configuration example of aluminum shell such as cylindrical or square structure, and in this shell, pour into the hermetically sealed ultracapacitor of nonaqueous electrolyte assembling becoming.
The invention has the beneficial effects as follows by proposing to form the preparation method of the novel active carbon electrode of adhesive, improved electrode structure intensity effectively, reduced the internal resistance of electrode based on difference.Ultracapacitor based on the novel active carbon electrode has the good operation reliability, the ultracapacitor of describing among the present invention is at industrial uninterrupted power supply, motor vehicle, wind power generation, and fields such as high-power military power supply, radio communication are widely used.
Description of drawings
Fig. 1 is an electrode sandwich construction schematic diagram
Fig. 2 is a circular super capacitor arrangement schematic diagram
Fig. 3 is square supercapacitor structures schematic diagram
Embodiment
The invention discloses a kind of ultracapacitor and the manufacture method thereof of the manufacturing technology scope that belongs to capacitor based on active carbon electrode.This capacitor is sealed in for example stainless steel or the interior configuration example of aluminum shell such as cylindrical structure or square structure by activated carbon positive pole and activated carbon negative pole superposition or after being wound as electrode cores.
Activated carbon positive pole and activated carbon negative pole are made of aluminium foil substrate, graphite electroconductive adhesive layer and active carbon coating stack respectively.Graphite electroconductive adhesive layer comprises adhesive and graphite material.Active carbon coating comprises active carbon material, acetylene black and adhesive.
Have stronger adhesive capacity between graphite electroconductive adhesive layer and the aluminium foil substrate, reduce the electrode internal resistance when can improve pole strength, above-mentioned technology can solve the technical barrier of adhesion strength difference between active carbon material and the aluminium foil.
In preferred implementation of the present invention, the positive pole of ultracapacitor is that with the difference of negative pole the adhesive ingredients that is adopted is different, adhesive in the positive pole is the mixture of polyvinylpyrrolidone and sodium carboxymethylcellulose, and the adhesive in the negative pole is the mixture of styrene butadiene rubber latex and sodium carboxymethylcellulose.Compare with traditional polytetrafluoroethylene-sodium carboxymethylcellulose adhesive, the new type bonding agent adhesion strength that this patent adopted improves, and can further solve the technical barrier of active carbon coating structural strength difference.The anodal polyvinylpyrrolidone that adopts can solve styrene butadiene rubber latex unsettled technical barrier under high potential.
Preferably, when the preparation activated carbon was anodal, in the gross mass of described graphite electroconductive adhesive layer, the mass ratio of anodal adhesive was 10% to 20%, for example is 10%, 15% or 20%; If the mass ratio of anodal adhesive is low excessively, then may cause adhesion strength to reduce; If the mass ratio of anodal adhesive is too high, may cause then that electrode hardens, fragility increases.
Preferably, in the gross mass of described anodal adhesive, the mass ratio of described polyvinylpyrrolidone is 20% to 50%, for example is 20%, 30%, 40% or 50%; If the mass ratio of described polyvinylpyrrolidone is low excessively, then may cause adhesion strength reduction, electrode material to come off; If the mass ratio of described polyvinylpyrrolidone is too high, then may cause the electrode internal resistance to raise.
In addition preferably, the mass ratio between described polyvinylpyrrolidone and the sodium carboxymethylcellulose is 1: 3 to 3: 1, more preferably 1: 3.
Further preferably, described graphite electroconductive adhesive layer is made by slurry, described slurry adopts following method preparation: deionized water is heated to 35 ℃ to 45 ℃ (is controlled in this temperature range, for example temperature can remain on arbitrary temp or the temperature range in this scope, down together), add described sodium carboxymethylcellulose and polyvinylpyrrolidone successively, stir then, add described graphite material again, after stirring, further adopt colloid mill to carry out milled processed.
Described graphite electroconductive adhesive layer can adopt spraying or the method for blade coating that described slurry is attached to the surface of described aluminium foil matrix, and the thickness of formed graphite electroconductive adhesive layer is 20 microns to 50 microns, for example is 20 microns, 30 microns, 40 microns or 50 microns.
In addition preferably, in the gross mass of described active carbon coating, the mass ratio of described anodal adhesive is 5% to 10%, for example is 5%, 7%, 8% or 10%.In addition preferably, in the gross mass of described anodal adhesive, the mass ratio of described polyvinylpyrrolidone is 20% to 50%, for example is 20%, 30%, 40% or 50%.Further preferably, the mass ratio between described polyvinylpyrrolidone and the sodium carboxymethylcellulose is 1: 3 to 3: 1, more preferably 1: 3.More preferably, the mass ratio of described active carbon material and acetylene black is 9: 1; In addition further preferably, described active carbon coating is made by slurry, described slurry adopts following method preparation: deionized water is heated to 35 ℃ to 45 ℃, add described sodium carboxymethylcellulose and polyvinylpyrrolidone successively, stir then, add described acetylene black and active carbon material more successively, after stirring, further adopt colloid mill to carry out milled processed.
In addition preferably, described active carbon coating adopts the method for blade coating that described slurry is attached to described graphite conductive adhesive laminar surface, formed active carbon coating thickness is 100 microns to 200 microns, for example can be 100 microns, 120 microns, 140 microns, 160 microns, 180 microns or 200 microns.
Preferably, when preparation activated carbon negative pole, in the gross mass of described graphite electroconductive adhesive layer, the mass ratio of described negative pole adhesive is 10% to 20%, for example is 10%, 15% or 20%; If the mass ratio of negative pole adhesive is low excessively, then may cause adhesion strength to reduce; If the mass ratio of negative pole adhesive is too high, may cause then that electrode hardens, fragility increases.
Preferably, in the gross mass of described negative pole adhesive, the mass ratio of described styrene butadiene rubber latex is 20% to 60%, for example is 20%, 30%, 40% or 50%; If the mass ratio of described styrene butadiene rubber latex is low excessively, then may cause adhesion strength reduction, electrode material to come off; If the mass ratio of described styrene butadiene rubber latex is too high, then may cause the electrode internal resistance to raise.In addition preferably, the mass ratio of described styrene butadiene rubber latex and sodium carboxymethylcellulose is 2: 3 to 3: 2, more preferably 2: 3.
In addition preferably, described graphite electroconductive adhesive layer is made by slurry, described slurry is prepared by following method: deionized water is heated to 55 ℃ to 65 ℃, add described sodium carboxymethylcellulose and styrene butadiene rubber latex successively, stir then, add described graphite material again, after stirring, further adopt colloid mill to carry out milled processed.
When the preparation negative pole, described graphite electroconductive adhesive layer can adopt the method for spraying or blade coating described slurry to be attached to the surface of described aluminium foil matrix, the thickness of formed graphite electroconductive adhesive layer is 20 microns to 50 microns, for example is 20 microns, 30 microns, 40 microns or 50 microns.
In addition preferably, in the gross mass of described active carbon coating, the mass ratio of described negative pole adhesive is 5% to 10%, for example is 5%, 7%, 8% or 10%.In addition preferably, in the gross mass of described negative pole adhesive, the mass ratio of described styrene butadiene rubber latex is 20% to 50%, for example is 20%, 30%, 40% or 50%.Further preferably, the mass ratio between described styrene butadiene rubber latex and the sodium carboxymethylcellulose is 2: 3 to 3: 2, more preferably 2: 3.In addition further preferably, the mass ratio of described active carbon material and acetylene black is 9: 1.In addition further preferably, described active carbon coating is made by slurry, described slurry adopts following method preparation: deionized water is heated to 55 ℃ to 65 ℃, add described sodium carboxymethylcellulose and styrene butadiene rubber latex successively, stir then, add described acetylene black and active carbon material more successively, after stirring, further adopt colloid mill to carry out milled processed.
In addition further preferably, described active carbon coating adopts the method for blade coating described slurry to be attached to the surface of described graphite electroconductive adhesive layer, the thickness of formed active carbon coating is 100 microns to 200 microns, for example can be 100 microns, 120 microns, 140 microns, 160 microns, 180 microns or 200 microns.
In another aspect of the present invention, a kind of ultracapacitor is provided, wherein, described ultracapacitor comprises positive pole, negative pole and shell, described positive pole and negative pole are respectively above-mentioned prepared electrode, described shell is stainless steel casing or aluminum shell, and described positive pole and negative pole successively superposition or coiling become electrode cores and be placed in the described shell, described body seal has nonaqueous electrolyte.
The electrode structure of ultracapacitor and capacitor arrangement be as shown in the figure:
Fig. 1 is the electrode structure schematic diagram, and wherein 1 is aluminium foil layer, and 2 and 4 is the graphite electroconductive adhesive layer of aluminium foil both sides, and 3 and 5 is the active carbon coating on conductive adhesive layer surface.
Fig. 2 is a circular super capacitor arrangement schematic diagram, and wherein 6 is electrode, and 7 is barrier film, and 8 is electrode cores, and 9 is drainage strip, and 10 is top cover, and 11 is electrode terminal, and 12 is shell.
Fig. 3 is square supercapacitor structures schematic diagram, and wherein 13 is liquid injection port
When the assembling ultracapacitor, described electrode can adopt methods such as thorn riveting or welding to connect drainage strip, after technologies such as stack and coiling, form electrode cores then, drainage strip after connecting top cover with calendering or welding manner, stainless steel or aluminum shell is finished the dry state encapsulation with putting into after electrode terminal is connected, the dry state packaging semi-finished product is carried out processed such as vacuum drying at utmost to remove the moisture of capacitor inside, finish the capacitor assembling after pouring into nonaqueous electrolyte at last and shutting liquid injection port.
Embodiment
By the following examples preferred implementation of the present invention is further detailed, but embodiment only for the purpose of illustration, can not be interpreted as the restriction to scope of the present invention, in other words, scope of the present invention is not limited to these embodiment.
Embodiment 1
1. anodal surperficial graphite electroconductive adhesive layer preparation.Get aluminium foil as electrode matrix, adopt slurry spraying coating process (in the present invention, also can adopt blade coating technology) preparation graphite electroconductive adhesive layer in its both side surface.Anodal graphite electroconductive adhesive layer is mixed with graphite material by anodal adhesive and is constituted, and mass ratio is 15: 85 between wherein anodal adhesive and the graphite.Anodal adhesive is the mixture of polyvinylpyrrolidone and sodium carboxymethylcellulose, and mass ratio is 1: 3.The pulp preparation process adds sodium carboxymethylcellulose fully to stir for deionized water heating and be controlled in 35 ℃ to 45 ℃ the scope in advance, thoroughly stirs after adding polyvinylpyrrolidone then.Add graphite and fully stir the formation uniform sizing material according to 15: 85 between anodal adhesive and the graphite ratios.After utilizing colloid mill to carry out milled processed the prepared slurry, adopt spraying method to be coated on the both sides of aluminium foil matrix, conductive adhesive layer thickness is 40 microns.
2. anodal active carbon coating preparation.The anodal graphite electroconductive adhesive layer surface-coated activated carbon layer that is preparing.Active carbon coating comprises anodal adhesive, active carbon material and acetylene black.Wherein, in the gross mass of active carbon coating, the mass ratio of anodal adhesive is 8%.Anodal adhesive is polyvinylpyrrolidone and sodium carboxymethylcellulose mixture, and polyvinylpyrrolidone and sodium carboxymethylcellulose optimum quality ratio are 1: 3.Active carbon material and acetylene black mass ratio are 9: 1 in the active carbon coating.The pulp preparation process is for deionized water heating and be controlled in 35 ℃ to 45 ℃ the scope, thoroughly stir after adding sodium carboxymethylcellulose and polyvinylpyrrolidone successively, add successively then and fully stir the step of going forward side by side behind acetylene black and the active carbon material and carry out the colloid mill milled processed.Coating method is scraped in the slurry employing be coated in the graphite conductive adhesive laminar surface uniformly, the thickness of prepared active carbon coating is 150 microns.
3. anodal roller process.The graphite electroconductive adhesive layer for preparing and the electrode of active carbon coating structure are carried out roller process, and handle, make positive pole thus 110 ℃ of oven dry.
4. the preparation of the graphite electroconductive adhesive layer of negative terminal surface.Get aluminium foil as electrode matrix, adopt slurry spraying preparation graphite electroconductive adhesive layer in its both side surface.Graphite electroconductive adhesive layer is the blend mixture of negative pole adhesive and graphite material, and wherein the mass ratio between negative pole adhesive and the graphite is 15: 85.The negative pole adhesive is styrene butadiene rubber latex and sodium carboxymethylcellulose mixture, and its optimum quality ratio is 2: 3.The pulp preparation process adds sodium carboxymethylcellulose earlier and fully stirs for deionized water heating and be controlled in 55 ℃ to 65 ℃ the scope, thoroughly stirs after adding styrene butadiene rubber latex then.Add graphite and fully stir the formation uniform sizing material according to 15: 85 ratios between negative pole adhesive and the graphite.Utilize colloid mill to carry out adopting spraying method to be coated on the both sides of aluminium foil matrix after the milled processed in prepared slurry, the thickness of graphite electroconductive adhesive layer is 40 microns.
5. the preparation of the active carbon coating of negative pole.Graphite electroconductive adhesive layer surface-coated active carbon coating at the negative pole for preparing.Active carbon coating is made of negative pole adhesive, active carbon material and acetylene black mixing.In the gross mass of active carbon coating, the mass ratio of negative pole adhesive is 8%.The negative pole adhesive is the mixture of styrene butadiene rubber latex and sodium carboxymethylcellulose, and the mass ratio of styrene butadiene rubber latex and sodium carboxymethylcellulose is 2: 3.In the gross mass of active carbon coating, the mass ratio of active carbon material and acetylene black is 9: 1.The pulp preparation process is for deionized water heating and be controlled in 55 ℃ to 65 ℃ the scope, thoroughly stir after adding sodium carboxymethylcellulose and styrene butadiene rubber latex successively, add successively then and fully stir the step of going forward side by side behind acetylene black and the active carbon material and carry out the colloid mill milled processed.Coating method is scraped in the slurry employing be coated with uniformly built in the graphite electroconductive adhesive layer surface, the thickness of prepared active carbon coating is 150 microns.
6. negative pole roller process.The graphite electroconductive adhesive layer for preparing and the electrode of active carbon coating structure are carried out roller process, and handle, obtain negative pole thus 110 ℃ of oven dry.
7. capacitor packaging technology process.As shown in Figures 2 and 3, prepared positive pole is connected drainage strip 9 with negative pole by methods such as thorn riveting or welding, after technologies such as stack and coiling, form electrode cores 8 with barrier film 7 then, with drainage strip with put into aluminum shell (in the present invention after electrode terminal 11 is connected, also can adopt stainless steel casing) in 12 in the calendering mode (in the present invention, also can adopt welding manner) finish the dry state encapsulation after connecting top cover 10, the dry state packaging semi-finished product is carried out processed by vacuum drying, at utmost to remove the moisture of capacitor inside, after pouring into nonaqueous electrolyte at last and shutting liquid injection port 13, make ultracapacitor.
Embodiment 2 and 3
Except following table 1 and 2 listed parameters, implement embodiment 2 and 3 in the mode similar to embodiment 1.
The anodal parameter relevant of table 1 preparation with material and technology
| Embodiment 1 | 15％ | 20％ | 1∶3 | 40 | 8％ | 20％ | 1∶3 | 9∶1 | 150 |
| Embodiment 2 | 10％ | 30％ | 1∶3 | 20 | 5％ | 35％ | 1∶3 | 9∶1 | 100 |
| Embodiment 3 | 20％ | 50％ | 1∶3 | 50 | 10％ | 50％ | 1∶3 | 9∶1 | 200 |
Annotate: first mass ratio is the vinylpyrrolidone in the adhesive of graphite electroconductive adhesive layer and the mass ratio of sodium carboxymethylcellulose; Second mass ratio is the polyvinylpyrrolidone in the adhesive of described active carbon coating and the mass ratio of sodium carboxymethylcellulose; The 3rd mass ratio is the mass ratio of active carbon material and acetylene black in the described active carbon coating.
The parameter relevant of table 2 preparation negative pole with material and technology
Annotate: the 4th mass ratio is the styrene butadiene rubber latex in the adhesive of graphite electroconductive adhesive layer and the mass ratio of sodium carboxymethylcellulose; The 5th mass ratio is the styrene butadiene rubber latex in the adhesive of described active carbon coating and the mass ratio of sodium carboxymethylcellulose; The 6th mass ratio is the mass ratio of active carbon material and acetylene black in the described active carbon coating.
The adhesion strength of active carbon material in the prepared electrode among each embodiment and aluminium foil matrix and energy storage density, discharge power and the working life of prepared ultracapacitor are measured, and the result is as shown in table 3 below.
The performance index of prepared electrode and ultracapacitor among each embodiment of table 3
| Embodiment | Adhesion strength (MPa) | Energy storage density (Wh/kg) | Discharge power (kW/kg) | Working life (ten thousand times) |
| Embodiment 1 | ?0.11 | 5.0 | 6.5 | 50 |
| Embodiment 2 | ?0.10 | 4.8 | 6.7 | 50 |
| Embodiment 3 | ?0.13 | 5.3 | 6.4 | 50 |
Annotate: adhesion strength is the adhesion strength between active carbon material and the aluminium foil matrix in the prepared active carbon electrode; Energy storage density, discharge power and working life are energy storage density, discharge power and the working life of prepared ultracapacitor.
Claims (9)
1. active carbon electrode, wherein, described active carbon electrode comprises aluminium foil substrate, graphite electroconductive adhesive layer and active carbon coating, and at superposition after rolling process handle and form.
2. active carbon electrode according to claim 1, wherein, described graphite electroconductive adhesive layer comprises adhesive and graphite material; Described active carbon coating comprises active carbon material, acetylene black and described adhesive.
3. active carbon electrode according to claim 1 and 2, wherein, described active carbon electrode is as positive pole, and described adhesive is anodal adhesive, comprises polyvinylpyrrolidone and sodium carboxymethylcellulose.
4. active carbon electrode according to claim 3, wherein, in the gross mass of described graphite electroconductive adhesive layer, the mass ratio of described anodal adhesive is 10% to 20%; Preferably, in the gross mass of described anodal adhesive, the mass ratio of described polyvinylpyrrolidone is 20% to 50%; In addition preferably, the mass ratio between described polyvinylpyrrolidone and the sodium carboxymethylcellulose is 1: 3; In addition preferably, described graphite electroconductive adhesive layer is made by slurry, described slurry adopts following method preparation: deionized water is heated to 35 ℃ to 45 ℃, add described sodium carboxymethylcellulose and polyvinylpyrrolidone successively, stir then, add described graphite material again, after stirring, further adopt colloid mill to carry out milled processed; In addition preferably, the method that described graphite electroconductive adhesive layer adopts spraying or blade coating is attached to the surface of described aluminium foil matrix with described slurry, and the thickness of formed graphite electroconductive adhesive layer is 20 microns to 50 microns.
5. active carbon electrode according to claim 3, wherein, in the gross mass of described active carbon coating, the mass ratio of described anodal adhesive is 5% to 10%; Preferably, in the gross mass of described anodal adhesive, the mass ratio of described polyvinylpyrrolidone is 20% to 50%; In addition preferably, the mass ratio between described polyvinylpyrrolidone and the sodium carboxymethylcellulose is 1: 3; In addition preferably, the mass ratio of described active carbon material and acetylene black is 9: 1; In addition preferably, described active carbon coating is made by slurry, described slurry adopts following method preparation: deionized water is heated to 35 ℃ to 45 ℃, add described sodium carboxymethylcellulose and polyvinylpyrrolidone successively, stir then, add described acetylene black and active carbon material more successively, after stirring, further adopt colloid mill to carry out milled processed; In addition preferably, described active carbon coating adopts the method for blade coating that described slurry is attached to described graphite conductive adhesive laminar surface, and formed active carbon coating thickness is 100 microns to 200 microns.
6. active carbon electrode according to claim 1 and 2, wherein, described active carbon electrode is as negative pole, and described adhesive is the negative pole adhesive, comprises styrene butadiene rubber latex and sodium carboxymethylcellulose.
7. active carbon electrode according to claim 6, wherein, in the gross mass of described graphite electroconductive adhesive layer, the mass ratio of described negative pole adhesive is 10% to 20%; Preferably, in the gross mass of described negative pole adhesive, the mass ratio of described styrene butadiene rubber latex is 20% to 60%; In addition preferably, the mass ratio of described styrene butadiene rubber latex and sodium carboxymethylcellulose is 2: 3; In addition preferably, described graphite electroconductive adhesive layer is made by slurry, described slurry is prepared by following method: deionized water is heated to 55 ℃ to 65 ℃, add described sodium carboxymethylcellulose and styrene butadiene rubber latex successively, stir then, add described graphite material again, after stirring, further adopt colloid mill to carry out milled processed; In addition preferably, the method that described graphite electroconductive adhesive layer adopts spraying or blade coating is attached to the surface of described aluminium foil matrix with described slurry, and the thickness of formed graphite electroconductive adhesive layer is 20 microns to 50 microns.
8. active carbon electrode according to claim 6, wherein, in the gross mass of described active carbon coating, the mass ratio of described negative pole adhesive is 5% to 10%; Preferably, in the gross mass of described negative pole adhesive, the mass ratio of described styrene butadiene rubber latex is 20% to 50%; In addition preferably, the mass ratio between described styrene butadiene rubber latex and the sodium carboxymethylcellulose is 2: 3; In addition preferably, the mass ratio of described active carbon material and acetylene black is 9: 1; In addition preferably, described active carbon coating is made by slurry, described slurry adopts following method preparation: deionized water is heated to 55 ℃ to 65 ℃, add described sodium carboxymethylcellulose and styrene butadiene rubber latex successively, stir then, add described acetylene black and active carbon material more successively, after stirring, further adopt colloid mill to carry out milled processed; In addition preferably, the method that described active carbon coating adopts blade coating is attached to the surface of described graphite electroconductive adhesive layer with described slurry, and the thickness of formed active carbon coating is 100 microns to 200 microns.
9. ultracapacitor, wherein, described ultracapacitor comprises positive pole, negative pole and shell, described positive pole and/or negative pole are claim 1 or 2 described electrodes, described shell is stainless steel casing or aluminum shell, and described positive pole and negative pole superposition or coiling successively become electrode cores and are placed in the described shell, and described body seal has nonaqueous electrolyte; Preferably, each described active carbon electrode of described just very claim 3 to 5, described negative pole are each described active carbon electrode of claim 6 to 8.
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