CN115295321A - Super capacitor and preparation method thereof - Google Patents
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- CN115295321A CN115295321A CN202210960682.5A CN202210960682A CN115295321A CN 115295321 A CN115295321 A CN 115295321A CN 202210960682 A CN202210960682 A CN 202210960682A CN 115295321 A CN115295321 A CN 115295321A
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/78—Cases; Housings; Encapsulations; Mountings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The application relates to the technical field of super capacitors and provides a super capacitor, which comprises a packaging shell, and a positive electrode, a negative electrode, a diaphragm and electrolyte which are positioned in the packaging shell, wherein the inner surface of the packaging shell is combined with a coating, the material of the coating comprises a gas adsorption material and a first binder, and the specific surface area of the gas adsorption material is more than 500m 2 The grain diameter is as follows: d50 is less than 50 mu m. The application provides a supercapacitor, because the internal surface of encapsulation casing combines there is the coating, not only increased the inside specific surface area of casing, the coating contains gas adsorption material moreover, can adsorb the produced gas of supercapacitor in a large number, consequently can reduce supercapacitor in long-term service produced gas to casing unit area's effort, reduce supercapacitor in service gas inflation and weeping proportion, prolong its life.
Description
Technical Field
The application belongs to the technical field of super capacitors, and particularly relates to a super capacitor and a preparation method thereof.
Background
The super capacitor has the characteristics of ultrahigh power density, ultrahigh charging speed, wider working temperature range, overlong cycle life, safety, maintenance-free property and the like, and therefore has wide application prospects in the fields of aerospace, rail transit, new energy automobiles and electronic industry. However, the super capacitor has the problems of gas generation, easy leakage and the like during long-term service, and the gas is mainly generated from two aspects, namely the decomposition of water existing in an electrode, and the oxidation or reduction decomposition of an electrolyte during long-term service.
The existing method for reducing the gas generation defect is to reduce the water content in the electrode through a baking process on one hand, and improve the voltage tolerance of the electrolyte on the other hand, so as to relieve the decomposition of the electrolyte. However, the gas generation problem is still difficult to solve by the current commercialized process and electrolyte system, so that the supercapacitor is easy to generate swelling, liquid leakage and other problems to lose effectiveness in long-term service, and particularly the swelling, liquid leakage and other problems are more serious at high temperature and high voltage.
Disclosure of Invention
The application aims to provide a super capacitor and a preparation method thereof, and aims to solve the problem that the conventional super capacitor is easy to generate air inflation, liquid leakage and the like in long-term service to cause failure.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the application provides a super capacitor, which comprises a packaging shell, and a positive electrode, a negative electrode, a diaphragm and electrolyte which are positioned in the packaging shell, and is characterized in that a coating is combined on the inner surface of the packaging shell, the material of the coating comprises a gas adsorption material and a first binder, and the specific surface area of the gas adsorption material is more than 500m 2 The grain diameter is as follows: d50 is less than 50 mu m.
In a second aspect, the present application provides a method for preparing a supercapacitor, comprising the steps of:
providing a shell, a gas adsorption material, a first binder, a positive electrode, a negative electrode, a diaphragm and electrolyte;
mixing the gas adsorption material and the first binder to form slurry, coating the slurry on the inner surface of the shell to form a coating, and thus obtaining the packaging shell;
and assembling the anode, the cathode, the diaphragm and the packaging shell, and then injecting electrolyte to obtain the super capacitor.
Compared with the prior art, the method has the following beneficial effects:
according to the supercapacitor provided by the first aspect of the application, the coating is combined on the inner surface of the packaging shell, so that the specific surface area inside the shell is increased, the acting force of gas generated by the supercapacitor in long-term service on the unit area of the shell can be reduced, and the specific surface area of a gas adsorption material contained in the coating is more than 500m 2 The gas has stronger adsorption effect on the generated gas, namely, the gas yield is reduced, so that the pressure of the gas is reduced; in addition, the grain diameter of the adsorbing material is less than 50 μm, so that the coating thickness is ensured to be thin, the occupied inner space is small, and the pressure of the gas is favorably reduced. Therefore, the inner surface of the packaging shell of the supercapacitor is combined with the coating, the effect of gas generated by the supercapacitor on the shell can be obviously reduced, the proportion of gas expansion and liquid leakage of the supercapacitor in service is reduced, and the service life of the supercapacitor is prolonged.
According to the preparation method of the supercapacitor provided by the second aspect of the application, the gas adsorption material and the first binder are mixed to form slurry, the slurry is coated on the inner surface of the shell to form a coating, the packaging shell is obtained, then the anode, the cathode, the diaphragm and the packaging shell are assembled, and electrolyte is injected to obtain the supercapacitor. The preparation process is simple, convenient and controllable, has low production cost and is easy for industrial production.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a preparation flowchart of a method for preparing a supercapacitor provided in an embodiment of the present application.
Detailed Description
In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the foregoing processes do not imply an execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not limit the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass described in the specification of the embodiments of the present application may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
The supercapacitor comprises a packaging shell, and a positive electrode, a negative electrode, a diaphragm and electrolyte which are positioned in the packaging shell, and is characterized in that a coating is combined on the inner surface of the packaging shell, the material of the coating comprises a gas adsorption material and a first binder, and the specific surface area of the gas adsorption material is more than 500m 2 The grain diameter is as follows: d50 is less than 50 μm.
According to the supercapacitor provided by the embodiment of the application, the coating is combined on the inner surface of the packaging shell, so that the specific surface area inside the shell is increased, the acting force of gas generated by the supercapacitor in long-term service on the unit area of the shell can be reduced, and the specific surface area of a gas adsorption material contained in the coating is larger than 500m 2 The pressure per gram has stronger adsorption effect on the generated gas, namely, the gas yield is reduced, so that the pressure of the gas is reduced; in addition, the grain diameter of the adsorbing material is less than 50 μm, so that the coating thickness is ensured to be thin, the occupied inner space is small, and the pressure of the gas is favorably reduced. Therefore, the inner surface of the packaging shell of the supercapacitor is combined with the coating, the effect of gas generated by the supercapacitor on the shell can be obviously reduced, the proportion of gas expansion and liquid leakage of the supercapacitor in service is reduced, and the service life of the supercapacitor is prolonged.
In the examples, the specific surface area of the gas-adsorbing material was > 500m 2 The grain diameter is as follows: d50 is less than 50 μm. The specific surface area of the gas adsorbing material provided by the embodiment of the application is more than 500m 2 The gas adsorption material has the advantages that the gas adsorption material has large surface area, the gas adsorption material has residual surface energy due to unbalanced stress, and when the gas such as hydrogen, carbon dioxide, carbon monoxide, ethylene, propylene, methane and acetonitrile generated by the supercapacitor collides with the surface of the gas adsorption material, the gas adsorption material can be attracted by unbalanced force to stay on the surface of the gas adsorption material, so that the gas generated by the supercapacitor is adsorbed in a large amount in a physical adsorption mode, the influence of gas pressure on the shell is reduced, namely the gas production is reduced, meanwhile, the gas adsorption material for forming the coating is ensured to be less, and therefore the coating occupies small space and the weight of the shell is increased less. The particle size is less than 50 mu m, so that the coating is ensured to be thin and occupy small internal space, thereby being beneficial to reducing the influence of gas pressure on the shell, reducing the proportion of gas expansion and liquid leakage of the super capacitor in service and prolonging the service life of the super capacitor.
In a preferred embodiment, the gas adsorbent material has a specific surface area of 1000m 2 /g～1800m 2 G, e.g. 1000m 2 /g、1100m 2 /g、1200m 2 /g、1300m 2 /g、1400m 2 /g、1500m 2 /g、1600m 2 /g、1700m 2 /g、1800m 2 (ii) in terms of/g. The particle size of the gas adsorption material meets the following requirements: 5 μm. Ltoreq. D50. Ltoreq.10 μm, for example, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm. In the specific surface area and the particle size range of the gas adsorption material provided by the embodiment, the effect of gas generated by the super capacitor on the shell can be obviously reduced, the proportion of gas expansion and liquid leakage is obviously reduced, the service life is obviously prolonged, the gas adsorption material can be used under the conditions of high pressure and high temperature, and meanwhile, the occupied space of the coating is small and the weight gain of the shell is small.
In the examples, the mass ratio of the gas adsorbent to the binder was (60 to 90): (10 to 40), for example, 60: 40. 65: 30. 70: 30. 75: 25. 80: 20. 85: 15. 90:10. in the mass ratio range of the gas adsorption material and the binder provided by the embodiment, the coating can adsorb a large amount of gas, the influence of gas pressure on the shell is reduced, and meanwhile, the coating and the shell have strong adhesive force and are not easy to demould and fall powder.
In an embodiment, the thickness of the coating is 50 to 1000 μm, e.g. 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, 1000 μm. In the thickness range of the coating provided by the embodiment, the coating can be ensured to adsorb a large amount of gas, so that the influence of the gas pressure on the shell is obviously reduced, and meanwhile, the occupied inner space is small, and the reduction of the gas pressure is facilitated. And is easy to process and control.
In an embodiment, the gas-adsorbing material comprises at least one of activated carbon, biomass carbon, capacitive carbon, conductive carbon black, carbon nanotubes, graphene, aerogel, alumina ceramic, silica gel, porous silica, and high molecular weight polymers. Preferably, the gas adsorption material is selected from one or more of activated carbon, biomass carbon and capacitance carbon. These adsorption material have great surface area, and the adsorption effect is strong, can adsorb the gas that produces in a large number, reduces the influence of the gas that ultracapacitor system produced to the casing.
In an embodiment, the first binder includes at least one of styrene butadiene rubber, polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride. The first binders have strong adhesive action, so that the coating and the shell have strong adhesive force and are not easy to demould and fall off.
In an embodiment, the positive electrode includes a positive electrode current collector and a positive electrode active layer combined on the surface of the positive electrode current collector, and the positive electrode current collector may include any one of an aluminum foil, a carbon-coated aluminum foil, an etched aluminum foil and a carbon cloth, or a composite positive electrode current collector formed by two of the aluminum foil, the carbon-coated aluminum foil, the etched aluminum foil and the carbon cloth. In a specific embodiment, the positive current collector is carbon-coated aluminum foil. The positive electrode active layer comprises a first active material, a first conductive agent and a second adhesive, and the mass ratio of the first active material to the first conductive agent to the second adhesive is (70-95): (2-15): (3-15). Preferably, the mass ratio of the first active material, the first conductive agent and the second binder is (80-90): (5-10): (5-10). Within the mass ratio range of the first active material, the first conductive agent and the second binder contained in the positive electrode active layer provided by the embodiment of the application, the positive electrode active layer has high capacity, low internal resistance and stable structure. For example, the mass ratio of the first active material, the first conductive agent, and the second binder is 70:2: 3. 95:15: 15. 80:5: 5. 90:10: 10. 85:7:8.
in an embodiment, the first active material comprises at least one of activated carbon, activated carbon fibers, graphene, carbon nanotubes, graphite. For example, the first active material is activated carbon. The positive electrode active materials provided by the embodiment of the application have high capacity, and can endow the positive electrode active layer with high capacity.
In an embodiment, the first conductive agent comprises at least one of conductive carbon black, graphene, carbon nanotubes, vapor Grown Carbon Fibers (VGCF), conductive graphite. For example, the first conductive agent is conductive carbon black. The first conductive agents provided by the embodiment of the application have high conductivity, and can reduce the internal resistance of the positive electrode and the negative electrode.
In an embodiment, the second adhesive comprises at least one of polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, sodium carboxymethyl cellulose, sodium alginate, polyacrylic acid. For example, the second adhesive is styrene butadiene rubber. The second adhesive provided by the embodiment of the application can effectively enhance the mechanical property of the positive active layer, and has low internal resistance.
In an embodiment, the negative electrode comprises a negative electrode current collector and a negative electrode active layer combined on the surface of the negative electrode current collector, and the negative electrode current collector comprises any one of aluminum foil, carbon-coated aluminum foil, etched aluminum foil and carbon cloth, or a composite positive electrode current collector formed by two of aluminum foil, carbon-coated aluminum foil, etched aluminum foil and carbon cloth. In a specific embodiment, the negative current collector is carbon-coated aluminum foil. The negative electrode active layer comprises a second active material, a second conductive agent and a third binder, and the mass ratio of the second active material to the second conductive agent to the third binder is (70-95): (2-15): (3-15). Preferably, the mass ratio of the second active material, the second conductive agent and the third binder is (80-90): (5-10): (5-10). In the mass ratio range of the second active material, the second conductive agent and the third binder contained in the negative electrode active layer provided in the embodiment of the present application, the negative electrode active layer can have high capacity, low internal resistance and stable structure. For example, the mass ratio of the second active material, the second conductive agent, and the third binder is 70:2: 3. 95:15: 15. 80:5: 5. 90:10: 10. 85:7:7.
in an embodiment, the second active material comprises at least one of activated carbon, activated carbon fibers, graphene, carbon nanotubes, graphite. For example, the second active material is activated carbon. The negative electrode active materials provided by the embodiment of the application have high capacity, and can endow a positive electrode active layer with high capacity.
In an embodiment, the second conductive agent includes at least one of conductive carbon black, graphene, carbon nanotubes, vapor Grown Carbon Fiber (VGCF), conductive graphite. For example, the second conductive agent is conductive carbon black. The second conductive agents provided by the embodiment of the application have high conductivity, and can reduce the internal resistance of the positive electrode and the negative electrode.
In an embodiment, the third adhesive comprises at least one of polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, sodium carboxymethylcellulose, sodium alginate, and polyacrylic acid. For example, the third adhesive is styrene butadiene rubber. The third adhesives provided by the embodiment of the application can effectively enhance the mechanical property of the positive active layer, and have low internal resistance.
In the examples, the surface density of the positive electrode active layer was 5 to 20mg/cm 2 E.g. 5mg/cm 2 、7mg/cm 2 、9mg/cm 2 、11mg/cm 2 、13mg/cm 2 、15mg/cm 2 、17mg/cm 2 、20mg/cm 2 . The surface density of the negative active layer is 5-20mg/cm 2 E.g. 5mg/cm 2 、7mg/cm 2 、9mg/cm 2 、11mg/cm 2 、13mg/cm 2 、15mg/cm 2 、17mg/cm 2 、20mg/cm 2 . Within the range of the surface density of the positive electrode active layer and the negative electrode active layer provided by the embodiment of the application, the capacity retention rate and the internal resistance stability of the super capacitor are improved, so that the super capacitor has excellent cycle performance.
In an embodiment, the solvent in the electrolyte comprises at least one of ethylene carbonate, propylene carbonate, gamma-butyrolactone, dimethyl carbonate, diethyl carbonate, butylene carbonate, ethylmethyl carbonate, and acetonitrile.
In an embodiment, the solute in the electrolyte comprises at least one of lithium perchlorate, lithium hexafluorophosphate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (oxalato) borate, lithium hexafluoroarsenate, tetraethylammonium tetrafluoroborate, spiro quaternary ammonium salts. The electrolyte provided by the embodiment of the application can further improve the capacity retention rate and the internal resistance stability of the super capacitor on the basis of the anode and the cathode, and improve the excellent cycle performance of the super capacitor.
In an embodiment, the separator included in the supercapacitor functions as a separator in a conventional manner, for example, the separator may be any one of polyethylene, polypropylene, polyethylene polypropylene copolymer, cellulose, polyethylene oxide and carbon paper.
A second aspect of the embodiments of the present application provides a method for manufacturing a supercapacitor, including the following steps:
s10: providing a shell, an adsorption material, a first binder, a positive electrode, a negative electrode, a diaphragm and electrolyte;
s20: mixing the adsorbing material and the first binder to form slurry, coating the slurry on the inner surface of the shell to form a coating, and thus obtaining the packaging shell;
s30: and assembling the anode, the cathode, the diaphragm and the packaging shell, and then injecting electrolyte to obtain the super capacitor.
According to the preparation method of the supercapacitor, the adsorption material and the first binder are mixed to form slurry, the slurry is coated on the inner surface of the shell to form a coating, the packaging shell is obtained, then the anode, the cathode and the diaphragm are assembled with the packaging shell, and electrolyte is injected into the packaging shell, so that the supercapacitor is obtained. The preparation process is simple, convenient and controllable, low in production cost and easy for industrial production.
In the above step S10, the housing is a conventional housing in the art. The positive electrode is the positive electrode contained in the above supercapacitor. Therefore, the step S10 provides the materials contained in the positive electrode as described above, and the preparation method thereof may adopt a conventional method in the art. For example, a material for preparing a positive electrode active layer included in a positive electrode is mixed with a solvent in proportion to prepare a positive electrode active layer slurry, the positive electrode active layer slurry is formed on one surface or two opposite surfaces of a positive electrode current collector to obtain a wet film layer, and then the wet film layer is subjected to drying treatment, rolling treatment, slitting treatment and slitting treatment to obtain the positive electrode. In an embodiment, the method of configuring the positive active layer slurry comprises: according to the mass ratio of the first active material to the first conductive agent to the second adhesive (70-95): (2-15): (3-15), mixing the positive electrode active material, the first conductive agent, the second adhesive and the solvent to obtain positive electrode active layer slurry. The concentration of the slurry of the positive active layer can be adjusted according to the actual film forming process requirements. The positive electrode active layer obtained by the roll press treatment has the surface density of the positive electrode active layer contained in the supercapacitor positive electrode as described above.
The negative electrode is the negative electrode contained in the supercapacitor above. Therefore, the material contained in the anode provided in step S10 is as described above. The preparation method of the cathode in the step S10 may adopt a conventional method in the art. For example, a material for preparing a negative electrode active layer included in a negative electrode is mixed with a solvent in a ratio to prepare a negative electrode active layer slurry, the negative electrode active layer slurry is formed on one surface or opposite two surfaces of a negative electrode current collector to obtain a wet film layer, and then the wet film layer is subjected to drying treatment, rolling treatment, slitting treatment, and slitting treatment to obtain the negative electrode. In an embodiment, the method of configuring the anode active layer slurry comprises: according to the mass ratio of the second active material to the second conductive agent to the third adhesive being (70-95): (2-15): (3-15), mixing the negative electrode active material, the second conductive agent and the third adhesive with a solvent to obtain negative electrode active layer slurry. The concentration of the slurry of the active layer of the negative electrode can be adjusted according to the actual film forming process requirements. The negative electrode active layer obtained by the roll press treatment has the surface density of the negative electrode active layer contained in the supercapacitor positive electrode as described above.
In the above step S20, the preparation method of the slurry includes: the adsorbing material and the binder are mixed according to the mass ratio of (60-90): (10-40) mixing to obtain slurry.
In the step S30, the method for assembling the positive electrode, the negative electrode, the separator and the package case may be a method conventional in the art.
The following description will be given with reference to specific examples.
Example 1
The embodiment provides a super capacitor and a preparation method thereof.
The super capacitor comprises a packaging shell, and a positive electrode, a negative electrode, a diaphragm and electrolyte which are positioned in the packaging shell; the positive pole includes anodal mass flow body and combines the anodal active layer at anodal mass flow body surface, and the anodal mass flow body chooses for use carbon-coated aluminium foil, and activated carbon, conductive carbon black, butadiene styrene rubber are chooseed for use to the material of anodal active layer, and activated carbon, conductive carbon black, butadiene styrene rubber's mass ratio is 85:7:7; the negative pole includes negative current collector and combines the negative pole active layer on negative current collector surface, and the negative current collector chooses for use charcoal cloth, and active carbon, conductive carbon black, sodium alginate are chooseed for use to the material of positive active layer, and the mass ratio of active carbon, conductive carbon black, sodium alginate is 85:7:7; the diaphragm is made of polyethylene, the electrolyte solvent is acetonitrile, and the solute is made of spiro quaternary ammonium salt of dipyrrolidine tetrafluoroborate; the packaging shell is made of an aluminum-plastic film material, the inner surface of the packaging shell is combined with a coating, and the coating is prepared from the following components in percentage by mass: 20 of activated carbon and styrene butadiene rubber, and the specific surface area of the activated carbon is 1500m 2 G, D50 is 10 μm and the thickness of the coating is 200. Mu.m.
The preparation method of the super capacitor comprises the following steps:
s10: providing a cylindrical super capacitor shell, activated carbon, styrene butadiene rubber, a positive plate, a negative plate, a diaphragm and electrolyte;
s20: according to the mass ratio of 80:20, mixing activated carbon and styrene butadiene rubber to form slurry, and coating the slurry on the inner surface of the cylindrical supercapacitor shell to form a coating to obtain a packaging shell;
s30: and rolling, slitting, cutting, welding and winding the positive plate, the negative plate and the diaphragm into a battery cell, then putting the battery cell into a packaging shell, and injecting electrolyte to obtain the super capacitor.
The super capacitor provided by the embodiment is subjected to a high-temperature float-charging performance test under a voltage condition of 3V.
Example 2
The embodiment provides a super capacitor and a preparation method thereof.
The super capacitor comprises a packaging shell, and a positive electrode, a negative electrode, a diaphragm and electrolyte which are positioned in the packaging shell; the positive pole includes anodal mass flow body and combines the anodal active layer at anodal mass flow body surface, and the anodal mass flow body chooses for use carbon-coated aluminium foil, and activated carbon, conductive carbon black, butadiene styrene rubber are chooseed for use to the material of anodal active layer, and activated carbon, conductive carbon black, butadiene styrene rubber's mass ratio is 85:7:7; the negative pole includes negative current collector and combines the negative pole active layer on negative current collector surface, and the negative current collector chooses for use charcoal cloth, and active carbon, conductive carbon black, sodium alginate are chooseed for use to the material of positive active layer, and the mass ratio of active carbon, conductive carbon black, sodium alginate is 85:7:7; the diaphragm is made of polyethylene, the electrolyte solvent is acetonitrile, and the solute is made of spiro quaternary ammonium salt of dipyrrolidine tetrafluoroborate; the packaging shell is made of an aluminum-plastic film material, the inner surface of the packaging shell is combined with a coating, and the coating is prepared from the following components in percentage by mass: 35 and polytetrafluoroethylene, and the specific surface area of the alumina ceramic particles is 501m 2 G, D50 is 15 μm and the thickness of the coating is 200. Mu.m.
The preparation method of the super capacitor comprises the following steps:
s10: providing a cylindrical super capacitor shell, alumina ceramic particles, polytetrafluoroethylene, a positive plate, a negative plate, a diaphragm and electrolyte; wherein the electrolyte solvent is acetonitrile, and the solute is dipyrrolidine spiro quaternary ammonium tetrafluoroborate.
S20: according to the mass ratio of 80:20, mixing alumina ceramic particles and polytetrafluoroethylene to form slurry, and coating the slurry on the inner surface of the cylindrical super capacitor shell to form a coating to obtain a packaging shell;
s30: and rolling, slitting, cutting, welding and winding the positive plate, the negative plate and the diaphragm into a battery cell, putting the battery cell into a packaging shell, and injecting electrolyte to obtain the super capacitor.
The supercapacitor provided by the embodiment is subjected to a high-temperature float-charging performance test under a voltage condition of 3V.
Example 3
The embodiment provides a super capacitor and a preparation method thereof.
The super capacitor comprises a packaging shell, and a positive electrode, a negative electrode, a diaphragm and electrolyte which are positioned in the packaging shell; the positive pole includes anodal mass flow body and combines the anodal active layer at anodal mass flow body surface, and the anodal mass flow body chooses for use carbon-coated aluminium foil, and activated carbon, conductive carbon black, butadiene styrene rubber are chooseed for use to the material of anodal active layer, and activated carbon, conductive carbon black, butadiene styrene rubber's mass ratio is 85:7:7; the negative pole includes negative current collector and combines the negative pole active layer on negative current collector surface, and the negative current collector chooses for use charcoal cloth, and active carbon, conductive carbon black, sodium alginate are chooseed for use to the material of positive active layer, and the mass ratio of active carbon, conductive carbon black, sodium alginate is 85:7:7; the diaphragm is made of polyethylene, the electrolyte solvent is acetonitrile, and the solute is made of dipyrrolidine spiro quaternary ammonium tetrafluoroborate; the packaging shell is made of an aluminum-plastic film material, the inner surface of the packaging shell is combined with a coating, and the coating is prepared from the following components in percentage by mass: 10 of activated carbon and styrene butadiene rubber, and the specific surface area of the activated carbon is 1800m 2 G, D50 of 49.5. Mu.m, and a coating thickness of 200. Mu.m.
The preparation method of the super capacitor comprises the following steps:
s10: providing a cylindrical super capacitor shell, activated carbon, styrene butadiene rubber, a positive plate, a negative plate, a diaphragm and electrolyte; wherein the electrolyte solvent is acetonitrile, and the solute is dipyrrolidine spiro quaternary ammonium tetrafluoroborate.
S20: according to the mass ratio of 90:10, mixing activated carbon and styrene butadiene rubber to form slurry, and coating the slurry on the inner surface of the cylindrical supercapacitor shell to form a coating to obtain a packaging shell;
s30: and rolling, slitting, cutting, welding and winding the positive plate, the negative plate and the diaphragm into a battery cell, putting the battery cell into a packaging shell, and injecting electrolyte to obtain the super capacitor.
The supercapacitor provided by the embodiment is subjected to a high-temperature float-charging performance test under a voltage condition of 3V.
Comparative example 1
The present comparative example provides a supercapacitor and a method of making the same.
The super capacitor comprises a packaging shell, and a positive electrode, a negative electrode, a diaphragm and electrolyte which are positioned in the packaging shell; the positive pole includes anodal mass flow body and combines the anodal active layer at anodal mass flow body surface, and the anodal mass flow body chooses for use carbon-coated aluminium foil, and activated carbon, conductive carbon black, butadiene styrene rubber are chooseed for use to the material of anodal active layer, and activated carbon, conductive carbon black, butadiene styrene rubber's mass ratio is 85:7:7; the negative pole includes negative current collector and combines the negative pole active layer on negative current collector surface, and the negative current collector chooses for use charcoal cloth, and active carbon, conductive carbon black, sodium alginate are chosen for use to the material of positive pole active layer, and the mass ratio of active carbon, conductive carbon black, sodium alginate is 85:7:7; the diaphragm is made of polyethylene, the electrolyte solvent is acetonitrile, and the solute is made of spiro quaternary ammonium salt of dipyrrolidine tetrafluoroborate; the packaging shell is made of an aluminum-plastic film material. The difference from examples 1 to 3 is that the package case of this comparative example does not contain a coating layer.
The preparation method of the super capacitor comprises the following steps:
s10: providing a positive plate, a negative plate, a diaphragm and electrolyte of a cylindrical super capacitor shell;
s20: and rolling, slitting, cutting, welding and winding the positive plate, the negative plate and the diaphragm into a battery cell, putting the battery cell into a packaging shell, and injecting electrolyte to obtain the super capacitor.
The supercapacitor provided by the embodiment is subjected to a high-temperature float-charging performance test under a voltage condition of 3V.
And (3) relevant performance test analysis:
the supercapacitors provided in the above examples 1-3 and comparative example 1 were respectively subjected to constant current charge and discharge test under 3V condition, and the floating charge performance at 65 ℃ for 1500h was observed, and the results are shown in table 1 below.
TABLE 1
The test results in table 1 show that the supercapacitor provided in examples 1 to 3 of the present application have a capacity retention rate of more than 83% and an internal resistance growth rate of less than 75% after being subjected to float-charging at a temperature of 3V and 65 ℃ for 1500 hours, and the supercapacitor provided in the comparative example has a capacity retention rate of only 60% and an internal resistance growth rate of up to 300% after being subjected to float-charging at a temperature of 3V and 65 ℃ for 1500 hours, and further has the occurrence of swelling and liquid leakage.
The above description is only a preferred embodiment of the present application and should not be taken as limiting the present application, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The supercapacitor comprises a packaging shell, and a positive electrode, a negative electrode, a diaphragm and electrolyte which are positioned in the packaging shell, and is characterized in that a coating is combined on the inner surface of the packaging shell, the coating is made of a material comprising a gas adsorption material and a first binder, and the specific surface area of the gas adsorption material is more than 500m 2 The particle diameter is as follows: d50 is less than 50 μm.
2. The supercapacitor of claim 1, wherein the gas adsorbent material has a specific surface area of 1000m 2 /g～1800m 2 The grain diameter is as follows: d50 is more than or equal to 5 mu m and less than or equal to 10 mu m.
3. The supercapacitor according to claim 1, wherein the mass ratio of the gas adsorbent to the binder is (60 to 90): (10-40); and/or
The thickness of the coating is 50-1000 μm.
4. The supercapacitor of any one of claims 1 to 3, wherein the gas adsorbing material comprises at least one of activated carbon, biomass carbon, conductive carbon black, carbon nanotubes, graphene, aerogel, alumina ceramic, porous silica, and high molecular weight polymers; and/or
The first binder comprises at least one of styrene butadiene rubber, polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene and polyvinylidene fluoride.
5. The supercapacitor according to claim 4, wherein the positive electrode comprises a positive electrode current collector and a positive electrode active layer bonded on the surface of the positive electrode current collector, the positive electrode active layer comprises a first active material, a first conductive agent and a second binder, and the mass ratio of the first active material, the first conductive agent and the second binder is (70-95): (2-15): (3-15); and/or
The negative electrode comprises a negative electrode current collector and a negative electrode active layer combined on the surface of the negative electrode current collector, the negative electrode active layer comprises a second active material, a second conductive agent and a third adhesive, and the mass ratio of the second active material to the second conductive agent to the third adhesive is (70-95): (2-15): (3-15).
6. The supercapacitor according to claim 5, wherein the mass ratio of the first active material, the first conductive agent, and the second binder is (80-90): (5-10): (5-10); and/or
The mass ratio of the second active material to the second conductive agent to the third adhesive is (80-90): (5-10): (5-10).
7. The supercapacitor of claim 5, wherein the first active material comprises at least one of activated carbon, activated carbon fibers, graphene, carbon nanotubes, graphite;
the first conductive agent comprises at least one of conductive carbon black, graphene, carbon nanotubes, vapor grown carbon fibers and conductive graphite;
the second adhesive comprises at least one of polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, sodium carboxymethylcellulose, sodium alginate and polyacrylic acid.
8. The supercapacitor of claim 5, wherein the second active material comprises at least one of activated carbon, activated carbon fibers, graphene, carbon nanotubes, graphite;
the second conductive agent comprises at least one of conductive carbon black, graphene, carbon nanotubes, vapor grown carbon fibers and conductive graphite;
the third adhesive comprises at least one of polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, sodium carboxymethylcellulose, sodium alginate and polyacrylic acid.
9. The supercapacitor according to any one of claims 5 to 8, wherein the solvent in the electrolyte comprises at least one of ethylene carbonate, propylene carbonate, γ -butyrolactone, dimethyl carbonate, diethyl carbonate, butylene carbonate, methyl ethyl carbonate, acetonitrile;
the solute in the electrolyte comprises at least one of lithium perchlorate, lithium hexafluorophosphate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (oxalato) borate, lithium hexafluoroarsenate, tetraethylammonium tetrafluoroborate and spiro quaternary ammonium salt.
10. A method for preparing a supercapacitor according to any one of claims 1 to 3, comprising the steps of:
providing a housing, the gas adsorbing material, the first binder, the positive electrode, the negative electrode, the separator, and the electrolyte;
mixing the gas adsorbing material and the first binder to form slurry, coating the slurry on the inner surface of the shell to form a coating, and thus obtaining the packaging shell;
and assembling the anode, the cathode, the diaphragm and the packaging shell, and then injecting the electrolyte to obtain the super capacitor.
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