CN101923962B - A kind of active carbon electrode and the ultracapacitor comprising this electrode - Google Patents
A kind of active carbon electrode and the ultracapacitor comprising this electrode Download PDFInfo
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- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of active carbon electrode and the ultracapacitor comprising this electrode.The invention also discloses the method manufacturing described electrode and described ultracapacitor.Described active carbon electrode comprises aluminium foil substrate, graphite electroconductive adhesive layer and active carbon coating, and is formed through rolling process process after superposition.Described graphite electroconductive adhesive layer comprises adhesive and graphite material; Described active carbon coating comprises active carbon material, acetylene black and described adhesive.Preferably, being polyvinylpyrrolidone and sodium carboxymethylcellulose mixture as adhesive described during positive pole, is styrene butadiene rubber latex and sodium carboxymethylcellulose mixture as adhesive described during negative pole.Prepared active carbon electrode has good electrology characteristic and structural strength, and institute's assembling capacitor has good energy storage characteristic and stability characteristic (quality), in field extensive uses such as industry, traffic, electronics, military affairs.
Description
Technical field
The present invention relates to supercapacitor technologies field, particularly comprise 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 storage apparatus, integrates the characteristics such as high-energy-density, high power density, long-life, and it also has the advantages such as non-maintaining, high reliability in addition, is a kind of new electronic component having both electric capacity and battery behavior.According to the difference of energy storage mechnism, it is mainly divided into " electric double layer type " ultracapacitor be based upon on interfacial electric double layer basis and " pseudo-capacitance type " ultracapacitor be based upon on " pseudo capacitance " basis.The character of material with carbon element is the decisive factor determining " electric double layer type " ultracapacitor performance.Comprising the specific area of material with carbon element, pore-size distribution, electrochemical stability and conductivity etc.Active carbon is had through studying the material with carbon element met the demands, carbon nano-fiber, CNT (carbon nano-tube) etc., the more typical patent of this respect is as the United States Patent (USP) (US6955694) of MAXWELL company of the U.S., the patent " there is the multi-electrode double layer capacitor of hermetic electrolyte seal " (CA1408121A) that the said firm applies in China, and the Chinese patent of Sino Power Star Co., Ltd. (SPSCAP) " active carbon fibre cloth/sprayed aluminium composite polar plate double electric layer capacitor and preparation method thereof " (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 object reaching storage power, such electrode material comprises metal oxide, nitride, high molecular polymer etc., and comparatively typical patent is as " composite super capacitor and preparation method thereof based on cobalt oxide and ruthenium-oxide " (ZL200810111892.7) of Tsing-Hua University.The core component of ultracapacitor is its electrode, and the key factor of restriction active carbon material bonding strength is adhesive, and in traditional handicraft, the polytetrafluoroethylene that adopts as adhesive more, there is the problem that adhesion strength is not high.The present invention proposes a kind of novel electrode, ultracapacitor and preparation method thereof based on this novel electrode, the use of new type bonding agent effectively can improve pole strength, ultracapacitor based on above-mentioned novel electrode has the features such as energy storage density is large, discharge power is high, stable performance, in traffic, the energy, space flight, green novel energy source and military domain, have important application.
Summary of the invention
In order to solve the problem, the invention provides a kind of active carbon electrode and using described electrode as the ultracapacitor of positive pole and/or negative pole.Specifically, the present invention has come by following technical solution.
1. an active carbon electrode, wherein, described active carbon electrode comprises aluminium foil substrate, graphite electroconductive adhesive layer and active carbon coating, and is formed through rolling process process after superposition; Wherein, described graphite electroconductive adhesive layer comprises adhesive and graphite material;
When described active carbon electrode is as positive pole, described adhesive is positive electrode binder, and in the gross mass of described graphite electroconductive adhesive layer, the mass ratio of the positive electrode binder in described graphite electroconductive adhesive layer is 10% to 20%;
When described active carbon electrode is as negative pole, described adhesive is negative electrode binder, and in the gross mass of described graphite electroconductive adhesive layer, the mass ratio of the negative electrode binder in described graphite electroconductive adhesive layer is 10% to 20%.
2. active carbon electrode according to claim 1, wherein, described active carbon coating comprises active carbon material, acetylene black and described adhesive.
3. active carbon electrode according to claim 2, wherein, described positive electrode binder, comprises polyvinylpyrrolidone and sodium carboxymethylcellulose.
4. active carbon electrode according to claim 3, wherein, in the gross mass of described positive electrode binder, the mass ratio of the polyvinylpyrrolidone in described positive electrode binder is 20% to 50%.
5. active carbon electrode according to claim 3, the polyvinylpyrrolidone in described positive electrode binder and the mass ratio between sodium carboxymethylcellulose are 1:3.
6. active carbon electrode according to claim 3, described graphite electroconductive adhesive layer is obtained by slurry, described slurry is adopted and is prepared with the following method: deionized water is heated to 35 DEG C to 45 DEG C, add described sodium carboxymethylcellulose and polyvinylpyrrolidone successively, then stir, add described graphite material again, after stirring, adopt colloid mill to carry out milled processed further.
7. active carbon electrode according to claim 6, described graphite electroconductive adhesive layer adopts the method for spraying or blade coating described slurry to be attached to the surface of described aluminium foil substrate, and the thickness of the graphite electroconductive adhesive layer formed is 20 microns to 50 microns.
8. active carbon electrode according to claim 2, wherein, when described active carbon electrode is as positive pole, in the gross mass of described active carbon coating, the mass ratio of the positive electrode binder in described active carbon coating is 5% to 10%.
9. active carbon electrode according to claim 2, the mass ratio of described active carbon material and acetylene black is 9:1.
10. active carbon electrode according to claim 3, described active carbon coating is obtained by slurry, described slurry is adopted and is prepared with the following method: deionized water is heated to 35 DEG C to 45 DEG C, add described sodium carboxymethylcellulose and polyvinylpyrrolidone successively, then stir, add described acetylene black and active carbon material successively again, after stirring, adopt colloid mill to carry out milled processed further.
11. active carbon electrodes according to claim 10, described active carbon coating adopts the method for blade coating described slurry to be attached to described graphite electroconductive adhesive layer surface, and the active carbon coating thickness formed is 100 microns to 200 microns.
12. active carbon electrodes according to claim 2, wherein, described negative electrode binder, comprises styrene butadiene rubber latex and sodium carboxymethylcellulose.
13. active carbon electrodes according to claim 12, wherein, in the gross mass of described negative electrode binder, the mass ratio of the styrene butadiene rubber latex in described negative electrode binder is 20% to 60%.
14. active carbon electrodes according to claim 12, the styrene butadiene rubber latex in described negative electrode binder and the mass ratio of sodium carboxymethylcellulose are 2:3.
15. active carbon electrodes according to claim 12, described graphite electroconductive adhesive layer is obtained by slurry, described slurry is prepared by the following method: deionized water is heated to 55 DEG C to 65 DEG C, add described sodium carboxymethylcellulose and styrene butadiene rubber latex successively, then stir, add described graphite material again, after stirring, adopt colloid mill to carry out milled processed further.
16. active carbon electrodes according to claim 15, described graphite electroconductive adhesive layer adopts the method for spraying or blade coating described slurry to be attached to the surface of described aluminium foil substrate, and the thickness of the graphite electroconductive adhesive layer formed is 20 microns to 50 microns.
17. active carbon electrodes according to claim 2, wherein, when described active carbon electrode is as negative pole, in the gross mass of described active carbon coating, the mass ratio of the negative electrode binder in described active carbon coating is 5% to 10%.
18. active carbon electrodes according to claim 12, described active carbon coating is obtained by slurry, described slurry is adopted and is prepared with the following method: deionized water is heated to 55 DEG C to 65 DEG C, add described sodium carboxymethylcellulose and styrene butadiene rubber latex successively, then stir, add described acetylene black and active carbon material successively again, after stirring, adopt colloid mill to carry out milled processed further.
19. active carbon electrodes according to claim 18, described active carbon coating adopts the method for blade coating described slurry to be attached to the surface of described graphite electroconductive adhesive layer, and the thickness of the active carbon coating formed is 100 microns to 200 microns.
20. 1 kinds of ultracapacitors, wherein, described ultracapacitor comprises positive pole, negative pole and shell, described positive pole and/or negative pole all use the active carbon electrode described in claim 1-19 any one, described shell is stainless steel casing or aluminum shell, and described positive pole and negative pole successively superposition or winding become electrode cores and are placed in described shell, and described body seal has nonaqueous electrolyte.
The present invention proposes a kind of novel active carbon electrode, based on the ultracapacitor of described active carbon electrode and the manufacture method of described active carbon electrode and described ultracapacitor.The structure of described ultracapacitor is after activated carbon positive pole and activated carbon negative pole superpose successively or be wound as electrode cores, to be sealed in such as stainless steel or aluminum shell configuration example as cylindrical or square structure, and in this shell, to pour into nonaqueous electrolyte be assembled into hermetically sealed ultracapacitor.
The invention has the beneficial effects as follows the preparation method by proposing the novel active carbon electrode based on difference composition adhesive, effectively improve electrode structure intensity, reducing the internal resistance of electrode.Ultracapacitor based on novel active carbon electrode has good functional reliability, the ultracapacitor described in the present invention is at industrial uninterrupted power supply, motor vehicle, wind power generation, and the fields such as high-power military power supply, radio communication are widely used.
Accompanying drawing explanation
Fig. 1 is electrode multilayer structural representation
Fig. 2 is circular supercapacitor structural representation
Fig. 3 is square figure super capacitor structural representation
Embodiment
The invention discloses a kind of ultracapacitor based on active carbon electrode and the manufacture method thereof of the manufacturing technology scope belonging to capacitor.This capacitor, by activated carbon positive pole and activated carbon negative pole superposition or after being wound as electrode cores, to be sealed in such as stainless steel or aluminum shell configuration example as cylindrical structure or square structure.
Activated carbon positive pole and activated carbon negative pole are superposed by aluminium foil substrate, graphite electroconductive adhesive layer and active carbon coating respectively and form.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 aluminium foil substrate, reduce electrode internal resistance while can improving pole strength, above-mentioned technique can solve the technical barrier of adhesion strength difference between active carbon material and aluminium foil.
In a preferred embodiment of the invention, the positive pole of ultracapacitor and the difference of negative pole are that adopted adhesive ingredients is different, adhesive in positive pole is the mixture of polyvinylpyrrolidone and sodium carboxymethylcellulose, and the adhesive in negative pole is the mixture of styrene butadiene rubber latex and sodium carboxymethylcellulose.Compared with traditional polytetrafluoroethylene-sodium carboxymethylcellulose adhesive, the new type bonding agent adhesion strength that this patent adopts improves, and can solve the technical barrier of active carbon coating structural strength difference further.Positive pole adopts polyvinylpyrrolidone can solve styrene butadiene rubber latex technical barrier unstable under high potential.
Preferably, when preparing activated carbon positive pole, in the gross mass of described graphite electroconductive adhesive layer, the mass ratio of positive electrode binder is 10% to 20%, such as, be 10%, 15% or 20%; If the mass ratio of positive electrode binder is too low, then adhesion strength may be caused to reduce; If the mass ratio of positive electrode binder is too high, then may causes that electrode hardens, fragility increases.
Preferably, in the gross mass of described positive electrode binder, the mass ratio of described polyvinylpyrrolidone is 20% to 50%, such as, be 20%, 30%, 40% or 50%; If the mass ratio of described polyvinylpyrrolidone is too low, then may cause that adhesion strength reduces, electrode material comes off; If the mass ratio of described polyvinylpyrrolidone is too high, then electrode internal resistance may be caused to raise.
In addition preferably, the mass ratio between described polyvinylpyrrolidone and sodium carboxymethylcellulose is 1:3 to 3:1, is more preferably 1:3.
Further preferably, described graphite electroconductive adhesive layer is obtained by slurry, described slurry is adopted and is prepared with the following method: deionized water is heated to 35 DEG C to 45 DEG C and (controls in this temperature range, such as temperature can remain on arbitrary temp within the scope of this or temperature range, lower with), add described sodium carboxymethylcellulose and polyvinylpyrrolidone successively, then stir, add described graphite material again, after stirring, adopt colloid mill to carry out milled processed further.
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 substrate, and the thickness of the graphite electroconductive adhesive layer formed is 20 microns to 50 microns, such as, be 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 positive electrode binder is 5% to 10%, such as, be 5%, 7%, 8% or 10%.In addition preferably, in the gross mass of described positive electrode binder, the mass ratio of described polyvinylpyrrolidone is 20% to 50%, such as, be 20%, 30%, 40% or 50%.Further preferably, the mass ratio between described polyvinylpyrrolidone and sodium carboxymethylcellulose is 1:3 to 3:1, is more preferably 1:3.It is further preferred that the mass ratio of described active carbon material and acetylene black is 9:1; In addition further preferably, described active carbon coating is obtained by slurry, described slurry is adopted and is prepared with the following method: deionized water is heated to 35 DEG C to 45 DEG C, add described sodium carboxymethylcellulose and polyvinylpyrrolidone successively, then stir, add described acetylene black and active carbon material successively again, after stirring, adopt colloid mill to carry out milled processed further.
In addition preferably, described active carbon coating adopts the method for blade coating described slurry to be attached to described graphite electroconductive adhesive layer surface, the active carbon coating thickness formed is 100 microns to 200 microns, such as, can be 100 microns, 120 microns, 140 microns, 160 microns, 180 microns or 200 microns.
Preferably, when preparing activated carbon negative pole, in the gross mass of described graphite electroconductive adhesive layer, the mass ratio of described negative electrode binder is 10% to 20%, such as, be 10%, 15% or 20%; If the mass ratio of negative electrode binder is too low, then adhesion strength may be caused to reduce; If the mass ratio of negative electrode binder is too high, then may causes that electrode hardens, fragility increases.
Preferably, in the gross mass of described negative electrode binder, the mass ratio of described styrene butadiene rubber latex is 20% to 60%, such as, be 20%, 30%, 40% or 50%; If the mass ratio of described styrene butadiene rubber latex is too low, then may cause that adhesion strength reduces, electrode material comes off; If the mass ratio of described styrene butadiene rubber latex is too high, then electrode internal resistance may be caused to raise.In addition preferably, the mass ratio of described styrene butadiene rubber latex and sodium carboxymethylcellulose is 2:3 to 3:2, is more preferably 2:3.
In addition preferably, described graphite electroconductive adhesive layer is obtained by slurry, described slurry is prepared by the following method: deionized water is heated to 55 DEG C to 65 DEG C, add described sodium carboxymethylcellulose and styrene butadiene rubber latex successively, then stir, add described graphite material again, after stirring, adopt colloid mill to carry out milled processed further.
When preparing 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 substrate, the thickness of the graphite electroconductive adhesive layer formed is 20 microns to 50 microns, such as, be 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 electrode binder is 5% to 10%, such as, be 5%, 7%, 8% or 10%.In addition preferably, in the gross mass of described negative electrode binder, the mass ratio of described styrene butadiene rubber latex is 20% to 50%, such as, be 20%, 30%, 40% or 50%.Further preferably, the mass ratio between described styrene butadiene rubber latex and sodium carboxymethylcellulose is 2:3 to 3:2, is 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 obtained by slurry, described slurry is adopted and is prepared with the following method: deionized water is heated to 55 DEG C to 65 DEG C, add described sodium carboxymethylcellulose and styrene butadiene rubber latex successively, then stir, add described acetylene black and active carbon material successively again, after stirring, adopt colloid mill to carry out milled processed further.
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 the active carbon coating formed is 100 microns to 200 microns, such as, can be 100 microns, 120 microns, 140 microns, 160 microns, 180 microns or 200 microns.
In another aspect of the present invention, provide a kind of ultracapacitor, wherein, described ultracapacitor comprises positive pole, negative pole and shell, described positive pole and negative pole are respectively above-mentioned obtained electrode, described shell is stainless steel casing or aluminum shell, and described positive pole and negative pole successively superposition or winding become electrode cores and be placed in 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 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 circular supercapacitor structural representation, 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 figure super capacitor structural representation, and wherein 13 is liquid injection port
When assembling ultracapacitor, described electrode can adopt method such as thorn riveting or welding etc. to connect drainage strip, then after the techniques such as superposition and winding, electrode cores is formed, put into after drainage strip is connected with electrode terminal after stainless steel or aluminum shell connect top cover with calendering or welding manner and complete dry state encapsulation, dry state packaging semi-finished product is carried out to the processed such as vacuum drying at utmost to remove the moisture of capacitor internal, finally pour into nonaqueous electrolyte and after shutting liquid injection port, complete capacitor assembling.
Embodiment
Be further detailed the preferred embodiment of the present invention by the following examples, 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 embodiments.
Embodiment 1
1. positive electrode surface graphite electroconductive adhesive layer preparation.Get aluminium foil as electrode base sheet, adopt slurry spraying coating process (in the present invention, also can adopt doctor blade process) to prepare graphite electroconductive adhesive layer in its both side surface.Positive pole graphite electroconductive adhesive layer to be mixed with graphite material by positive electrode binder and forms, and wherein between positive electrode binder and graphite, mass ratio is 15:85.Positive electrode binder is the mixture of polyvinylpyrrolidone and sodium carboxymethylcellulose, and mass ratio is 1:3.Slurry preparation process is heated by deionized water and control, in the scope of 35 DEG C to 45 DEG C, to add sodium carboxymethylcellulose in advance and fully stir, and thoroughly stirs after then adding polyvinylpyrrolidone.Ratio according to the 15:85 between positive electrode binder and graphite adds graphite and fully stirs formation uniform sizing material.After utilizing colloid mill to carry out milled processed in prepared slurry, adopt spraying method to be coated on the both sides of aluminium foil substrate, conductive adhesive layer thickness is 40 microns.
2. positive-active carbon coat preparation.The positive pole graphite electroconductive adhesive layer surface-coated activated carbon layer prepared.Active carbon coating comprises positive electrode binder, active carbon material and acetylene black.Wherein, in the gross mass of active carbon coating, the mass ratio of positive electrode binder is 8%.Positive electrode binder is polyvinylpyrrolidone and sodium carboxymethylcellulose mixture, and polyvinylpyrrolidone and sodium carboxymethylcellulose optimum quality ratio are 1:3.In active carbon coating, active carbon material and acetylene black mass ratio are 9:1.Slurry preparation process is heated by deionized water and control in the scope of 35 DEG C to 45 DEG C, thoroughly stir after adding sodium carboxymethylcellulose and polyvinylpyrrolidone successively, fully stir after then adding acetylene black and active carbon material successively and carry out colloid mill milled processed further.Adopted by slurry knife coating procedure to be coated in graphite electroconductive adhesive layer surface uniformly, the thickness of prepared active carbon coating is 150 microns.
3. positive pole roller process.The electrode of the graphite electroconductive adhesive layer prepared and active carbon coating structure is carried out roller process, and at 110 DEG C of drying and processings, obtained positive pole thus.
4. the preparation of the graphite electroconductive adhesive layer of negative terminal surface.Get aluminium foil as electrode base sheet, adopt pulp spraying to be coated with preparation graphite electroconductive adhesive layer in its both side surface.Graphite electroconductive adhesive layer is the blend mixture of negative electrode binder and graphite material, and the mass ratio wherein between negative electrode binder and graphite is 15:85.Negative electrode binder is styrene butadiene rubber latex and sodium carboxymethylcellulose mixture, and its optimum quality ratio is 2:3.Slurry preparation process is heated by deionized water and control, in the scope of 55 DEG C to 65 DEG C, first to add sodium carboxymethylcellulose and fully stir, and thoroughly stirs after then adding styrene butadiene rubber latex.Add graphite according to the 15:85 ratio between negative electrode binder and graphite and fully stir and form uniform sizing material.Adopt spraying method to be coated on the both sides of aluminium foil substrate after utilizing colloid mill to carry out 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.In the graphite electroconductive adhesive layer surface-coated active carbon coating of the negative pole prepared.Active carbon coating is made up of the mixing of negative electrode binder, active carbon material and acetylene black.In the gross mass of active carbon coating, the mass ratio of negative electrode binder is 8%.Negative electrode binder 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.Slurry preparation process is heated by deionized water and control in the scope of 55 DEG C to 65 DEG C, thoroughly stir after adding sodium carboxymethylcellulose and styrene butadiene rubber latex successively, fully stir after then adding acetylene black and active carbon material successively and carry out colloid mill milled processed further.Adopted by slurry knife coating procedure to be coated with uniformly built in graphite electroconductive adhesive layer surface, the thickness of prepared active carbon coating is 150 microns.
6. negative pole roller process.The electrode of the graphite electroconductive adhesive layer prepared and active carbon coating structure is carried out roller process, and at 110 DEG C of drying and processings, obtains negative pole thus.
7. capacitor assembling technical process.As shown in Figures 2 and 3, prepared positive pole is connected drainage strip 9 with negative pole by method such as thorn riveting or welding etc., then with barrier film 7 through superposing and forming electrode cores 8 after the technique such as winding, aluminum shell is put into (in the present invention after being connected with electrode terminal 11 by drainage strip, also can adopt stainless steel casing) in 12 in the mode of calendering (in the present invention, also can adopt welding manner) connect top cover 10 after complete dry state encapsulation, by vacuum drying, processed is carried out to dry state packaging semi-finished product, at utmost to remove the moisture of capacitor internal, finally pour into nonaqueous electrolyte after shutting liquid injection port 13, obtained ultracapacitor.
Embodiment 2 and 3
Except the parameter listed by following table 1 and 2, implement embodiment 2 and 3 in the mode similar to embodiment 1.
The parameter relevant with materials and process of positive pole prepared by table 1
Note: the first mass ratio is the mass ratio of vinylpyrrolidone in the adhesive of graphite electroconductive adhesive layer and sodium carboxymethylcellulose; Second mass ratio is the mass ratio of polyvinylpyrrolidone in the adhesive of described active carbon coating and sodium carboxymethylcellulose; 3rd mass ratio is the mass ratio of active carbon material and acetylene black in described active carbon coating.
The parameter relevant with materials and process of negative pole prepared by table 2
Note: the 4th mass ratio is the mass ratio of styrene butadiene rubber latex in the adhesive of graphite electroconductive adhesive layer and sodium carboxymethylcellulose; 5th mass ratio is the mass ratio of styrene butadiene rubber latex in the adhesive of described active carbon coating and sodium carboxymethylcellulose; 6th mass ratio is the mass ratio of active carbon material and acetylene black in active carbon coating in described active carbon coating.
Measure the energy storage density of the adhesion strength of the active carbon material in electrode obtained in each embodiment and aluminium foil substrate and obtained ultracapacitor, discharge power and working life, result is as shown in table 3 below.
Electrode obtained in each embodiment of table 3 and the performance index of ultracapacitor
| 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 |
Note: adhesion strength is the adhesion strength in obtained active carbon electrode between active carbon material and aluminium foil substrate; Energy storage density, discharge power and working life are the energy storage density of obtained ultracapacitor, discharge power and working life.
Claims (20)
1. an active carbon electrode, wherein, described active carbon electrode comprises aluminium foil substrate, graphite electroconductive adhesive layer and active carbon coating, and is formed through rolling process process after superposition; Wherein, described graphite electroconductive adhesive layer comprises adhesive and graphite material;
When described active carbon electrode is as positive pole, described adhesive is positive electrode binder, and in the gross mass of described graphite electroconductive adhesive layer, the mass ratio of the positive electrode binder in described graphite electroconductive adhesive layer is 10% to 20%;
When described active carbon electrode is as negative pole, described adhesive is negative electrode binder, and in the gross mass of described graphite electroconductive adhesive layer, the mass ratio of the negative electrode binder in described graphite electroconductive adhesive layer is 10% to 20%.
2. active carbon electrode according to claim 1, wherein, described active carbon coating comprises active carbon material, acetylene black and described adhesive.
3. active carbon electrode according to claim 2, wherein, described positive electrode binder, comprises polyvinylpyrrolidone and sodium carboxymethylcellulose.
4. active carbon electrode according to claim 3, wherein, in the gross mass of described positive electrode binder, the mass ratio of the polyvinylpyrrolidone in described positive electrode binder is 20% to 50%.
5. active carbon electrode according to claim 3, the polyvinylpyrrolidone in described positive electrode binder and the mass ratio between sodium carboxymethylcellulose are 1:3.
6. active carbon electrode according to claim 3, described graphite electroconductive adhesive layer is obtained by slurry, described slurry is adopted and is prepared with the following method: deionized water is heated to 35 DEG C to 45 DEG C, add described sodium carboxymethylcellulose and polyvinylpyrrolidone successively, then stir, add described graphite material again, after stirring, adopt colloid mill to carry out milled processed further.
7. active carbon electrode according to claim 6, described graphite electroconductive adhesive layer adopts the method for spraying or blade coating described slurry to be attached to the surface of described aluminium foil substrate, and the thickness of the graphite electroconductive adhesive layer formed is 20 microns to 50 microns.
8. active carbon electrode according to claim 2, wherein, when described active carbon electrode is as positive pole, in the gross mass of described active carbon coating, the mass ratio of the positive electrode binder in described active carbon coating is 5% to 10%.
9. active carbon electrode according to claim 2, the mass ratio of described active carbon material and acetylene black is 9:1.
10. active carbon electrode according to claim 3, described active carbon coating is obtained by slurry, described slurry is adopted and is prepared with the following method: deionized water is heated to 35 DEG C to 45 DEG C, add described sodium carboxymethylcellulose and polyvinylpyrrolidone successively, then stir, add described acetylene black and active carbon material successively again, after stirring, adopt colloid mill to carry out milled processed further.
11. active carbon electrodes according to claim 10, described active carbon coating adopts the method for blade coating described slurry to be attached to described graphite electroconductive adhesive layer surface, and the active carbon coating thickness formed is 100 microns to 200 microns.
12. active carbon electrodes according to claim 2, wherein, described negative electrode binder, comprises styrene butadiene rubber latex and sodium carboxymethylcellulose.
13. active carbon electrodes according to claim 12, wherein, in the gross mass of described negative electrode binder, the mass ratio of the styrene butadiene rubber latex in described negative electrode binder is 20% to 60%.
14. active carbon electrodes according to claim 12, the styrene butadiene rubber latex in described negative electrode binder and the mass ratio of sodium carboxymethylcellulose are 2:3.
15. active carbon electrodes according to claim 12, described graphite electroconductive adhesive layer is obtained by slurry, described slurry is prepared by the following method: deionized water is heated to 55 DEG C to 65 DEG C, add described sodium carboxymethylcellulose and styrene butadiene rubber latex successively, then stir, add described graphite material again, after stirring, adopt colloid mill to carry out milled processed further.
16. active carbon electrodes according to claim 15, described graphite electroconductive adhesive layer adopts the method for spraying or blade coating described slurry to be attached to the surface of described aluminium foil substrate, and the thickness of the graphite electroconductive adhesive layer formed is 20 microns to 50 microns.
17. active carbon electrodes according to claim 2, wherein, when described active carbon electrode is as negative pole, in the gross mass of described active carbon coating, the mass ratio of the negative electrode binder in described active carbon coating is 5% to 10%.
18. active carbon electrodes according to claim 12, described active carbon coating is obtained by slurry, described slurry is adopted and is prepared with the following method: deionized water is heated to 55 DEG C to 65 DEG C, add described sodium carboxymethylcellulose and styrene butadiene rubber latex successively, then stir, add described acetylene black and active carbon material successively again, after stirring, adopt colloid mill to carry out milled processed further.
19. active carbon electrodes according to claim 18, described active carbon coating adopts the method for blade coating described slurry to be attached to the surface of described graphite electroconductive adhesive layer, and the thickness of the active carbon coating formed is 100 microns to 200 microns.
20. 1 kinds of ultracapacitors, wherein, described ultracapacitor comprises positive pole, negative pole and shell, described positive pole and/or negative pole all use the active carbon electrode described in claim 1-19 any one, described shell is stainless steel casing or aluminum shell, and described positive pole and negative pole successively superposition or winding become electrode cores and are placed in described shell, and described body seal has nonaqueous electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010129905.0A CN101923962B (en) | 2010-03-23 | 2010-03-23 | A kind of active carbon electrode and the ultracapacitor comprising this electrode |
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| CN104916445A (en) * | 2015-04-16 | 2015-09-16 | 宁波南车新能源科技有限公司 | Electrode for high compacted density and low contact internal resistance super capacitor, and preparation method thereof |
| CN105788887B (en) * | 2016-04-28 | 2019-02-26 | 中航锂电（洛阳）有限公司 | A kind of compound binding agent, using pole piece of compound binding agent preparation and preparation method thereof, application |
| CN107017096B (en) * | 2017-04-01 | 2019-07-19 | 苏州海凌达电子科技有限公司 | A kind of preparation method and applications of modified graphite electrode material |
| CN110428978A (en) * | 2019-07-28 | 2019-11-08 | 五邑大学 | One kind being based on NiMoO4The preparation method of the energy storage electrode of@graphite composite material |
| CN110797213B (en) * | 2019-12-12 | 2021-09-17 | 广东风华高新科技股份有限公司 | Super capacitor pole piece with C transition layer and preparation method thereof |
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| CN1483210A (en) * | 2000-05-12 | 2004-03-17 | ��ʤ�����ɷ�����˾ | Electrochemical double layer capacitor having carbon powder electrodes |
| CN101271767A (en) * | 2008-04-23 | 2008-09-24 | 江苏集晟电子科技有限公司 | Electrochemical super-capacitor and its production method |
| CN101436654A (en) * | 2007-11-13 | 2009-05-20 | 深圳市慧通天下科技股份有限公司 | Ferric phosphate lithium type safety high power lithium ion battery |
| CN101442120A (en) * | 2008-12-29 | 2009-05-27 | 朱经纬 | Electrode material and electrode containing the electrode and electrochemistry energy storage device containing the electrode |
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| KR100542887B1 (en) * | 2003-08-27 | 2006-01-11 | (주)에스와이하이테크 | Manufacturing Method for Electrode of electronic dual layer Capacitor and its Binder |
| WO2007032064A1 (en) * | 2005-09-14 | 2007-03-22 | Kitagawa Seiki Kabushiki Kaisha | Electrode for electric double layer capacitor and process for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1483210A (en) * | 2000-05-12 | 2004-03-17 | ��ʤ�����ɷ�����˾ | Electrochemical double layer capacitor having carbon powder electrodes |
| CN101436654A (en) * | 2007-11-13 | 2009-05-20 | 深圳市慧通天下科技股份有限公司 | Ferric phosphate lithium type safety high power lithium ion battery |
| CN101271767A (en) * | 2008-04-23 | 2008-09-24 | 江苏集晟电子科技有限公司 | Electrochemical super-capacitor and its production method |
| CN101442120A (en) * | 2008-12-29 | 2009-05-27 | 朱经纬 | Electrode material and electrode containing the electrode and electrochemistry energy storage device containing the electrode |
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