CN114999829A - Low-impedance capacitor and preparation method thereof - Google Patents

Low-impedance capacitor and preparation method thereof Download PDF

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CN114999829A
CN114999829A CN202210604109.0A CN202210604109A CN114999829A CN 114999829 A CN114999829 A CN 114999829A CN 202210604109 A CN202210604109 A CN 202210604109A CN 114999829 A CN114999829 A CN 114999829A
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capacitor
electrolyte
electrolytic paper
aluminum
fibers
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CN114999829B (en
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邵志飞
汪海霞
林小亮
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Shenzhen Okcap Capacitor Co ltd
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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
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/145—Liquid electrolytic capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
    • H01G13/02—Machines for winding capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
    • H01G13/04—Drying; Impregnating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/035—Liquid electrolytes, e.g. impregnating materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/13—Energy storage using capacitors

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Abstract

The application relates to the technical field of capacitors, and particularly discloses a low-impedance capacitor and a preparation method thereof. A low-impedance capacitor comprises an electrode plate, electrolytic paper and electrolyte, wherein the electrolytic paper comprises the following substances in parts by weight: 85-95 parts of softwood pulp fibers, 5-15 parts of Chinese alpine rush fibers and 0.1-1 part of nanofibrillar cellulose, wherein the beating degree of the Chinese alpine rush fibers is 30-50 DEG SR, and the softwood pulp fibers are the softwood pulp fibers which are beaten at a high concentration and have the beating degree of 70-90 DEG SR. The preparation method comprises the steps of S1, dipping treatment; s2, preparing a capacitor. The low impedance type capacitor can be used in the fields of automobiles, notebook computers, ballasts and the like, and has the advantages of high frequency and low impedance.

Description

Low-impedance capacitor and preparation method thereof
Technical Field
The application relates to the field of capacitors, in particular to a low-impedance capacitor and a preparation method thereof.
Background
The capacitor is a container for storing electric charges, and comprises a positive electrode, a negative electrode and a medium, wherein when a voltage is applied between the positive electrode and the negative electrode of the capacitor, the capacitor stores the electric charges. The capacitors can be roughly classified into organic dielectric capacitors, inorganic dielectric capacitors, electrolytic capacitors, electrothermal capacitors, air dielectric capacitors and the like according to the classification of dielectrics, wherein the aluminum electrolytic capacitors are widely applied at present, and the aluminum electrolytic capacitors can be widely applied to industries such as notebook computers, ballasts, automobile electronics and the like.
The aluminum electrolytic capacitor comprises two electrode plates and electrolyte, and the two electrode plates are separated by the electrolyte. When a current flows through a circuit including a capacitor, the capacitor, a resistor, and the like in the circuit have a back-blocking effect on the current, which is called an impedance effect. The current in the circuit is reduced due to the generation of impedance, and in order to reduce the impedance of the capacitor, an electrolyte with high water content is mostly adopted at present, so that the conductivity of the electrolyte is increased, and the impedance is reduced.
In view of the above-mentioned related art, the inventor believes that the volume of the electrolyte with a high water content is large, which results in a small amount of electrolyte in the capacitor when the capacitor is applied to a precision instrument, and thus the capacitor still has the defects of poor high frequency performance and high impedance.
Disclosure of Invention
In order to overcome the defect that the capacitor is high in impedance, the application provides a low-impedance capacitor and a preparation method thereof.
In a first aspect, the present application provides a low impedance capacitor, which adopts the following technical solution:
a low-impedance capacitor comprises an electrode plate, electrolytic paper and electrolyte, wherein the electrolytic paper comprises the following substances in parts by weight: 85-95 parts of softwood pulp fibers, 5-15 parts of Chinese alpine rush fibers and 0.1-1 part of nanofibrillar cellulose, wherein the beating degree of the Chinese alpine rush fibers is 30-50 DEG SR, and the softwood pulp fibers are the softwood pulp fibers which are beaten at a high concentration and have the beating degree of 70-90 DEG SR.
Through adopting above-mentioned technical scheme, at first, this application technical scheme carries out the conduction of electric charge with electrolyte on the electrolytic paper, through the electrolyte of load on the electrolytic paper, because the electrolytic paper has good electrical property, can reduce the impedance of condenser, the condenser volume of constituteing simultaneously is less, can be applied to less precision instruments and maintain lower impedance.
Secondly, according to the method, the softwood pulp fibers, the Chinese alpine rush fibers and the nanofibril cellulose are matched to prepare the electrolytic paper, and the fiber cohesive force in the electrolytic paper is enhanced due to the hydrogen bond structure on the nanofibril cellulose, so that the structure of the electrolytic paper is more compact, the pore structure of the electrolytic paper is reduced, the dielectric property and the tensile property of the electrolytic paper are improved, the impedance of a capacitor is reduced, and meanwhile, the occurrence of the fracture phenomenon of the electrolytic paper is reduced. And the Chinese alpine rush fibers and the nano fibril fibers can be interwoven with each other to form a three-dimensional mesh structure, so that the compactness of the electrolytic paper is further increased, a certain porosity of the electrolytic paper is kept, the absorption effect of the electrolytic paper on the electrolyte is improved, and the impedance of the capacitor is stably reduced.
And finally, the beating degree of the Chinese alpine rush fibers, the beating degree of the softwood pulp fibers and the beating concentration are optimized, and the devillicate fibrillation degrees of the softwood pulp fibers and the Chinese alpine rush fibers are increased, so that the softwood pulp fibers and the Chinese alpine rush fibers are easier to form a net structure in the electrolytic paper, and the tensile strength of the electrolytic paper is increased.
Preferably, the Chinese alpine rush fiber is modified by a modifier, and the modifier comprises one or two of sodium hydroxide and acrylamide.
By adopting the technical scheme, firstly, the Chinese alpine rush is modified by adopting sodium hydroxide, the sodium hydroxide can be diffused into the fiber cell wall, hemicellulose, resin, pigment and the like in a Chinese alpine rush fiber crystallization area are dissolved and removed, etching tunnels are formed on the fiber surface, more hydrogen bond binding sites are exposed, and the binding effect among fibers in the electrolytic paper is enhanced.
And secondly, the Chinese alpine rush is modified by adopting acrylamide, so that carboxyethyl can be introduced into the Chinese alpine rush fibers, hydrogen bond bonding between the Chinese alpine rush fibers is reduced, the Chinese alpine rush fibers are favorably devillicate and broomed, and the bonding effect between the fibers in the electrolytic paper is improved.
And finally, modifying the Chinese alpine rush by adopting sodium hydroxide and acrylamide together, firstly etching the Chinese alpine rush, reducing the crystallization of the Chinese alpine rush fiber, accelerating the decomposition and conversion of the acrylamide into carboxyethyl under an alkaline condition, synergistically improving the fibrillation of the Chinese alpine rush fiber and the combination effect of other fibers, stably improving the adsorption effect of the electrolytic paper on the electrolyte, namely improving the charge circulation effect and reducing the impedance of the capacitor.
Preferably, the softwood pulp fibers are preprocessed by biological enzymes, and the biological enzymes comprise any one of cellulase and pulping enzyme.
By adopting the technical scheme, the softwood pulp fibers are pretreated by adopting the cellulase or the pulping enzyme, the outer layer of the secondary wall of the fibers can be loosened, the water absorption and the swelling of the softwood pulp fibers are promoted, the fibrillation of the softwood pulp fibers is facilitated, and the combination effect among the fibers in the electrolytic paper is further improved.
Preferably, the electrode plate comprises an aluminum-based composite material doped with graphene, and the aluminum-based composite material is of a three-dimensional structure.
By adopting the technical scheme, since the graphene has a three-dimensional structure and a higher specific surface area, the graphene is doped into the aluminum electrode, a non-aggregated three-dimensional space form can be formed, the specific surface area of the electrode plate is increased, the contact sufficiency between the electrolyte plate and the electrolyte is improved, and the transfer of charges is facilitated; meanwhile, as the graphene can grow perpendicular to the aluminum electrode, charge transmission and storage paths can be optimized, the specific capacitance of the capacitor is improved, and the impedance of the capacitor can be reduced, so that the capacitor has the characteristic of high-frequency low impedance.
Preferably, the aluminum-based composite material further comprises manganese dioxide, and the aluminum-based composite material is in an open porous structure.
By adopting the technical scheme, manganese dioxide is introduced into the aluminum-based composite material, so that the graphene is loaded with a manganese dioxide nanosheet structure, the aluminum-based composite material still keeps a porous three-dimensional structure, and the porous three-dimensional structure is an open and non-agglomerated structure, so that repeated contact between an electrode plate and electrolyte is facilitated, electron transfer, ion conduction and electrolyte diffusion are remarkably promoted, a charge transmission path is further optimized, and the impedance of a capacitor is reduced. And due to the coating of the manganese dioxide nanosheets on the graphene, the manganese dioxide is used as a pseudo capacitor to be matched with the rest components in the aluminum-based composite material, so that the specific surface area of the electrode plate is optimized, the specific capacitance of the capacitor is further increased, and the electrochemical stability of the capacitor can be improved.
Preferably, the preparation of the aluminum matrix composite material comprises the following steps: pretreatment: soaking the aluminum foil in hydrochloric acid, etching, taking out to obtain an etched aluminum foil, and sequentially soaking the etched aluminum foil in a sodium hydroxide solution and a nitric acid solution to obtain a hole aluminum foil; preparing a composite material: placing the hole aluminum foil in a vacuum environment, heating, performing plasma treatment to obtain a plasma aluminum foil, introducing carbon source gas, and performing deposition treatment to obtain an intermediate; and (3) placing the intermediate into a potassium permanganate solution, stirring and mixing, carrying out constant-temperature treatment, taking out the intermediate, washing and drying to obtain the aluminum matrix composite.
By adopting the technical scheme, the aluminum foil is treated by hydrochloric acid, sodium hydroxide and nitric acid, impurities and oil stains on the aluminum foil are removed, a nucleation center is provided for aluminum element dissolution, then plasma treatment is carried out on the etched aluminum foil, the aluminum foil can be treated, and under the treatment of the plasma, an oxide film on the surface of the aluminum foil is softened and collapsed to be sunk into an aluminum foil substrate, so that an etching gallery is formed. Depositing graphene on the plasma aluminum foil to form Al between the graphene and the plasma aluminum foil 4 C 3 The layer and the carbon layer greatly optimize the charge transfer path and reduce the resistance of the capacitor. Finally, formed on aluminum foilThe deposition density of graphene on the aluminum foil can be optimized by etching the tunnel, the thickness of the graphene is effectively increased, and the specific capacitance of the capacitor is improved.
In addition, as the manganese dioxide is used as an electronic conductor, the electric conduction effect can be accelerated, the impedance of the capacitor is reduced, the self-repairing effect is strong, the performance of automatically repairing and isolating defects in an oxide film can be realized, the stability of the capacitor is improved, and the electrochemical performance of the capacitor is improved.
Preferably, the electrolyte comprises one or two of polyaniline and sol electrolyte.
By adopting the technical scheme, firstly, the polyaniline is used as the electrolyte, the polyaniline can effectively impregnate the electrolytic paper, the operation temperature is low, the influence of high-temperature operation on the capacitor is reduced, and a coating film is easily formed on the electrode plate to maintain the stability of the electrode plate.
Secondly, the sol electrolyte is adopted as the electrolyte, and the sol electrolyte can absorb more liquid due to the sol electrolyte form, so that after the sol electrolyte is adsorbed on the electrolytic paper, a better water retention effect can be maintained, the charge transmission effect of the capacitor is further maintained, and the stability of the capacitor is improved.
Finally, polyaniline and the sol electrolyte are matched to serve as the electrolyte, on one hand, the viscosity of the electrolyte is reduced, so that the electrolyte can be fully absorbed by the electrolytic paper, on the other hand, the adsorption effect of the electrolytic paper and the retention effect of the electrolyte can be improved through the water retention effect of the sol electrolyte, and the stability and the electrochemical effect of the capacitor are effectively improved.
Preferably, the polyaniline is doped with a doping acid, and the doping acid comprises any one of sulfuric acid, benzenesulfonic acid, D-camphor-10-sulfonic acid and dodecylbenzenesulfonic acid.
By adopting the technical scheme, the polyaniline is doped and modified by the doping acid, so that the strong interaction among polyaniline molecular chains is reduced, the conformations in polyaniline molecules and among the polyaniline molecules are improved, the charge delocalization on the molecular chains is facilitated, the main chain conjugation level is improved, the motion resistance of current carriers is reduced, the charge transportation effect of the polyaniline is improved, and the electrochemical performance of the capacitor is improved.
In addition, polyaniline and the nanofibril cellulose can be combined to form a fine nanorod structure, so that the combination effect between the electrolyte and the electrolytic paper is further enhanced, and the electrochemical effect of the capacitor is improved.
In a second aspect, the present application provides a method for manufacturing a low impedance capacitor, which adopts the following technical scheme:
a method for preparing a low-impedance capacitor, S1, dipping treatment: dipping the electrode plate and the electrolytic paper in the electrolyte, performing vacuum treatment under reduced pressure, repeatedly dipping and drying to obtain the dipped electrode plate and the electrolytic paper; s2, capacitor preparation: sequentially stacking and winding the electrode plates and the electrolytic paper to obtain a winding core, dipping the winding core in the diluted electrolyte, performing vacuum treatment under reduced pressure, repeatedly dipping and drying to obtain a dipped winding core; putting the impregnated roll core into an aluminum shell, sealing and aging to obtain a capacitor; wherein the aging treatment adopts pulse voltage to perform aging at room temperature.
Through adopting above-mentioned technical scheme, at first, in the flooding in-process, adopt vacuum impregnation's mode, can make the inside gas escape of capacitor core package, be favorable to gas-liquid exchange, electrolyte is changeed and is steeped in the electrolytic paper, effectively improves the electrochemistry effects such as electric capacity of condenser.
Secondly, when the capacitor is soaked, the electrolyte is diluted, the viscosity of the electrolyte is reduced, the soaking effect of the electrolyte on the electrolytic paper is accelerated, and the diluent can be quickly evaporated under a vacuum environment, so that the electrolyte can be firmly loaded on the electrolytic paper, the pores of the electrolytic paper and the electrode plate are fully filled, the soaking is repeated, and the electrochemical performance of the capacitor is stably improved.
Finally, in the aging treatment, the pulse voltage is adopted for aging, the pulse period is long, the charging time is long, so the aging efficiency is high, the effect is excellent, and the electrochemical effect of the capacitor is further improved.
In summary, the present application has the following beneficial effects:
1. the electrolytic paper is adopted to adsorb the electrolyte, so that the free flow of the electrolyte is reduced, the contact area between the electrolyte and the electrode plate is increased, the electrochemical performance of the capacitor is improved, and the size of the capacitor is reduced, so that the capacitor can be applied to a precision instrument; and moreover, the softwood pulp fibers, the Chinese alpine rush fibers and the nano fibril fibers are matched to prepare the electrolytic paper, a dense interwoven mesh structure can be formed in the electrolytic paper, the absorption effect of the electrolytic paper on the electrolyte is improved, the possibility of breakage of the electrolytic paper is reduced, the transportation effect of charges in the capacitor is facilitated, the impedance of the capacitor is reduced, and the electrochemical performance of the capacitor is improved.
2. In the application, an aluminum-based composite material is preferably adopted as the electrode plate, the electrode plate is subjected to plasma treatment at first, etching pores are formed on the electrode plate, more active functional groups are exposed, and then the electrode plate is subjected to polarity doping treatment, so that graphene vertically grows on the electrode plate, and a manganese dioxide nanosheet is coated on the graphene to jointly form an open three-dimensional porous structure, the specific surface area of the electrode plate and the transport path of electrons in the capacitor are optimized, the specific capacitance of the capacitor is increased, and meanwhile, the impedance of the capacitor is reduced.
3. According to the method, the impregnation effect of the electrolyte on the electrolytic paper is enhanced in a vacuum impregnation mode, the content of the electrolyte in the capacitor is improved, the flow resistance of charges in the capacitor is reduced, the aging treatment is performed on the capacitor in a pulse aging mode, the aging treatment speed is high, and the electrochemical effect of the capacitor is further improved.
Detailed Description
The present application will be described in further detail with reference to examples.
In the embodiment of the present application, the selected drugs of the apparatus are as follows, but not limited to:
the instrument comprises: the tester comprises a TH2832 type LCR digital bridge capacitance-inductance resistance tester of Peng measuring electronics technology Limited company in Dongguan city, ZX6591 type leakage current of new precision electronics Limited company caused by Changzhou city, and PECVD plasma vapor deposition equipment of Bona heat kiln Limited company in Zhengzhou.
Medicine preparation: the nanofibrillar cellulose is CNF of Wuhan La Na white pharmaceutical chemical company, GFY-4301 type pulping enzyme of Xiasang (Beijing) biological technology development company, and the resin is carbomer 940 resin of Qingdao Yinuxin new material company and conductive polyaniline of Guangzhou Rui Shi biological technology company.
Preparation example
Preparation of Chinese alpine rush fiber
Preparation example 1
Taking 0.5kg of Chinese alpine rush and 100kg of sodium hydroxide solution with the mass fraction of 15%, stirring and mixing, continuously stirring for 4h at the temperature of 40 ℃, carrying out suction filtration, and washing with water to obtain the dried Chinese alpine rush. Pulping, and adjusting the pulping degree to 30 DEG SR to obtain the modified Chinese alpine rush fiber 1.
Preparation examples 2 to 3
The difference from preparation example 1 is that: the beating degree is respectively adjusted to 40 degrees SR and 50 degrees SR, and the modified Chinese alpine rush fiber 2-3 is obtained.
Preparation example 4
Taking 0.5kg of Chinese alpine rush and 100kg of sodium hydroxide solution with the mass fraction of 15%, stirring and mixing to obtain dispersion, adding 10kg of acrylamide solution with the mass fraction of 10% into the dispersion, continuing stirring, carrying out squeezing treatment to obtain squeezed slurry with the mass fraction of 20%, sealing, placing in a 70 ℃ water bath for reaction, washing with water, and carrying out suction filtration to obtain the dried Chinese alpine rush. Pulping, and adjusting the pulping degree to 30 DEG SR to obtain the modified Chinese alpine rush fiber 4.
Preparation example 5
Mixing herba Clerodendranthi Spicati 0.5kg and water 100kg under stirring, absorbing water and swelling for 24 hr to obtain swollen herba Clerodendranthi Spicati fiber, pulping, and adjusting pulping degree to 30 ° SR to obtain herba Clerodendranthi Spicati fiber.
Preparation of softwood pulp fibers
Preparation example 6
5kg of softwood pulp fibers and 100kg of water are mixed, the mixture absorbs water to swell for 4 hours, the pulping concentration is adjusted to be 20 percent to obtain pulping liquid, the pulping degree is controlled to be 70 DEG SR, and the pulping is carried out according to the national standard QBT3702-1999 pulping Walli (Valley) pulping machine method to obtain the softwood pulp fibers 1.
Preparation examples 7 to 8
The difference from preparation 6 is that: and respectively adjusting the beating degree to 85 and 90 degrees SR to obtain the softwood pulp fibers 2-3.
Preparation example 9
The difference from preparation 6 is that: the beating concentration was adjusted to 1.57%, and softwood pulp fibers 4 were obtained.
Preparation example 10
The difference from preparation 6 is that: 2.5g of cellulase was added to 10kg of the beating liquid, and beating was carried out to obtain softwood pulp fibers 5.
Preparation example 11
The difference from preparation 6 is that: 2.5g of pulping enzyme is added into 10kg of pulping liquid for pulping to obtain softwood pulp fibers 6.
Examples of production of aluminum-based composite Material
Preparation example 12
Pretreatment: soaking the aluminum foil in 1M sodium hydroxide solution for 20min, and taking out to obtain a primary aluminum foil; and (3) soaking the primary aluminum foil in 1M hydrochloric acid solution, adjusting the temperature to 80 ℃, etching for 5min, and taking out to obtain the etched aluminum foil. And sequentially soaking the etched aluminum foil in 0.3M sodium hydroxide solution for 10min and 0.5M nitric acid solution for 10min to obtain the hole aluminum foil.
Preparing a composite material: and (3) placing the hole aluminum foil in a vacuum device, adjusting the pressure to be below 5Pa, and introducing 40ccm argon and 20ccm hydrogen to obtain the three-dimensional aluminum foil. Adjusting the pressure to 200Pa, heating to 550 ℃, adjusting the etching pressure to 400Pa and the radio frequency power to 200W, carrying out plasma treatment, and etching for 10min to obtain the plasma aluminum foil. And (3) introducing carbon source gas methane into the vacuum device, closing hydrogen, adjusting the pressure to 650Pa, and depositing for 60min to obtain an intermediate, namely the aluminum-based composite material 1 serving as the electrode plate 1.
Preparation example 13
The difference from preparation example 12 is that: dissolving 0.474kg of potassium permanganate in 60kg of water, stirring and mixing, and magnetically stirring to obtain a potassium permanganate solution; and (3) putting the intermediate into a potassium permanganate solution, transferring the intermediate into a high-pressure kettle, reacting at the constant temperature of 160 ℃ for 24 hours, taking out, cooling, taking out a solid, washing and drying to obtain the aluminum-based composite material 2 serving as the electrode plate 2.
Preparation example 14
The difference from preparation example 12 is that: without plasma treatment, the aluminum-based composite material 3 was obtained as the electrode sheet 3.
Preparation example of polyaniline
Preparation examples 15 to 17
Sodium dodecyl benzene sulfonate, ammonium persulfate and aniline monomers are respectively weighed, and the specific mass is shown in table 1. Dissolving sodium dodecyl benzene sulfonate in water, stirring and mixing to obtain a mixed solution, adding aniline monomer into the mixed solution, stirring and mixing, adding sulfuric acid with the mass fraction of 10% as doping acid, stirring and mixing to obtain a doping solution. Adding ammonium persulfate into the doped solution, continuously stirring, continuously reacting for 2h, performing suction filtration, retaining a filter cake, washing with water until the washing liquid is almost colorless, and washing with acetone until the washing liquid is light yellow. And (3) drying the filter cake at 80 ℃ for 24h, taking out, and grinding to obtain the polyaniline 1-3.
TABLE 1 PREPARATION EXAMPLES 15-17 POLYENYLENE PHENYLENE COMPOSITION
Figure DEST_PATH_IMAGE001
Preparation example 18
The difference from preparation 17 is that: polyaniline 4 was prepared using dodecylbenzenesulfonic acid as the doping acid instead of sulfuric acid in preparation example 17.
Preparation example 19
The difference from preparation 17 is that: polyaniline 5 was prepared using D-camphor-10-sulfonic acid as the doping acid instead of sulfuric acid in preparation example 17.
Preparation example 20
The difference from preparation 17 is that: polyaniline 6 was prepared using p-toluenesulfonic acid as a doping acid instead of sulfuric acid in preparation example 17.
Example of preparation of Sol electrolyte
Preparation example 21
0.5kg of resin and 19.5kg of 35% potassium hydroxide solution were mixed together to obtain a sol electrolyte.
Examples
Examples 1 to 3
In one aspect, the application provides a low impedance type capacitor, which comprises an electrode plate, electrolytic paper and electrolyte, wherein the electrolytic paper comprises softwood pulp fibers, Chinese alpine rush fibers and nanofibril cellulose, and the specific mass is shown in table 2.
In another aspect, the present application provides a method for making a low impedance capacitor, comprising the steps of:
preparing electrolytic paper: preparing the softwood pulp fiber, the Chinese alpine rush fiber and the nano fibril cellulose by adopting a papermaking method.
Preparing an electrolyte: mixing polyaniline, sol electrolyte, m-phenol and glacial acetic acid, wherein the specific mass is shown in Table 3, and obtaining the electrolyte.
Dipping treatment: and (3) dipping the electrode plate and the electrolytic paper in the electrolyte, taking out, drying, performing vacuum treatment under reduced pressure, repeatedly dipping and drying, and repeating for 15 times to obtain the dipped electrode plate and the electrolytic paper.
Preparing a capacitor: sequentially stacking and winding the electrode plates and the electrolytic paper to obtain a winding core, dipping the winding core in the electrolyte, performing vacuum treatment under reduced pressure, repeatedly dipping and drying, and repeating for 5 times to obtain a dipped winding core; and (3) putting the impregnated roll core into an aluminum shell, sealing, adding 65V pulse direct current voltage at two ends of the capacitor, aging for 1h, and performing positive and negative treatment twice respectively to obtain the capacitor 1-3.
Table 2 examples 1-3 electrolytic paper compositions
Figure 913510DEST_PATH_IMAGE002
Table 3 examples 1-3 electrolyte compositions
Figure DEST_PATH_IMAGE003
Examples 4 to 7
The difference from example 2 is that: capacitors 4-7 were prepared using the modified chinese alpine rush fibers 1-4 instead of the chinese alpine rush fibers of example 2.
Examples 8 to 12
The difference from example 2 is that: capacitors 8-12 were prepared using softwood pulp fibers 2-6 instead of softwood pulp fibers of example 2.
Examples 13 to 14
The difference from example 2 is that: capacitors 13 to 14 were prepared using electrode sheets 2 to 3 instead of electrode sheet 1 in example 2.
Examples 15 to 20
The difference from example 2 is that: capacitors 15 to 20 were prepared using polyaniline 1 to 6 instead of polyaniline in example 2.
Example 21
The difference from example 2 is that: a capacitor 21 was prepared using a sol electrolyte instead of the polyaniline in example 1.
Example 22
The difference from example 2 is that: the capacitor 22 was prepared by adding 3kg of sol electrolyte to the electrolyte.
Comparative example
Comparative example 1
This comparative example is different from example 2 in that an electrolytic paper was prepared using softwood pulp fibers in the comparative example instead of the electrolytic paper in example 2 to prepare a capacitor 23.
Comparative example 2
This comparative example is different from example 2 in that a copper sulfate solution having a mass fraction of 40% was used as an electrolyte in place of the electrolyte in example 2 to prepare a capacitor 24.
Performance test
And (3) detecting electrical properties: the resistance and capacitance of the capacitors 1-24 at 150kHz were measured using an LCR meter, and the leakage current of the capacitors was measured using a leakage current tester.
TABLE 4 Performance test of examples 1-22 and comparative examples 1-2
Figure 17601DEST_PATH_IMAGE004
The comparison of the performance tests in combination with table 4 can find that:
(1) by combining examples 1-3 with comparative examples 1-2, it can be found that: the capacitor manufactured in examples 1 to 3 had a decreased resistance and a decreased leakage current and an increased capacitance, which indicates that the softwood pulp fibers, the Chinese alpine rush fibers and the nanofibrillar cellulose of the present application manufactured the electrolytic paper could form an interwoven network structure in the electrolytic paper, thereby increasing the adsorption and retention effects of the electrolytic paper on the electrolyte, decreasing the movement resistance of charges in the capacitor, i.e., decreasing the resistance of the capacitor, and improving the dielectric effect of the capacitor. As can be seen from table 4, the electrochemical performance of the capacitor produced in example 3 is better, indicating that the ratio of the components in the electrolytic paper in example 3 is more suitable.
(2) Comparing the combination of examples 4-7 and example 3, it can be found that: the capacitors obtained in examples 4 to 7 had decreased resistance and leakage current and increased capacitance, which indicates that the present application optimizes the beating degree of Chinese alpine rush fibers, and improves the fibrillation degree of Chinese alpine rush fibers. The crystal region of the Chinese alpine rush fiber can be damaged by modifying the Chinese alpine rush fiber by adopting the modifier, and the carboxyethyl is introduced to the Chinese alpine rush fiber, so that not only is the devillicate fibrillation of the Chinese alpine rush fiber promoted, but also the bonding effect among the fibers in the electrolytic paper can be promoted. As can be seen from Table 4, the electrochemical properties of the capacitors obtained in examples 5 and 7 are good, which indicates that the beating degree of the Chinese alpine rush fibers is proper in example 5 and the modifier is proper in example 7.
(3) A comparison of examples 8-9, example 10, examples 11-12 and example 3 has been found: the capacitors obtained in examples 8 to 12 had decreased resistance and leakage current and increased capacitance, which indicates that the present application optimizes the beating degree and beating concentration of softwood pulp fibers, improves the fibrillation degree of softwood pulp fibers, and contributes to the bonding effect between the fibers in the electrolytic paper. In addition, the softwood pulp fibers are pretreated by adopting the biological enzyme, so that the fiber wall layer can be loosened and damaged, the devillicate fibrillation of the softwood pulp fibers is further improved, and the absorption effect of the electrolytic paper on the electrolyte is improved. As can be seen from table 4, the electrochemical performance of the capacitor produced in example 8 is good, indicating that the beating degree of softwood pulp fibers in example 8 is more suitable.
(4) A comparison of examples 13-14 with example 3 shows that: the resistance and the leakage current of the capacitor prepared in the examples 1 to 3 are improved, and the capacitance is reduced, which shows that the graphene and manganese dioxide nanosheet vertically grown on the aluminum foil optimizes the transport path of charges in the capacitor and stably reduces the resistance of the capacitor. As can be seen from table 4, the electrochemical performance of the capacitor obtained in example 13 is better, and it is demonstrated that the structure of the aluminum-based composite material in example 13 is suitable.
(5) A comparison of examples 15-17, examples 18-20 and example 3 has been found: the capacitors manufactured in examples 15-20 have reduced impedance and leakage current and increased capacitance, which indicates that the electrolyte is diluted, the viscosity of the electrolyte is reduced, the absorption effect of the electrolyte on the electrolyte is improved, and the diluent can be volatilized quickly under a vacuum environment, so that the loading effect of the electrolyte on the electrolyte is improved stably. The doped sensitivity of the polyaniline is realized by adopting the doping acid, so that the interaction among polyaniline molecular chains can be reduced, the motion resistance of current carriers is reduced, and the impedance of the capacitor is reduced. As can be seen from table 4, the electrochemical performance of the capacitors obtained in example 17 and example 18 is good, which indicates that the ratio of polyaniline is suitable in example 17, and the doping acid is suitable in example 18.
(6) A comparison of examples 21-22 with example 3 shows that: the capacitors obtained in examples 21 to 22 had decreased resistance and leakage current and increased capacitance, which indicates that the use of aniline and sol electrolyte in combination in the present application can increase the retention of electrolyte by the electrolytic paper, i.e., increase the charge transfer rate in the capacitor and improve the resistance of the capacitor. As can be seen from table 4, the electrochemical performance of the capacitor prepared in example 22 is better, which indicates that the mixture ratio of the components in the electrolyte in example 22 is more suitable.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims (9)

1. A low-impedance capacitor is characterized by comprising electrode plates, electrolytic paper and electrolyte, wherein the electrolytic paper comprises the following substances in parts by weight: 85-95 parts of softwood pulp fibers, 5-15 parts of Chinese alpine rush fibers and 0.1-1 part of nanofibrillar cellulose, wherein the beating degree of the Chinese alpine rush fibers is 30-50 DEG SR, and the softwood pulp fibers are the softwood pulp fibers which are beaten at a high concentration and have the beating degree of 70-90 DEG SR.
2. A low impedance capacitor as recited in claim 1, wherein: the Chinese alpine rush fiber is modified by a modifier, and the modifier comprises one or two of sodium hydroxide and acrylamide.
3. A low impedance capacitor as recited in claim 2, wherein: the softwood pulp fibers are preprocessed by biological enzyme, and the biological enzyme comprises any one of cellulase and pulping enzyme.
4. A low impedance type capacitor as claimed in claim 1, wherein: the electrode plate comprises an aluminum-based composite material doped with graphene, and the aluminum-based composite material is of a three-dimensional structure.
5. A low impedance capacitor as claimed in claim 4, wherein: the aluminum-based composite material also comprises manganese dioxide, and the aluminum-based composite material is in an open porous structure.
6. A low impedance capacitor according to claim 5, wherein said aluminum matrix composite is prepared by the steps of:
pretreatment: soaking the aluminum foil in hydrochloric acid, etching, taking out to obtain an etched aluminum foil, and sequentially soaking the etched aluminum foil in a sodium hydroxide solution and a nitric acid solution to obtain a hole aluminum foil;
preparing a composite material: placing the hole aluminum foil in a vacuum environment, heating, performing plasma treatment to obtain a plasma aluminum foil, introducing a carbon source gas, and performing deposition treatment to obtain an intermediate; and (3) placing the intermediate into a potassium permanganate solution, stirring and mixing, carrying out constant-temperature treatment, taking out the intermediate, washing and drying to obtain the aluminum matrix composite.
7. A low impedance capacitor as recited in claim 1, wherein: the electrolyte comprises one or two of polyaniline and sol electrolyte.
8. A low impedance capacitor as recited in claim 7, wherein: the polyaniline is doped by doping acid, and the doping acid comprises any one of sulfuric acid, benzenesulfonic acid, D-camphor-10-sulfonic acid and dodecylbenzenesulfonic acid.
9. A method of forming a low impedance capacitor as claimed in any one of claims 1 to 8, comprising the steps of:
s1, immersion treatment: taking the electrode plate and the diluted electrolytic paper to be dipped in the electrolyte, performing vacuum treatment under reduced pressure, repeatedly dipping and drying to obtain the dipped electrode plate and the electrolytic paper;
s2, preparing a capacitor: sequentially stacking and winding the electrode plates and the electrolytic paper to obtain a winding core, dipping the winding core in the electrolyte, performing vacuum treatment under reduced pressure, repeatedly dipping and drying to obtain a dipped winding core; putting the impregnated roll core into an aluminum shell, sealing and aging to obtain a capacitor; wherein the aging treatment adopts pulse voltage to perform aging at room temperature.
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Publication number Priority date Publication date Assignee Title
JPH11102684A (en) * 1998-08-18 1999-04-13 Nippon Kodoshi Corp Separator paper for alkaline battery
CN101187185A (en) * 2003-12-09 2008-05-28 浙江凯恩特种材料股份有限公司 High tightness electrolytic capacitor paper and its preparation method
CN105609319A (en) * 2016-01-29 2016-05-25 西北师范大学 Flaky titanium carbide-loaded manganese dioxide composite material for super capacitor electrode material and preparation of flaky titanium carbide-loaded manganese dioxide composite material
CN109722945A (en) * 2018-11-30 2019-05-07 山东鲁南新材料股份有限公司 The resistance to breakdown combined electrolysis kraft capacitor paper of one kind and its production method
CN112064411A (en) * 2020-08-07 2020-12-11 浙江哲丰新材料有限公司 Preparation method of low-basis-weight high-strength glassine paper
CN114263069A (en) * 2021-12-31 2022-04-01 浙江凯恩新材料有限公司 Low-voltage low-loss electrolytic capacitor paper and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11102684A (en) * 1998-08-18 1999-04-13 Nippon Kodoshi Corp Separator paper for alkaline battery
CN101187185A (en) * 2003-12-09 2008-05-28 浙江凯恩特种材料股份有限公司 High tightness electrolytic capacitor paper and its preparation method
CN105609319A (en) * 2016-01-29 2016-05-25 西北师范大学 Flaky titanium carbide-loaded manganese dioxide composite material for super capacitor electrode material and preparation of flaky titanium carbide-loaded manganese dioxide composite material
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CN114263069A (en) * 2021-12-31 2022-04-01 浙江凯恩新材料有限公司 Low-voltage low-loss electrolytic capacitor paper and preparation method and application thereof

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