CN102637531B - Electrode of supercapacitor, preparation method of electrode and preparation method of slurry of electrode - Google Patents
Electrode of supercapacitor, preparation method of electrode and preparation method of slurry of electrode Download PDFInfo
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- CN102637531B CN102637531B CN201210074635.7A CN201210074635A CN102637531B CN 102637531 B CN102637531 B CN 102637531B CN 201210074635 A CN201210074635 A CN 201210074635A CN 102637531 B CN102637531 B CN 102637531B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/14—Arrangements or processes for adjusting or protecting hybrid or EDL capacitors
- H01G11/16—Arrangements or processes for adjusting or protecting hybrid or EDL capacitors against electric overloads, e.g. including fuses
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention provides a preparation method of slurry for an electrode of a supercapacitor, the electrode of the supercapacitor and a preparation method of the electrode of the supercapacitor. A eight-stage slurry preparation process is adopted in the preparation method of the slurry, and the preparation method of the slurry comprises the following steps of: I, dry mixing; II, wet mixing; III, lumping; IV, rubber mixing; V, roasting; VI, pelleting; VII, smashing; and VIII, slurry forming. The preparation method of the slurry can be used for increasing the solid content of the slurry, reducing the using amount of an adhesive, improving the dispersing effect of the slurry, realizing the quantitative control for the slurry preparation process and achieving better process stability and consistency. The electrode prepared by using the slurry has the advantages that the strength of the electrode is enhanced, the internal resistance of the electrode is reduced, the electrochemical stability and the structural stability of the electrode are improved, the reliability of the supercapacitor with the electrode is improved, and the service life of the supercapacitor is prolonged.
Description
Technical field
The present invention relates to ultracapacitor, relate in particular to the preparation method of a kind of electrode for super capacitor and preparation method thereof and a kind of electrode of super capacitor slurry.
Background technology
Ultracapacitor is a kind of Novel energy storage apparatus, integrate the characteristics such as high-energy-density, high power density, long-life (more than hundreds thousand of times), in addition it also has that capacity is large, internal resistance is little, the speed that discharges and recharges is fast, operating temperature range is wide (40 ℃～65 ℃), non-maintaining, high reliability, has application very widely in fields such as new forms of energy (wind energy and solar energy), communication, digital electric, electric power, automobile, engineering machinery, military affairs and Aero-Space.
Electrode is the core component of ultracapacitor, is made up of active material layer and collector, and its performance quality has critical impact to capacity, the internal resistance etc. of ultracapacitor.Conventionally, the Fabrication Technology of Electrode of ultracapacitor adopts slurry coating process, on collector, applies the mixed slurry of active material, conductive agent and binding agent, then drying, roll-in obtain activated carbon electrodes.Wherein, slurry preparation is the most key step in this kind of cloth of coating-type technology for preparing electrode.But, traditional electrode pulping process is and adopts single step slurrying, and pulping process is that dependence experience or qualitativeization observation analysis carry out to a great extent, therefore made slurry exists solid content low, dispersion effect is poor and unstable, the defects such as viscosity is larger and unstable, thus make that be coated with electrode exists that bonding is not firm, dry linting, pliability not and binding agent stop up the problems such as active carbon duct, further affect the chemical properties such as its capacity, internal resistance.
Summary of the invention
The present invention is the defect that solves above prior art, and a kind of electrode of super capacitor slurry and preparation method thereof is provided.
This electrode of super capacitor adopts eight segmentation pulping process preparations by the preparation method of slurry, and described eight segmentation pulping process comprise the steps:
I, be dry mixed, the mixer that is placed in sealing by active material and electric conducting material carries out high speed dispersion and is mixed to get dry mash;
II, wet mixing,, toward the solvent and the dispersant that add certain proportioning in step I gained dry mash, stir into wet-milling powder;
III, agglomerating,, toward a certain amount of dispersant of the continuous interpolation of Step II gained material relaying, suitably reduces mixing speed, makes it to form to have certain flexible bulk elastic material;
IV, glue refining, be smelt sheet elastic material by the bulk elastic material glue of Step II I gained;
V, baking, remove the moisture in the sheet elastic material of step IV gained, obtains dry sheet elastic material;
VI, granulation, be ground into the fine particle of certain particle diameter by the dry sheet elastic material of step V gained;
VII, pulverizing, be ground into powder by the fine particle of step VI gained;
VIII, pulping add a certain amount of dispersant, solvent and binding agent, and stir into slurry in step VII gained material.
Also can adopt following preferred technical scheme according to this electrode of super capacitor of embodiment by the preparation method of slurry:
In described Step II, III, IV, VI, VII, VIII, control temperature at 20 ℃～55 ℃, the solid content of described step VIII is controlled at 25%～35%.
Described active material is at least one in active carbon, CNT (carbon nano-tube), carbon black, nano carbon fiber, charcoal-aero gel, Graphene, metal oxide, conducting polymer and organic carbonizing production, and described active material is the form of powder or fiber.
Described electric conducting material is selected from least one in electrically conductive graphite, conductive black and acetylene black.
Described dispersant is selected from one or several in sodium carboxymethylcellulose, water-base cement, polytetrafluoroethylene and Kynoar.
Described solvent is selected from one or more in water, 1-METHYLPYRROLIDONE, ethanol, propyl alcohol and isopropyl alcohol.
Described the first binding agent is selected from one or several in sodium carboxymethylcellulose, water-base cement, polytetrafluoroethylene, Kynoar, butadiene-styrene rubber, and described the second binding agent is selected from one or several in Kynoar, polytetrafluoroethylene, polyphenylene sulfide, polyethylene and polypropylene.
The present invention also provides a kind of preparation method of electrode for super capacitor, and it comprises the steps:
A. slurrying, prepares slurry by active material, electric conducting material, dispersant, binding agent and solvent;
B. slurry coating, is coated on collector by steps A gained slurry, becomes preliminary treatment electrode;
C. dry, toast to remove volatile ingredient wherein by described preliminary treatment electrode;
D. roll-in, by step C gained preliminary treatment pole piece roll-in compacting, becomes electrode;
It is characterized in that, described steps A adopts aforementioned arbitrary described preparation method preparation.
According to embodiment, the preparation method of electrode for super capacitor of the present invention also can adopt following preferred technical scheme:
Described slurry coating adopts extruding, transfer or blade coating mode.
In described slurry, each solid matter comprises: the described active material of 60～100 mass parts, the described electric conducting material of 0～15 mass parts, the described dispersant of 0～5 mass parts, described binding agent comprises the first binding agent of 0～10 mass parts and the second binding agent of 0～10 mass parts.
In described step C, adopt hot air drier to toast described preliminary treatment electrode, the hot air temperature of described hot air drier is set as near the boiling point of solvent.
Described collector is aluminium foil or corrosive aluminum foil, and aluminum foil thickness is preferably 10 μ m～50 μ m.
The present invention also provides a kind of electrode for super capacitor, comprise slurry and collector, described slurry is coated on described collector, wherein, described slurry adopts aforementioned arbitrary described ultracapacitor slurry, adopts preparation method's preparation of aforementioned arbitrary described electrode for super capacitor.
Preferably, described collector is aluminium foil or corrosive aluminum foil.
Further preferred, the thickness of described aluminium foil or corrosive aluminum foil is 10 μ m～50 μ m.
Preferred again, the thickness that is coated on the slurry on described collector is 40 μ m～400 μ m.
By a large amount of tests, applicant finds according to aforesaid I～VIII step operation, this slurry preparation method can improve slurry solid content, reduce the use amount of bonding agent, improve the dispersion effect of slurry, reduce the viscosity of slurry, realize the slurry preparation process that preparation dispersiveness and caking property are good controlled.The electrode that uses this slurry to prepare has improved pole strength, reduce the internal resistance of electrode, improve the electrical conductance of electrode, improved electrochemical stability and the structural stability of electrode, strengthened by the reliability of the ultracapacitor of this electrode fabrication and increase the service life.
Accompanying drawing explanation
Fig. 1 is eight segmentation pulping process flow figure of the present invention;
Fig. 2 is the preparation flow schematic diagram of electrode of super capacitor of the present invention;
Fig. 3 is the scanning electron microscope (SEM) photograph of 2000 times of the prepared super capacitor electrode slices of the embodiment of the present invention 1;
Fig. 4 is the scanning electron microscope (SEM) photograph of 5000 times of the prepared super capacitor electrode slices of the embodiment of the present invention 1;
Fig. 5 is the scanning electron microscope (SEM) photograph of 10000 times of the prepared super capacitor electrode slices of the embodiment of the present invention 1.
Embodiment
Eight segmentation pulping process flows of the present invention as shown in Figure 1, mainly comprise the following steps:
I, be dry mixed, the mixer that is placed in sealing by active material and conductive agent carries out high speed dispersion and is mixed to get dry mash;
II, wet mixing,, toward the solvent and the dispersant that add certain proportioning in step I gained dry mash, stir into wet-milling powder; In this step, control temperature at 20 ℃～55 ℃, control solid content 70%～80%.
III, agglomerating,, toward a certain amount of dispersant of the continuous interpolation of Step II gained material relaying, increases mixing speed, makes it to form to have flexible bulk elastic material; Control solid content 50～60%, and keep temperature of charge at 20 ℃～55 ℃.
IV, glue refining, be smelt sheet elastic material by the bulk elastic material of Step II I gained with flour stranding machine glue; And keep temperature of charge at 20 ℃～55 ℃.
V, baking, remove the moisture in the sheet elastic material of step IV gained by convection oven, obtains dry sheet elastic material.
VI, granulation, be ground into the fine particle of 2～10mm by the dry sheet elastic material of step V gained; And keep temperature of charge at 20 ℃～55 ℃.
VII, pulverizing, be ground into the powder of 0.01～0.1mm by the fine particle of step VI gained; And keep temperature of charge at 20 ℃～55 ℃.
VIII, pulping add a certain amount of dispersant, solvent and binding agent, and stir into slurry in step VII gained material.Specifically comprise the steps: 1) in step VII gained mixed material, add a certain amount of dispersant and solvent, controlling solid content is 30%～40%, vacuum high speed dispersion stirs certain hour and obtains slurry, and to adjust slurry viscosity be 1200mPaS～2500mPaS; 2) in step 1) gained slurry, add the first binding agent after dilution process, vacuum stirring certain hour, adjustment slurry viscosity is 1000mPaS～2000mPaS; 3) toward step 2) add the second binding agent emulsion through ultrasonic processing in gained slurry, vacuum stirring certain hour, controlling solid content is 25～35%, adjustment viscosity is 1000mPaS～2000mPaS.
" solvent and the conducting resinl of certain proportioning " in abovementioned steps II can be determined according to solid content, as long as can meet the requirement of solid content.Similarly, aforementioned " a certain amount of conducting resinl ", " a small amount of conducting resinl " are also to determine according to solid content.
Aforementioned eight steps are overall processes, and a large amount of tests show, by complete so whole process, can solve the problem that solid content is low simultaneously, dispersion effect is poor and viscosity is larger.
The present invention practices in two processes at agglomerating, glue, can solve following two problems, 1, dispersion effect problem: owing to being at solid-state state but not under solution (liquid state) state, tiny conductive particle being disperseed, so do not deposit (can avoid) phenomenon that conductive agent is reunited after dispersion.The existence of appropriate bonding agent, can guarantee that fine particle conductive agent disperses closely bonding of rear and active material.2, solid content problem: bonding agent/dispersant is act on material lip-deep, particle is less, the surface area of whole material is just larger, the amount of the required use of bonding agent/dispersant is just more, and the quantity of solvent that the use amount of bonding agent/dispersant needs is at most large, the ratio of solid matter in whole slurry reduces, and causes solid content low.Simultaneously in granulation and pulverizing two steps, because the particle that agglomerating, two steps of glue white silk are made into is above the body of combining closely of active material and conductive particle, the granularity of whole particle is increased, thereby specific area obviously diminishes, like this, in follow-up pulping operation, can obtain the slurry of viscosity lower (being that binding agent is less).Meanwhile, conductive agent is dispersed preferably, can obviously reduce the use amount of the conductive agent that particle is less, specific area is large, thereby improves solid content.
Large and the solid content low of viscosity is two complementary factors, because after slurry makes, require viscosity within the specific limits, could normally carry out next process processing, has controlled solid content well, has also just solved viscosity problem.
Above eight steps, previous section is mainly the dispersion of particle and bonding, is to reduce specific surface, increases dispersed.Aft section has drying course, and the bonding agent that main cause is used before and after being is different with dicyandiamide solution, and follow-up pulping need to be avoided the impact of forward part solvent.
The preparation flow schematic diagram of electrode for super capacitor of the present invention is as Fig. 2, and it mainly comprises the steps:
A. slurrying, prepares slurry by active material, conductive agent, dispersant, binding agent and solvent;
B. slurry coating, is coated on collector by steps A gained slurry, becomes preliminary treatment electrode;
C. dry, toast to remove volatile ingredient wherein by described preliminary treatment electrode;
D. roll-in, by step C gained preliminary treatment pole piece roll-in compacting, becomes electrode.
Below in conjunction with accompanying drawing, the present invention is described in further detail, so that those skilled in the art can be implemented according to this with reference to specification word.
Embodiment 1
First, by proportioning, the water of the first binding agent of the dispersant of the conductive black of the active carbon of 100 parts of mass parts, 9.3 parts of mass parts, 3.1 parts of mass parts, 3.5 parts of mass parts and 220 parts of mass parts is mixed with to slurry, slurry preparation process is as follows:
Active carbon and conductive black are placed in to the bipyramid efficient material mixer high speed batch mixing 8 hours of sealing, the dry blend that obtains fully mixing; Then add water and dispersant (dispersant temperature is controlled at 20～55 ℃), control solid content 70%～80%, use power mixer to stir 1h, batch mixing becomes wet-milling powder.Continue to add dispersant, control solid content 50%～60%, increase mixing speed, make it formation and there is flexible bulk material (pliability refers to that object is after stress deformation, not the character of frangibility); Use flour stranding machine that bulk material glue is smelt to sheet resilient materials; The convection oven that sheet resilient materials is placed in to 120 ℃ is toasted 8h, obtains dry sheet resilient materials; Use comminutor dry sheet resilient materials to be a granulated into the fine particle of particle diameter 2mm～10mm; Use pulverizer fine particle to be ground into the powder of 0.01～0.1mm.Test shows, by granulation and two steps of pulverizing, can obtain the powder of better effect.In powder, add dispersant and water, control solid content 36%～38%, use power mixer to stir 1h.Then vacuum high-speed stirred 0.5h, adds water to adjust slurry viscosity as 1200mPaS～2500mPaS, presents without bubble and obvious particle.Add the first binding agent (the common methods for dilution process here, as dilute with water etc.) after dilution process, vacuum stirring 0.5h, obtains described coating sizing-agent; Secondly, adopt coating machine to coat with the coating speed of 10m/min on the corrosive aluminum foil of 30 μ m, the thickness of coating is between 80 μ m～400 μ m; Then, by described coating pole piece through a heat drying apparatus to remove the water in pole piece; Finally, described dry pole piece is finally made to electrode for super capacitor of the present invention by twin rollers roll-in.In above step, each addition of dispersant and water need meet the prerequisite of controlling solid content.
Calculating after tested, is 1800PaS by the prepared slurry viscosity of eight segmentation pulping process of the present invention, and solid content is 34.1%.This has improved the solid content of slurry than the pulp-making method of prior art, has reduced the viscosity of coating sizing-agent; Further, by adopting activated carbon particles and conductive black distribution of particles excellent in uniform (seeing accompanying drawing 3-5) in described slurry coating gained pole piece, and through 5 nothing fractures of doubling, fall to expect phenomenon, pliability is good.This rubbing method compared to existing technology, reduces the internal resistance of electrode, improves the electrical conductance of electrode, improves electrochemical stability and the structural stability of electrode, strengthens by the reliability of the ultracapacitor of this electrode fabrication and increases the service life.
In this embodiment, described dispersant comprises one or several of sodium carboxymethylcellulose (CMC), water-base cement, polytetrafluoroethylene (PTFE), Kynoar (PVDF).The first binding agent comprises one or several in sodium carboxymethylcellulose (CMC), water-base cement, polytetrafluoroethylene (PTFE), Kynoar (PVDF), butadiene-styrene rubber (SBR).
In this embodiment, described heat drying apparatus adopts hot air drier, and hot air temperature is to be better set near the boiling point of solvent, by except desolventizing, obtains electrode of the present invention.
Embodiment 2
First, by proportioning, the water of the first binding agent of the dispersant of the electrically conductive graphite that comprises active carbon, 9.3 parts of mass parts of 100 parts of mass parts, 3.8 parts of mass parts, 3.4 parts of mass parts, 272 parts of mass parts is mixed with to slurry, slurry preparation process is as follows:
Active carbon and conductive black are placed in to the bipyramid efficient material mixer high speed batch mixing 8 hours of sealing, the dry blend that obtains fully mixing; Then add water and dispersant (dispersant temperature is controlled at 20～55 ℃), control solid content 70%～80%, use power mixer to stir 1h, batch mixing becomes wet-milling powder.Continue to add dispersant, control solid content 50%～60%, increase mixing speed, make it formation and there is flexible bulk material; Use flour stranding machine that bulk material glue is smelt to sheet resilient materials; The convection oven that sheet resilient materials is placed in to 120 ℃ is toasted 8h, obtains dry sheet resilient materials; Use comminutor dry sheet resilient materials to be a granulated into the fine particle of particle diameter 2mm～10mm; Use pulverizer fine particle to be ground into the powder of 0.01～0.1mm.In powder, add dispersant and water, control solid content 36%～38%, use power mixer to stir 1h.Then vacuum high-speed stirred 0.5h, adjustment slurry viscosity is 1200mPaS～2500mPaS, presents without bubble and obvious particle.Add the first binding agent after dilution process, vacuum stirring 1h, obtains described coating sizing-agent; Secondly, adopt coating machine to coat with the coating speed of 3m/min on the corrosive aluminum foil of 30 μ m, the thickness of coating is between 80 μ m～400 μ m; Then, by described coating pole piece through a heat drying apparatus to remove the volatile ingredient (solvent etc.) in electrode; Finally, described dry pole piece is finally made to electrode for super capacitor of the present invention by twin rollers roll-in.
Calculating after tested, is 1700mPaS by the prepared slurry viscosity of eight segmentation pulping process of the present invention, and solid content is 29.5%.This has improved the solid content of slurry than the pulp-making method of prior art, has reduced the viscosity of coating sizing-agent; Further, by adopting activated carbon particles and electrically conductive graphite distribution of particles excellent in uniform in described slurry coating gained pole piece, and through 5 nothing fractures of doubling, fall to expect phenomenon, pliability is good.This rubbing method compared to existing technology, reduces the internal resistance of electrode, improves the electrical conductance of electrode, improves electrochemical stability and the structural stability of electrode, strengthens with the reliability of the ultracapacitor of this electrode fabrication and growth useful life.
In this embodiment, described dispersant comprises one or several of sodium carboxymethylcellulose (CMC), water-base cement, polytetrafluoroethylene (PTFE), Kynoar (PVDF).The first binding agent comprises one or several in sodium carboxymethylcellulose (CMC), water-base cement, polytetrafluoroethylene (PTFE), Kynoar (PVDF), butadiene-styrene rubber (SBR).
In this embodiment, described heat drying apparatus adopts hot air drier, and hot air temperature is to be better set near the boiling point of solvent, by except desolventizing, obtains electrode of the present invention.
Embodiment 3
First, by proportioning, the water of the second binding agent of the first binding agent of the dispersant of the conductive black of the active carbon of 80 parts of mass parts, 5 parts of mass parts, 2 parts of mass parts, 3 parts of mass parts, 3 parts of mass parts and 296 parts of mass parts is mixed with to slurry.Wherein, active carbon is YP-50, and distributors is Kuraray Chemical Co.Ltd., Shin-hankyu Bldg.9F.Blvd.C-237,1-12-39Umeda Kiataku, Osaka, 530-8611, Japan; Conductive black is SUPER S, and distributors is TIMCAL Belgium S.A., B-1050Bruxelles, Belgium; Dispersant is WAL CRT30000P, and distributors is CM industrial chemical co., Ltd; The first binding agent is LA133, and distributors is CHENGDU INDIGO POWER SOURCES CO., LTD; The second binding agent is SFN-1, the ZHONGHAO CHENGUANG RESERRCH INSTITUTE OF CHEMICAL INDUSTAY of distributors.Slurry preparation process is as follows:
Active carbon and conductive black are placed in to the bipyramid efficient material mixer high speed batch mixing 8 hours of sealing, the dry blend that obtains fully mixing; Then add water and dispersant (dispersant temperature is controlled at 20～55 ℃), control solid content 70%～80%, use power mixer to stir 1h, batch mixing becomes wet-milling powder.Continue to add dispersant, control solid content 50%～60%, increase mixing speed, make it formation and there is flexible bulk material; Use flour stranding machine that bulk material glue is smelt to sheet resilient materials; The convection oven that sheet resilient materials is placed in to 120 ℃ is toasted 8h, obtains dry sheet resilient materials; Use comminutor dry sheet resilient materials to be a granulated into the fine particle of particle diameter 2mm～10mm; Use pulverizer fine particle to be ground into the powder of 0.01～0.1mm.In powder, add dispersant and water, control solid content 36%～38%, use power mixer to stir 1h.Then vacuum high-speed stirred 0.5h, adjustment slurry viscosity is 1200mPaS～2500mPaS, presents without bubble and obvious particle.Add the first binding agent after dilution process, vacuum stirring 1.5h, adds the second bonding agent, and vacuum stirring 0.5h regulates viscosity 1200mPaS～2500mPaS, obtains described coating sizing-agent; Secondly, adopt coating machine to coat with the coating speed of 10m/min on the corrosive aluminum foil of 30 μ m, the thickness of coating is between 40 μ m～400 μ m; Then, by described coating pole piece through a heat drying apparatus to remove the volatile ingredient (solvent etc.) in electrode; Finally, described dry pole piece is finally made to electrode for super capacitor of the present invention by twin rollers roll-in.
Calculating after tested, is 1750mPaS by the prepared slurry viscosity of eight segmentation pulping process of the present invention, and solid content is 34.5%.This has improved the solid content of slurry than the pulp-making method of prior art, has reduced the viscosity of coating sizing-agent; Further, by adopting activated carbon particles and conductive black distribution of particles excellent in uniform in described slurry coating gained pole piece, and through doubling 5 times and above nothing fracture, fall to expect phenomenon, pliability is good.This rubbing method compared to existing technology, reduces the internal resistance of electrode, improves the electrical conductance of electrode, improves electrochemical stability and the structural stability of electrode, strengthens with the reliability of the ultracapacitor of this electrode fabrication and growth useful life.
Although embodiment of the present invention are open as above, but it is not restricted to listed utilization in specification and execution mode, it can be applied to various applicable the field of the invention completely, for those skilled in the art, can easily realize other modification, therefore do not deviating under the universal that claim and equivalency range limit, the present invention is not limited to specific details and illustrates here and the legend of describing.
Claims (10)
1. a preparation method for slurry for electrode of super capacitor, is characterized in that described slurry adopts eight segmentation pulping process preparations, and described eight segmentation pulping process comprise the steps:
I, be dry mixed, the mixer that is placed in sealing by active material and electric conducting material carries out high speed dispersion and is mixed to get dry mash;
II, wet mixing,, toward the solvent and the dispersant that add certain proportioning in step I gained dry mash, stir into wet-milling powder;
III, agglomerating,, toward a certain amount of dispersant of the continuous interpolation of Step II gained material relaying, suitably reduces mixing speed, makes it to form to have certain flexible bulk elastic material;
IV, glue refining, be smelt sheet elastic material by the bulk elastic material glue of Step II I gained;
V, baking, remove the moisture in the sheet elastic material of step IV gained, obtains dry sheet elastic material;
VI, granulation, be ground into the fine particle of certain particle diameter by the dry sheet elastic material of step V gained;
VII, pulverizing, be ground into powder by the fine particle of step VI gained;
VIII, pulping add a certain amount of dispersant, solvent and binding agent, and stir into slurry in step VII gained material.
2. the preparation method of slurry for electrode of super capacitor as claimed in claim 1, is characterized in that: in described Step II, III, IV, VI, VII, VIII, control temperature at 20 ℃～55 ℃, the solid content of described step VIII is controlled at 25%～35%.
3. the preparation method of slurry for electrode of super capacitor as claimed in claim 1, is characterized in that: described binding agent comprises the first binding agent and the second binding agent.
4. the preparation method of slurry for electrode of super capacitor as claimed in claim 1, it is characterized in that: described active material is at least one in active carbon, CNT (carbon nano-tube), carbon black, nano carbon fiber, charcoal-aero gel, Graphene, metal oxide, conducting polymer and organic carbonizing production, and described active material is the form of powder or fiber.
5. the preparation method of slurry for electrode of super capacitor as claimed in claim 1, is characterized in that: described electric conducting material is selected from least one in electrically conductive graphite, conductive black and acetylene black.
6. the preparation method of slurry for electrode of super capacitor as claimed in claim 1, is characterized in that: described dispersant is selected from one or several in sodium carboxymethylcellulose, water-base cement, polytetrafluoroethylene and Kynoar.
7. the preparation method of slurry for electrode of super capacitor as claimed in claim 3, it is characterized in that: described the first binding agent is selected from one or several in sodium carboxymethylcellulose, water-base cement, polytetrafluoroethylene, Kynoar, butadiene-styrene rubber, described the second binding agent is selected from one or several in Kynoar, polytetrafluoroethylene, polyphenylene sulfide, polyethylene and polypropylene.
8. a preparation method for electrode for super capacitor, comprises the steps:
A. slurrying, prepares slurry by active material, electric conducting material, dispersant, binding agent and solvent;
B. slurry coating, is coated on collector by steps A gained slurry, becomes preliminary treatment electrode;
C. dry, toast to remove volatile ingredient wherein by described preliminary treatment electrode;
D. roll-in, by step C gained preliminary treatment pole piece roll-in compacting, becomes electrode;
It is characterized in that the preparation method as described in described steps A employing is as arbitrary in claim 1～7.
9. the preparation method of electrode for super capacitor as claimed in claim 8, is characterized in that: described slurry coating adopts extruding, transfer or blade coating mode.
10. the preparation method of electrode for super capacitor as claimed in claim 8, it is characterized in that: in described slurry, each solid matter comprises: the described active material of 60～100 mass parts, the described electric conducting material of 0～15 mass parts, the described dispersant of 0～5 mass parts, described binding agent comprises the first binding agent of 0～10 mass parts and the second binding agent of 0～10 mass parts.
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| CN110459410A (en) * | 2019-07-24 | 2019-11-15 | 中国科学院山西煤炭化学研究所 | A preparation method of supercapacitor slurry and supercapacitor prepared by using supercapacitor slurry |
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Family Cites Families (5)
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| KR100377950B1 (en) * | 2000-06-16 | 2003-03-29 | 성남전자공업주식회사 | Method for manufacturing lithium polymer battery |
| AU2002214042A1 (en) * | 2000-11-09 | 2002-05-21 | Foc Frankenburg Oil Company Est. | A supercapacitor and a method of manufacturing such a supercapacitor |
| CN102044345A (en) * | 2009-10-13 | 2011-05-04 | 上海空间电源研究所 | Preparation method of active carbon electrode for double electric layer capacitor |
| CN101980396A (en) * | 2010-09-08 | 2011-02-23 | 秦皇岛市芯驰光电科技有限公司 | Method for preparing lithium ion battery anode paste |
| CN102148363A (en) * | 2011-03-10 | 2011-08-10 | 湖南丰源业翔晶科新能源股份有限公司 | Preparation method of stable slurry of lithium ion battery |
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Address after: 518057 Guangdong city of Shenzhen province Nanshan District Gao Xin Road No. 009 China Technology Development Institute Technology Park building three, 202 building, room 306 Patentee after: TIG TECHNOLOGY CO., LTD. Address before: 518057 Guangdong city of Shenzhen province Nanshan District Gao Xin Road No. 009 China Technology Development Institute Technology Park building three, 202 building, room 306 Patentee before: Shenzhen City TIG New Energy Technologies Co., Ltd. |