CN110491685B - Preparation method and application of graphene supercapacitor slurry - Google Patents
Preparation method and application of graphene supercapacitor slurry Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 105
- 239000002002 slurry Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 92
- 239000006185 dispersion Substances 0.000 claims abstract description 45
- 238000004898 kneading Methods 0.000 claims abstract description 45
- 239000000853 adhesive Substances 0.000 claims abstract description 39
- 230000001070 adhesive effect Effects 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 238000005096 rolling process Methods 0.000 claims abstract description 9
- 238000004804 winding Methods 0.000 claims abstract description 9
- 239000007772 electrode material Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims description 33
- 239000003990 capacitor Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 15
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000011149 active material Substances 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 238000009830 intercalation Methods 0.000 claims description 4
- 230000002687 intercalation Effects 0.000 claims description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 230000033116 oxidation-reduction process Effects 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 claims description 2
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- VPOIXCYASUPXIC-UHFFFAOYSA-J tetrasodium oxalate Chemical compound C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-].[Na+].[Na+].[Na+].[Na+] VPOIXCYASUPXIC-UHFFFAOYSA-J 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 1
- 238000004146 energy storage Methods 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 2
- 238000010924 continuous production Methods 0.000 abstract 1
- 238000007865 diluting Methods 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 4
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910009361 YP-50F Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012257 stirred material Substances 0.000 description 1
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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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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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
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/60—Liquid electrolytes characterised by the solvent
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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
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
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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
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
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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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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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- Crystallography & Structural Chemistry (AREA)
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a preparation method of graphene supercapacitor slurry and a graphene supercapacitor prepared from the graphene supercapacitor slurry, and belongs to the technical field of supercapacitor energy storage devices. The preparation method of the graphene supercapacitor slurry comprises the following steps: adding graphene powder into a dispersion liquid of an adhesive, stirring and dispersing to prepare an adhesive dispersion liquid containing graphene, kneading and stirring the graphene adhesive dispersion liquid and an electrode active material in batches, diluting with a solvent, stirring and dispersing to finally obtain a slurry, and preparing the supercapacitor through coating, rolling, slitting, winding, injecting and other processes. The slurry is simple and rapid in preparation method, continuous production is easy to realize, the obtained slurry graphene is good in dispersibility, the prepared pole piece has low membrane resistivity, and the prepared graphene supercapacitor has high energy density, low direct-current resistance and high power density.
Description
Technical Field
The invention belongs to the technical field of new energy storage devices, and particularly relates to a preparation method of graphene supercapacitor slurry and a graphene supercapacitor prepared from the graphene supercapacitor slurry.
Background
The super capacitor has the advantages of high power density, long cycle life, excellent low temperature and safety performance and the like, and has huge application prospects in the fields of start-stop power supplies of electric automobiles, urban public rail transit, large-scale photovoltaic and wind power energy storage of the electric automobiles. In order to meet the increasing demands, the invention is always a hot point for research and invention in order to improve the performance of the super capacitor from the aspects of materials, processes and the like and prepare capacitor products with high energy density, high power density and long cycle life.
Graphene has a great application prospect in the field of supercapacitors due to its large specific surface area and high conductivity, but graphene must be well dispersed in the use process to exert its excellent characteristics, however, the problem of graphene dispersion has been concerned by the scientific and industrial circles, and usually auxiliary materials such as dispersants are added, but on one hand, the addition of dispersants brings increased cost, on the other hand, these materials do not have any benefit to the improvement of supercapacitors, but rather, energy density and power density are reduced. The graphene-like carbon nanomaterial has a high oil absorption value, so that graphene with low solid content has high viscosity, and therefore, the graphene is directly added into the active electrode, so that the graphene is difficult to disperse, the excellent performance of the graphene cannot be exerted, and the solid content of the slurry is reduced, so that the surface density and the compaction density of a pole piece are influenced, and the energy density of a capacitor is further influenced. Patent CN 106847534 is an acid treatment of activated carbon, in which graphene oxide is dissolved in a solvent and then undergoes a condensation reaction with a polymer to obtain a graphene oxide colloid with positive charges on the surface, and a graphene oxide-coated activated carbon composite slurry is formed by an electrostatic self-assembly technique, so that graphene and an active material can be well compounded.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of graphene supercapacitor slurry and a graphene supercapacitor prepared by using the graphene supercapacitor slurry, in particular to a preparation method of capacitance composite electrode slurry.
The invention is realized by the following technical scheme.
A preparation method of graphene supercapacitor slurry comprises the following steps:
1) graphene adhesive dispersion liquid preparation
Adding graphene into a dispersion liquid of an adhesive for stirring and dispersing, wherein the mass ratio of the graphene to the adhesive is 1: 2-1: 20, the solid content of the graphene is 0.1% -10%, the stirring speed is 10-100 r/min, the dispersing speed is 800-3000 r/min, and the stirring and dispersing time is 30-600 min;
2) kneading and mixing the electrode active material and the graphene binder dispersion liquid step by step
Firstly, taking 20-70% of the total amount of the graphene adhesive dispersion liquid prepared in the step 1), adding an active electrode material into the adhesive graphene mixed liquid, and kneading, stirring and mixing in a first step, wherein the electrode active material comprises a conductive agent and one or a mixture of more of active carbon, active carbon fibers, capacitance carbon, graphite or carbon materials in other forms, and the specific surface area of the active carbon material is more than 1500m2The solid content of kneading is 30-90%, the stirring speed is 5-100 r/min, and the kneading time is 10-180 min; then adding the rest graphene adhesive dispersion liquid prepared in the step 1) into the mixture obtained after the first-step kneading and stirring, and carrying out second-step kneading and stirring, wherein the solid content of the second-step kneading is 25-85%, and the whole material ratio is as follows: the active material is graphene adhesive dispersion liquid, wherein the conductive agent accounts for 70-95%, 4.5-20%, 0.5-10%, the kneading and stirring speed is 5-100 r/min, and the kneading and stirring time is 30-600 min;
3) adding a solvent to dilute and disperse
After the step 2) is finished, adding a solvent into a stirring tank for dilution, stirring and dispersion, wherein the whole stirring and dispersion process is carried out in a vacuum environment, the main purpose of dispersion under the vacuum condition is to eliminate bubbles and avoid influencing the dispersion uniformity of materials, the solid content is 20-80%, the stirring speed is 10-100 r/min, the dispersion speed is 500-3000 r/min, the stirring and dispersion time is 10-600 min, and the graphene supercapacitor slurry is prepared, wherein the viscosity range of the graphene supercapacitor slurry is 3000-8000 mPa.S.
Further, the graphene in the step 1) is prepared by an oxidation-reduction method, a physical stripping method, a physical intercalation or a chemical intercalation, and the adhesive is one or more of polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, sodium carboxymethylcellulose and sodium alginate.
Further, the concentration of graphene in the graphene adhesive dispersion liquid in the step 1) is 0.5-5%, the concentration of graphene is too low, a complete conductive network cannot be formed, the internal resistance of the super capacitor is increased, the concentration of graphene is too high, the dispersion difficulty is high, the solid content of slurry is reduced, and the stability is poor; the ratio of the graphene to the adhesive is 1: 5-1: 15, the ratio is too low, the content of the adhesive is low, and the electrode plate is easy to fall off powder to influence the performance of the device. The proportion is too high, the proportion of the adhesive is too high, the internal resistance is increased, and the energy density of the device is reduced.
Further, in the step 1), the stirring speed is 20-50 r/min, the dispersing speed is 1000-2000 rpm, the stirring dispersing time is 60-300 min, the stirring dispersing speed is too low, the time is too short, the mixing among particles is not facilitated, the stirring dispersing speed is too high, the stirring time is too long, the stirring efficiency is reduced, and the loss of equipment is large.
Further, the solid content of the first-step kneading and stirring in the step 2) is 30-90%, the first-step kneading and stirring speed is 5-100 r/min, and the kneading time is 10-180 min; and in the second step, the solid content of the second step is 25-85%, and the kneading and stirring time is 30-600 min.
Further, the solvent in the step 3) is one of water, ethanol and nitrogen methyl pyrrolidone or a mixed solvent of a plurality of solvents.
Further, in the step 3), the stirring speed is 20-50 rpm, the dispersing speed is 1000-2000 rpm, and the stirring dispersing time is 60-300 min.
A graphene supercapacitor prepared by using graphene supercapacitor slurry is prepared by coating, rolling, slitting, winding and injecting the prepared graphene supercapacitor slurry to prepare the graphene supercapacitor, wherein a current collector used for coating is a carbon-coated aluminum foil, and an electrolyte solvent injected into the capacitor comprises one or more of ethylene carbonate, propylene carbonate, gamma-butyrolactone, dimethyl carbonate, diethyl carbonate, butylene carbonate, ethyl methyl carbonate and acetonitrile; solute in the electrolyte is at least one of sodium perchlorate, sodium hexafluorophosphate, sodium trifluoromethanesulfonate, sodium bis (trifluoromethanesulfonyl) imide, sodium bisoxalate, sodium hexafluoroarsenate, tetraethylene glycol dimethyl ether, tetraethylammonium tetrafluoroborate and spiro quaternary ammonium salt.
The method comprises the steps of premixing and dispersing graphene and a binder solution, kneading and stirring active materials step by step, adding a solvent, stirring and dispersing at a high speed, premixing and dispersing the graphene and the binder solution, kneading and stirring the active materials step by step, adding the solvent, stirring and dispersing at a high speed, and compared with the prior art, the method has the following beneficial effects that:
1. the graphene can be dispersed at low cost, and meanwhile, no dispersing agent is introduced, so that the proportion of the electrode active material is favorably improved;
2. the obtained slurry has high solid content, can realize high-surface-density coating, solves the problems of low solid content and low coating surface density of the traditional stirring process, and further improves the energy density of the super capacitor;
3. the process operation is simple, the standardized and stabilized production is easy to realize, the slurry after being stirred can be directly connected into coating equipment for subsequent processing without further treatment, and the production efficiency is greatly improved.
Detailed Description
The invention will be further illustrated by the following examples and accompanying tables. In the following examples, all proportions are mass ratios unless otherwise specified.
Example 1
1) Adding graphene into a dispersion liquid of sodium carboxymethylcellulose (CMC), wherein the concentration of the graphene is 0.5%, and the ratio of the graphene to the CMC is 1: 8;
2) after the step 1), adding the obtained graphene adhesive solution into a stirring tank and activated carbon in batches for kneading and mixing, wherein the solid content of the first kneading and mixing is 50%, the kneading and stirring speed is 20rpm, and the kneading and stirring time is 20 min; after the first stirring is finished, adding the dispersion liquid of the rest graphene and the adhesive, wherein the whole solid content of the mixed sample is 40%, kneading and stirring at 20rpm for 120min, and the whole proportion of the activated carbon, the adhesive and the graphene is 95.5:4: 0.5;
3) adding deionized water after the step 2) is finished, stirring and dispersing, wherein the whole solid content of the slurry is 38%, the stirring speed is 50r/min, the dispersing speed is 2000r/min, and the stirring and dispersing time is 60 min; in addition, this step was carried out under vacuum throughout the stirring dispersion process, and the viscosity and solid content were measured after the stirring of the above slurry was completed.
Then coating and rolling to obtain the super capacitor pole piece using the slurry, and then carrying out the procedures of stripping, winding, injecting liquid, sealing and the like to obtain the super capacitor using the slurry. The obtained capacitor is tested for the performance of capacity, direct current resistance and the like, wherein the test current density is 1A/g.
Example 2
1) Adding graphene into a dispersion solution of sodium carboxymethylcellulose (CMC), wherein the concentration of the graphene is 0.5%, and the ratio of the graphene to the CMC is 1: 15;
2) after the step 1), adding the obtained graphene adhesive solution into a stirring tank and activated carbon in batches for kneading and mixing, wherein the solid content of the first kneading and mixing is 60%, the kneading and stirring speed is 20rpm, and the kneading and stirring time is 20 min; after the first stirring is finished, adding the dispersion liquid of the rest graphene and the adhesive, wherein the whole solid content of the mixed sample is 50%, kneading and stirring at 20rpm for 120min, and the whole proportion of the activated carbon, the adhesive and the graphene is 92:7.5: 0.5;
3) and adding deionized water to stir and disperse after the step 2) is finished, wherein the whole solid content of the slurry is 43%, the stirring speed is 50r/min, the dispersing speed is 2000r/min, and the stirring and dispersing time is 60 min.
Then coating and rolling to obtain the super capacitor pole piece using the slurry, and then carrying out the procedures of stripping, winding, injecting liquid, sealing and the like to obtain the super capacitor using the slurry. The obtained capacitor is tested for the performance of capacity, direct current resistance and the like, wherein the test current density is 1A/g.
Example 3
1) Adding graphene into a dispersion solution of sodium carboxymethylcellulose (CMC), wherein the concentration of the graphene is 1%, and the ratio of the graphene to the CMC is 1: 5;
2) after the step 1), adding the obtained graphene adhesive solution into a stirring tank and activated carbon in batches for kneading and mixing, wherein the solid content of the first kneading and mixing is 48%, the kneading and stirring speed is 20rpm, and the kneading and stirring time is 20 min; after the first stirring is finished, adding the dispersion liquid of the rest graphene and the adhesive, wherein the whole solid content of the mixed sample is 38%, and kneading and stirring at 20rpm for 120min, wherein the whole proportion of the activated carbon, the adhesive and the graphene is 94:5: 1;
3) and adding deionized water to stir and disperse after the step 2) is finished, wherein the solid content of the whole slurry is 32%, the stirring speed is 50r/min, the dispersing speed is 2000r/min, and the stirring and dispersing time is 60 min.
And then coating and rolling to obtain the pole piece of the super capacitor using the slurry, testing the resistivity of the obtained pole piece, and then carrying out the procedures of stripping, winding, injecting liquid, sealing and the like to obtain the super capacitor using the slurry. The obtained capacitor is tested for the performance of capacity, direct current resistance and the like, wherein the test current density is 1A/g.
Example 4
1) Adding graphene into the dispersion liquid of SBR, wherein the concentration of the graphene is 1%, and the ratio of the graphene to the SBR is 1: 5;
2) after the step 1), adding the obtained graphene adhesive solution into a stirring tank and activated carbon in batches for kneading and mixing, wherein the solid content of the first kneading and mixing is 60%, the kneading and stirring speed is 20rpm, and the kneading and stirring time is 20 min; after the first stirring is finished, adding the dispersion liquid of the rest graphene and the adhesive, wherein the solid content of the whole mixed sample is
50 percent, kneading and stirring at 20rpm for 120min, wherein the integral proportion of the activated carbon, the adhesive and the graphene is 94:5: 1;
3) and (3) adding deionized water after the step 2) is finished, stirring and dispersing, wherein the solid content of the whole slurry is designed to be 40%, the stirring speed is 50r/min, the dispersing speed is 2000r/min, and the stirring and dispersing time is 60 min.
And then coating and rolling to obtain the pole piece of the super capacitor using the slurry, testing the resistivity of the obtained pole piece, and then carrying out the procedures of stripping, winding, injecting liquid, sealing and the like to obtain the super capacitor using the slurry. The obtained capacitor is tested for the performance of capacity, direct current resistance and the like, wherein the test current density is 1A/g.
Comparative example 1
Mixing activated carbon, a graphene conductive agent and a CMC adhesive according to a ratio of 94:5:1 proportion, and adding deionized water for dispersion, wherein the stirring speed is 50r/min, the dispersion speed is 2000r/min, the stirring dispersion time is 600min, the designed solid content of the slurry is 23%, the whole stirring dispersion process is carried out in vacuum, and the viscosity and the solid content are tested after the slurry is stirred.
And then coating and rolling to obtain the pole piece of the super capacitor using the slurry, testing the resistivity of the obtained pole piece, and then carrying out the procedures of stripping, winding, injecting liquid, sealing and the like to obtain the super capacitor using the slurry. The obtained capacitor is tested for the performance of capacity, direct current resistance and the like, wherein the test current density is 1A/g.
Comparative example 2
Mixing activated carbon, a graphene conductive agent and an SBR adhesive according to a ratio of 94:5:1 proportion, and adding deionized water for dispersion, wherein the stirring speed is 50r/min, the dispersion speed is 2000r/min, the stirring dispersion time is 600min, the designed solid content of the stirred material is 28%, the whole stirring dispersion process is carried out under vacuum, and the viscosity and the solid content are tested after the stirring of the slurry is finished.
And then coating and rolling to obtain the pole piece of the super capacitor using the slurry, testing the resistivity of the obtained pole piece, and then carrying out the procedures of stripping, winding, injecting liquid, sealing and the like to obtain the super capacitor using the slurry. The obtained capacitor is tested for the performance of capacity, direct current resistance and the like, wherein the test current density is 1A/g.
The activated carbon used in examples 1-6 was YP-50F, and the electrolyte used was a PC solvent system.
Table 1 shows the performance data of the slurry, the electrode sheet and the capacitor in each example, and it can be seen from the data that the graphene electrode slurry used in the present invention has higher slurry solid content and lower viscosity than the conventional process, and the prepared super capacitor has low direct current resistance, high energy density and power density.
Table 1.
In view of the numerous embodiments of the present invention, the verified performance and the final conclusion of each embodiment are close to each other, and are not described herein. Meanwhile, the experimental parameters which are listed and not listed in the embodiment of the invention only represent an example of a technical scheme, namely a feasible scheme, and strict matching and limiting relations do not exist among the parameters, wherein the parameters can be replaced with each other without departing from the axiom and the requirement of the invention, except for special statement.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and the technical solutions of the embodiment are equally replaced by one or more technical parameters to form a new technical solution, which is also within the scope of the present invention; it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A preparation method of graphene supercapacitor slurry is characterized by comprising the following steps:
1) graphene adhesive dispersion liquid preparation
Adding graphene into a dispersion liquid of an adhesive for stirring and dispersing, wherein the mass ratio of the graphene to the adhesive is 1: 2-1: 20, the solid content of the graphene is 0.1% -10%, the stirring speed is 10-100 r/min, the dispersing speed is 800-3000 r/min, and the stirring and dispersing time is 30-600 min;
2) kneading and mixing the electrode active material and the graphene binder dispersion liquid step by step
Firstly, taking 20-70% of the total amount of the graphene adhesive dispersion liquid prepared in the step 1), adding an active electrode material into the adhesive graphene mixed liquid, and kneading, stirring and mixing in a first step, wherein the electrode active material comprises one or a mixture of more of active carbon, active carbon fiber and graphite, and the specific surface area of the active carbon material is more than 1500m2The solid content of kneading is 30-90%, the stirring speed is 5-100 r/min, and the kneading time is 10-180 min; then adding the rest graphene adhesive dispersion liquid prepared in the step 1) into the mixture obtained after the first-step kneading and stirring, and carrying out second-step kneading and stirring, wherein the solid content of the second-step kneading is 25-85%, and the whole material ratio is as follows: active materials are adhesive, namely graphene =70% -95%, 4.5% -20%, 0.5% -10%, the kneading and stirring speed is 5-100 r/min, and the kneading and stirring time is 30-600 min;
3) adding a solvent to dilute and disperse
After the step 2) is finished, adding a solvent into a stirring tank for dilution, stirring and dispersion, wherein the whole stirring and dispersion process is carried out in a vacuum environment, the solid content is 20% -80%, the stirring speed is 10-100 r/min, the dispersion speed is 500-3000 r/min, and the stirring and dispersion time is 10-600 min, so that the graphene supercapacitor slurry is prepared, wherein the viscosity range of the graphene supercapacitor slurry is 3000-8000 mPa.S.
2. The method for preparing graphene supercapacitor slurry according to claim 1, wherein the method comprises the following steps: the graphene in the step 1) is prepared by an oxidation-reduction method, a physical stripping method, a physical intercalation or a chemical intercalation, and the adhesive is one or more of polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, sodium carboxymethylcellulose and sodium alginate.
3. The method for preparing graphene supercapacitor slurry according to claim 1, wherein the method comprises the following steps: the graphene adhesive dispersion liquid in the step 1) has the concentration of 0.5-5% of graphene, and the ratio of graphene to adhesive is 1: 5-1: 15.
4. The method for preparing graphene supercapacitor slurry according to claim 1, wherein the method comprises the following steps: in the step 1), the stirring speed is 20-50 r/min, the dispersing speed is 1000-2000 rpm, and the stirring dispersing time is 60-300 min.
5. The method for preparing graphene supercapacitor slurry according to claim 1, wherein the method comprises the following steps: the solvent in the step 3) is one or a mixture of a plurality of solvents of water, ethanol and nitrogen methyl pyrrolidone.
6. The method for preparing graphene supercapacitor slurry according to claim 1, wherein the method comprises the following steps: in the step 3), the stirring speed is 20-50 rpm, the dispersing speed is 1000-2000 rpm, and the stirring dispersing time is 60-300 min.
7. A graphene supercapacitor made using the graphene supercapacitor slurry made by the method of claim 1, wherein: coating, rolling, slitting, winding and injecting the prepared graphene supercapacitor slurry to prepare a graphene supercapacitor, wherein a current collector used for coating is a carbon-coated aluminum foil, and an electrolyte solvent injected into the capacitor comprises one or more of ethylene carbonate, propylene carbonate, gamma-butyrolactone, dimethyl carbonate, diethyl carbonate, butylene carbonate, methyl ethyl carbonate and acetonitrile; solute in the electrolyte is at least one of sodium perchlorate, sodium hexafluorophosphate, sodium trifluoromethanesulfonate, sodium bis (trifluoromethanesulfonyl) imide, sodium bisoxalate, sodium hexafluoroarsenate, tetraethylene glycol dimethyl ether, tetraethylammonium tetrafluoroborate and spiro quaternary ammonium salt.
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