CN114999829B - Low-impedance capacitor and preparation method thereof - Google Patents

Low-impedance capacitor and preparation method thereof Download PDF

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CN114999829B
CN114999829B CN202210604109.0A CN202210604109A CN114999829B CN 114999829 B CN114999829 B CN 114999829B CN 202210604109 A CN202210604109 A CN 202210604109A CN 114999829 B CN114999829 B CN 114999829B
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electrolyte
capacitor
electrolytic paper
aluminum
composite material
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CN114999829A (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
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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
    • H01G9/004—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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    • 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. The 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 needlebush wood pulp fiber, 5-15 parts of Chinese alpine rush fiber and 0.1-1 part of nanofibrillar cellulose, wherein the beating degree of the Chinese alpine rush fiber is 30-50 DEG SR, and the needlebush wood pulp fiber is the needlebush wood pulp fiber with the beating degree of 70-90 DEG SR after high-concentration beating. The preparation method comprises S1, dipping treatment; s2, preparing a capacitor. The low-impedance 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 present application relates to the field of capacitors, and in particular, to a low impedance capacitor and a method of making the same.
Background
A capacitor is a container for storing electric charge and comprises a positive electrode, a negative electrode and a medium, and when a voltage is applied between the positive electrode and the negative electrode of the capacitor, the capacitor stores electric charge. Capacitors can be roughly classified into organic dielectric capacitors, inorganic dielectric capacitors, electrolytic capacitors, electrothermal capacitors, air dielectric capacitors and the like according to dielectric classifications, wherein aluminum electrolytic capacitors are widely applied at present, and can be widely applied to industries such as notebook computers, ballasts, automobile electronics and the like.
The aluminum electrolytic capacitor includes two electrode sheets and an electrolyte, the two electrode sheets being separated by the electrolyte. When a current flows through a circuit including a capacitor, the resistance, and the like in the circuit have a back-blocking effect on the current, and this effect is called an impedance effect. In order to reduce the impedance of the capacitor, an electrolyte with higher water content is mostly adopted at present, and the conductivity of the electrolyte is increased, so that the impedance is reduced.
With respect to the above-mentioned related art, the inventors consider that the volume of the electrolyte having a high water content is large, and when the capacitor is applied to a precision instrument, the electrolyte in the capacitor is small, and thus the capacitor still has the defects of poor high-frequency property and high impedance.
Disclosure of Invention
In order to overcome the defect of higher impedance of the capacitor, 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 scheme:
the 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 fiber, 5-15 parts of Chinese alpine rush fiber and 0.1-1 part of nanofibrillar cellulose, wherein the beating degree of the Chinese alpine rush fiber is 30-50 DEG SR, and the softwood pulp fiber is the softwood pulp fiber with the beating degree of 70-90 DEG SR after high-concentration beating.
Through adopting above-mentioned technical scheme, at first, this application technical scheme is loaded electrolyte on the electrolysis paper, carries out the conduction of electric charge through the electrolyte that loads on the electrolysis paper, because the electrolysis paper has good electrical properties, can reduce the impedance of condenser, and the condenser volume of constituteing simultaneously is less, can be applied to less precision instrument and maintain lower impedance.
Secondly, the needled wood pulp fiber, the Chinese alpine rush fiber and the nanofibrillar cellulose are adopted to prepare the electrolytic paper in a matched manner, and the hydrogen bond structure on the nanofibrillar cellulose enables the cohesive force of the fiber in the electrolytic paper to be enhanced, namely 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 fracture phenomenon of the electrolytic paper is reduced. The Chinese alpine rush fibers and the nanofibrillar fibers can be mutually interwoven to form a three-dimensional net structure, so that the tightness of the electrolytic paper is further increased, the electrolytic paper maintains a certain porosity, the absorption effect of the electrolytic paper on the electrolyte is improved, and the impedance of the capacitor is stably reduced.
Finally, the beating degree of the Chinese alpine rush fibers, the beating degree and the beating concentration of the softwood pulp fibers are optimized, the degree of fibrillation of the softwood pulp fibers and the Chinese alpine rush fibers is increased, the softwood pulp fibers and the Chinese alpine rush fibers are enabled to form a net structure in the electrolytic paper more easily, and the tensile strength of the electrolytic paper is increased.
Preferably, the Chinese alpine rush fiber is Chinese alpine rush fiber modified by a modifier, and the modifier comprises one or two of sodium hydroxide and acrylamide.
Through adopting above-mentioned technical scheme, firstly, adopt sodium hydroxide to carry out the modification to the chinese alpine rush, sodium hydroxide can diffuse to inside the fibre cell wall, and hemicellulose, resin and pigment etc. in chinese alpine rush fibre crystallization district are dissolved and are got rid of to form etching tunnel on the fibre surface, expose more hydrogen bond bonding sites, strengthened the bonding effect between each fibre in the electrolytic paper.
Secondly, the modification treatment is carried out on the Chinese alpine rush by adopting the acrylamide, so that carboxyethyl can be introduced into the Chinese alpine rush fibers, the hydrogen bond combination among the Chinese alpine rush fibers is reduced, the Chinese alpine rush fibers are favorably split into filaments, and the combination effect among the fibers in the electrolytic paper is improved.
Finally, sodium hydroxide and acrylamide are adopted to jointly modify the Chinese alpine rush, the Chinese alpine rush is firstly subjected to etching treatment, the crystallization of Chinese alpine rush fibers is reduced, in addition, under alkaline conditions, the decomposition and conversion of the acrylamide into carboxyethyl are quickened, the fibrillation of the Chinese alpine rush fibers and the combination effect between the Chinese alpine rush fibers and other fibers are synergistically improved, the adsorption effect of electrolytic paper on electrolyte is stably improved, namely, the charge transfer effect is improved, and the impedance of a capacitor is reduced.
Preferably, the softwood pulp fiber is a softwood pulp fiber pretreated by biological enzymes, wherein the biological enzymes comprise any one of cellulase and pulping enzyme.
Through adopting above-mentioned technical scheme, adopt cellulase or beating enzyme to carry out preliminary treatment to the softwood pulp fibre, can loose fibre secondary wall external layer, promote the softwood pulp fibre to absorb water moist rising, be favorable to the softwood pulp fibre to divide silk brooming, further improved the bonding effect between each fibre in the electrolytic paper.
Preferably, the electrode sheet comprises an aluminum-based composite material doped with graphene, and the aluminum-based composite material has a three-dimensional structure.
By adopting the technical scheme, as the graphene has a three-dimensional structure and a higher specific surface area, the graphene is doped into the aluminum electrode, a non-agglomerated 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 graphene can grow perpendicular to the aluminum electrode, charge transmission and storage paths can be optimized, specific capacitance of the capacitor can be improved, impedance of the capacitor can be reduced, and the capacitor can obtain high-frequency low-impedance characteristics.
Preferably, the aluminum-based composite material further comprises manganese dioxide, and the aluminum-based composite material has an open porous structure.
By adopting the technical scheme, the manganese dioxide is introduced into the aluminum-based composite material, so that the graphene is loaded with the manganese dioxide nano sheet structure, the aluminum-based composite material still maintains a porous three-dimensional structure, and the porous three-dimensional structure is of an open and non-agglomerated structure, thereby being beneficial to repeated contact between the electrode sheet and electrolyte, remarkably promoting electron transfer, ion conduction and electrolyte diffusion, further optimizing a charge transmission path and reducing the impedance of a capacitor. And due to the coating of the manganese dioxide nano-sheet 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 sheet 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-based composite material comprises the following steps: pretreatment: immersing the aluminum foil in hydrochloric acid, etching, taking out to obtain etched aluminum foil, and immersing the etched aluminum foil in sodium hydroxide and nitric acid solution in sequence 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 an ionic aluminum foil, introducing carbon source gas, and performing deposition treatment to obtain an intermediate; and (3) placing the intermediate in a potassium permanganate solution, stirring and mixing, performing constant-temperature treatment, taking out the intermediate, washing and drying to obtain the aluminum-based composite material.
Through adopting above-mentioned technical scheme, through hydrochloric acid, sodium hydroxide and nitric acid treatment aluminium foil, impurity and greasy dirt on the removal aluminium foil provide the nucleation center for the aluminium element is dissolved, carries out plasma treatment to etching aluminium foil again, can handle the aluminium foil, under plasma's treatment, the oxidation film on aluminium foil surface softens and collapses, falls into the aluminium foil substrate, forms etching tunnel. Then depositing graphene on the ion aluminum foil, and forming Al between the graphene and the ion aluminum foil 4 C 3 The layers and carbon layer greatly optimize the charge transport path and reduce the resistance of the capacitor. Finally, the etching tunnel formed on the aluminum foil can optimize the deposition density of the graphene on the aluminum foil, effectively increase the thickness of the graphene and improve the specific capacitance of the capacitor.
In addition, as the manganese dioxide is used as an electron conductor, the electric conduction effect can be accelerated, the impedance of the capacitor is reduced, the self-repairing effect is stronger, the performance of defects in the oxide film can be automatically repaired and isolated, 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.
Through adopting above-mentioned technical scheme, firstly, adopt polyaniline as electrolyte, polyaniline can effectively impregnate the electrolytic paper, and operating temperature is low, has reduced the influence of high temperature operation to the condenser to the coating film is formed on the electrode slice relatively easily, maintains the stability of electrode slice.
Secondly, the sol electrolyte is adopted as electrolyte, and due to the sol electrolyte form, more liquid can be absorbed, and after the sol electrolyte is adsorbed on the electrolytic paper, a better water-retaining 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 sol electrolyte are matched to be used as electrolyte, so that on one hand, the viscosity of the electrolyte is reduced, the electrolyte can be fully absorbed by the electrolyte, and on the other hand, the adsorption effect of the electrolyte and the holding 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 polyaniline doped with 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 doping acid, so that the strong interaction between polyaniline molecular chains is reduced, the conformation in the polyaniline molecules and between the polyaniline molecules is improved, the charge delocalization on the molecular chains is facilitated, the conjugation level of a main chain is improved, the movement resistance of carriers is reduced, the charge transport effect of the polyaniline is improved, and the electrochemical performance of the capacitor is improved.
And the polyaniline and the nanofibrillar 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 preparation method of a low-impedance capacitor comprises the following steps of S1, dipping treatment: immersing the electrode sheet and the electrolytic paper in electrolyte, performing vacuum treatment under reduced pressure, repeatedly immersing and drying to obtain the immersed electrode sheet and electrolytic paper; s2, preparing a capacitor: sequentially stacking and winding the electrode sheet and the electrolytic paper to obtain a winding core, immersing the winding core in diluted electrolyte, performing vacuum treatment under reduced pressure, repeatedly immersing and drying to obtain an immersed winding core; placing the impregnated winding core into an aluminum shell, and 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, at the dipping process, adopt the mode of vacuum impregnation, can make the inside gaseous discharge of condenser core package, be favorable to gas-liquid exchange, electrolyte is more easy to impregnate in the electrolytic paper, effectively improves the electric capacity etc. electrochemical effect of condenser.
Secondly, when in impregnation, the electrolyte is diluted, the viscosity of the electrolyte is reduced, the impregnation effect of the electrolyte on the electrolyte is accelerated, and in a vacuum environment, the diluent can be quickly evaporated, so that the electrolyte can be firmly loaded on the electrolyte, the pores of the electrolyte and the electrode plate are fully filled, and the impregnation is repeated, thereby stably improving the electrochemical performance of the capacitor.
Finally, in the aging process, the pulse voltage is adopted for aging, the pulse period is long, and the charging time is long, so that 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. because the electrolytic paper is adopted to adsorb the electrolyte, 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 precise instrument; in addition, the needled wood pulp fiber, the Chinese alpine rush fiber and the nanofibrillar fiber are matched to prepare the electrolytic paper, a compact and interlaced net structure can be formed in the electrolytic paper, the absorption effect of the electrolytic paper on the electrolytic solution 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 method, an aluminum-based composite material is preferably adopted as an electrode slice, plasma treatment is firstly carried out on the electrode slice, etching holes are formed in the electrode slice and more active functional groups are exposed, then, the electrode slice is subjected to polarity doping treatment, so that graphene vertically grows on the electrode slice, and manganese dioxide nano-sheets are coated on the graphene to jointly form an open three-dimensional porous structure, the specific surface area of the electrode slice and the transportation path of electrons in a 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 dipping effect of the electrolyte on the electrolytic paper is enhanced through the vacuum dipping mode, the content of the electrolyte in the capacitor is improved, the flow resistance of charges in the capacitor is reduced, the capacitor is subjected to aging treatment through the pulse aging mode, the aging treatment speed is high, and the electrochemical effect of the capacitor is further improved.
Detailed Description
The present application is described in further detail below with reference to examples.
In the embodiment of the present application, the selected instrument medicines are shown below, but not limited to:
instrument: ZX6591 leakage current of new precision electronic Co., ltd., zhengzhou, bona thermal kiln Co., ltd., a PECVD plasma vapor deposition device of the same, which is a test instrument for measuring capacitance, inductance and resistance of a TH2832 LCR digital bridge, which is a test instrument for measuring capacitance, inductance and resistance of electronic technologies, inc., of Dongguan, city, etc.
Medicine: the nanofibrillar cellulose is CNF of Wuhan-Han-Nabai pharmaceutical chemical industry Co., ltd, GFY-4301 pulping enzyme of Xia Cheng (Beijing) biotechnology development Co., ltd, and the resin is carbomer 940 resin of Qingdao Yinuo Xin New material Co., ltd, conductive polyaniline of Guangzhou Rui Shi biotechnology Co., ltd.
Preparation example
Preparation example of Chinese alpine rush fiber
Preparation example 1
Mixing 0.5kg of Chinese alpine rush and 100kg of sodium hydroxide solution with the mass fraction of 15%, stirring and mixing, continuously stirring for 4 hours at 40 ℃, filtering, washing with water, and obtaining the dried Chinese alpine rush. Pulping, and adjusting the beating degree to 30 DEG SR to obtain the modified Chinese alpine rush fiber 1.
PREPARATION EXAMPLES 2-3
The difference from the preparation example 1 is that: and respectively regulating the beating degree to 40 DEG SR and 50 DEG SR to obtain the modified Chinese alpine rush fiber 2-3.
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 a dispersion liquid, adding 10kg of acrylamide solution with the mass fraction of 10% into the dispersion liquid, continuously stirring, squeezing to obtain a squeezed slurry with the mass fraction of 20%, sealing, placing in a water bath at 70 ℃ for reaction, washing with water, and suction filtering to obtain the dried Chinese alpine rush. Pulping, and adjusting the beating degree to 30 DEG SR to obtain the modified Chinese alpine rush fiber 4.
Preparation example 5
Mixing 0.5kg of Chinese alpine rush with 100kg of water under stirring, absorbing water, swelling for 24h to obtain swollen Chinese alpine rush fiber, pulping, and adjusting the pulping degree to 30 DEG SR to obtain Chinese alpine rush fiber.
Preparation of softwood pulp fiber
Preparation example 6
Mixing 5kg of softwood pulp fiber with 100kg of water, swelling for 4 hours by absorbing water, adjusting the pulping concentration to 20%, obtaining pulping liquid, controlling the pulping degree to be 70 DEG SR, and pulping according to the national standard QBT3702-1999 laboratory pulping Valley (Valley) pulping method to obtain the softwood pulp fiber 1.
Preparation examples 7 to 8
The difference from preparation example 6 is that: the beating degree is respectively adjusted to be 85 degrees and 90 degrees SR, and the softwood pulp fiber 2-3 is obtained.
Preparation example 9
The difference from preparation example 6 is that: the pulping concentration was adjusted to 1.57% to obtain softwood pulp fiber 4.
Preparation example 10
The difference from preparation example 6 is that: to 10kg of the pulping liquor, 2.5g of cellulase was added, and pulping was carried out to obtain softwood pulp fiber 5.
PREPARATION EXAMPLE 11
The difference from preparation example 6 is that: to 10kg of the pulping liquor, 2.5g of a pulping enzyme was added, and pulping was carried out to obtain softwood pulp fiber 6.
Preparation example of aluminum-based composite Material
Preparation example 12
Pretreatment: soaking aluminum foil in 1M sodium hydroxide solution for 20min, and taking out to obtain primary aluminum foil; and immersing the primary aluminum foil in a 1M hydrochloric acid solution, adjusting the temperature to 80 ℃, etching for 5min, and taking out to obtain the etched aluminum foil. And immersing the etched aluminum foil in a 0.3M sodium hydroxide solution for 10min and a 0.5M nitric acid solution for 10min in sequence to obtain the hole aluminum foil.
Preparing a composite material: and placing the hole aluminum foil in a vacuum device, adjusting the pressure to be lower than 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, adjusting the radio frequency power to 200W, performing plasma treatment, and etching for 10min to obtain the ion 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) placing the intermediate into a potassium permanganate solution, transferring the potassium permanganate solution into an autoclave, reacting for 24 hours at a constant temperature of 160 ℃, taking out, cooling, taking out the solid, washing, and drying to obtain the aluminum-based composite material 2 serving as the electrode slice 2.
PREPARATION EXAMPLE 14
The difference from preparation example 12 is that: the aluminum-based composite material 3 was obtained as the electrode sheet 3 without performing plasma treatment.
Polyaniline preparation example
Preparation examples 15 to 17
Sodium dodecyl benzene sulfonate, ammonium persulfate and aniline monomers were weighed separately 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 monomers into the mixed solution, stirring and mixing, adding sulfuric acid with the mass fraction of 10% as doping acid, and stirring and mixing to obtain a doping solution. Ammonium persulfate is added into the doping solution, stirring is continued, reaction is continued for 2 hours, suction filtration is performed, a filter cake is reserved, water washing is performed until the washing liquid is almost colorless, and acetone washing is performed until the washing liquid is light yellow. And (3) drying the filter cake at 80 ℃ for 24 hours, taking out, and grinding to obtain polyaniline 1-3.
TABLE 1 preparation examples 15-17 polyaniline compositions
Figure DEST_PATH_IMAGE001
PREPARATION EXAMPLE 18
The difference from preparation example 17 is that: polyaniline 4 was prepared using dodecylbenzenesulfonic acid as doping acid instead of sulfuric acid in preparation example 17.
Preparation example 19
The difference from preparation example 17 is that: polyaniline 5 was prepared using D-camphor-10-sulfonic acid as doping acid instead of sulfuric acid in preparation example 17.
Preparation example 20
The difference from preparation example 17 is that: polyaniline 6 was prepared using p-toluenesulfonic acid as doping acid instead of sulfuric acid in preparation example 17.
Preparation example of sol electrolyte
Preparation example 21
0.5kg of resin and 19.5kg of potassium hydroxide solution with a mass fraction of 35% were taken and mixed to obtain a sol electrolyte.
Examples
Examples 1 to 3
In one aspect, the present application provides a low impedance capacitor comprising an electrode sheet, an electrolytic paper, and an electrolyte, the electrolytic paper comprising softwood pulp fibers, chinese alpine rush fibers, and nanofibrillar cellulose, the specific mass being as shown in table 2.
In another aspect, the present application provides a method for manufacturing a low impedance capacitor, comprising the steps of:
preparing electrolytic paper: taking softwood pulp fiber, chinese alpine rush fiber and nanofibrillar cellulose, and preparing the electrolytic paper by adopting a papermaking mode.
Preparing an electrolyte: polyaniline, sol electrolyte, meta-phenol and glacial acetic acid are taken and mixed, and the specific mass is shown in table 3, so that the electrolyte is obtained.
Dipping treatment: immersing the electrode slice and the electrolytic paper in the electrolyte, taking out, drying, decompressing and vacuum treating, repeating the immersing and drying for 15 times, and obtaining the immersed electrode slice and electrolytic paper.
Preparing a capacitor: sequentially stacking and winding the electrode sheet and the electrolytic paper to obtain a winding core, immersing the winding core in the electrolyte, performing vacuum treatment under reduced pressure, repeatedly immersing and drying, and repeating for 5 times to obtain an immersed winding core; and (3) putting the impregnated winding core into an aluminum shell, sealing, and adding 65V pulse direct current voltage at two ends of the capacitor for aging for 1h, wherein the positive and negative directions are respectively twice to obtain the capacitor 1-3.
TABLE 2 examples 1-3 electrolytic paper composition
Figure 913510DEST_PATH_IMAGE002
TABLE 3 electrolyte compositions of examples 1-3
Figure DEST_PATH_IMAGE003
Examples 4 to 7
The difference from example 2 is that: the modified asparagus fiber 1-4 was used to replace the asparagus fiber in example 2 to prepare the capacitor 4-7.
Examples 8 to 12
The difference from example 2 is that: instead of the softwood pulp fibers in example 2, softwood pulp fibers 2-6 were used to prepare capacitors 8-12.
Examples 13 to 14
The difference from example 2 is that: capacitors 13-14 were fabricated using electrode sheet 2-3 instead of electrode sheet 1 in example 2.
Examples 15 to 20
The difference from example 2 is that: capacitors 15-20 were prepared using polyaniline 1-6 instead of polyaniline in example 2.
Example 21
The difference from example 2 is that: a sol electrolyte was used instead of the polyaniline in example 1 to prepare a capacitor 21.
Example 22
The difference from example 2 is that: to the electrolyte, 3kg of sol electrolyte was added to prepare a capacitor 22.
Comparative example
Comparative example 1
This comparative example differs from example 2 in that in this comparative example, an electrolytic paper was prepared using softwood pulp fiber instead of the electrolytic paper in example 2, and a capacitor 23 was prepared.
Comparative example 2
This comparative example differs from example 2 in that a 40% by mass copper sulfate solution was used as an electrolyte in place of the electrolyte in example 2 to prepare the capacitor 24.
Performance test
And (3) electrical property detection: the impedance 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 for examples 1-22, comparative examples 1-2
Figure 17601DEST_PATH_IMAGE004
The comparison of performance tests in combination with Table 4 can be found:
(1) Comparison of examples 1-3 and comparative examples 1-2 shows that: the capacitor prepared in examples 1-3 has reduced impedance and leakage current and improved capacitance, which means that the interleaved network structure can be formed in the electrolytic paper by preparing the electrolytic paper from the softwood pulp fiber, the Chinese alpine rush fiber and the nanofibrillar cellulose, thereby improving the adsorption effect and the retention effect of the electrolytic paper on the electrolyte, reducing the movement resistance of charges in the capacitor, namely reducing the resistance of the capacitor, and improving the dielectric effect of the capacitor. As can be seen from Table 4, the electrochemical properties of the capacitor obtained in example 3 were excellent, indicating that the ratio of the components in the electrolytic paper in example 3 was appropriate.
(2) As can be seen from the comparison of examples 4-7 and example 3: the capacitor prepared in examples 4-7 has reduced impedance and leakage current, and improved capacitance, which indicates that the application optimizes the beating degree of the Chinese alpine rush fiber, and improves the degree of fibrillation of the Chinese alpine rush fiber. The modification treatment of the Chinese alpine rush fiber by the modifier can destroy the crystallization area of the Chinese alpine rush fiber, and the carboxyethyl is introduced to the Chinese alpine rush fiber, so that the split fibrillation of the Chinese alpine rush fiber is promoted, and the bonding effect among fibers in the electrolytic paper is also promoted. As can be seen from Table 4, the electrochemical properties of the capacitors prepared in example 5 and example 7 are better, which means that the beating degree of the Gracilaria verrucosa fiber in example 5 is more suitable and the modifier in example 7 is more suitable.
(3) Comparison of examples 8-9, 10, 11-12 and 3 can be found: the capacitor prepared in examples 8-12 had a reduced impedance and leakage current and increased capacitance, indicating that the present application optimizes the freeness and freeness of softwood pulp fibers, improves the degree of split fibrillation of softwood pulp fibers, and facilitates the bonding between fibers in electrolytic paper. In addition, the biological enzyme is adopted to pretreat the softwood pulp fiber, so that the fiber wall layer can be loosened and destroyed, the fibrillation of the softwood pulp fiber 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 properties of the capacitor prepared in example 8 were better, indicating that the freeness of the softwood pulp fibers in example 8 was more suitable.
(4) The comparison of examples 13-14 and example 3 can be found: the capacitor prepared in examples 1-3 has improved impedance and leakage current, and reduced capacitance, which indicates that the graphene and manganese dioxide nanoplatelets are vertically grown on the aluminum foil, so that the transport path of charges in the capacitor is optimized, and the impedance of the capacitor is stably reduced. As can be seen from Table 4, the electrochemical properties of the capacitor obtained in example 13 were good, indicating that the structure of the aluminum-based composite material in example 13 was suitable.
(5) Comparison of examples 15-17, examples 18-20 and example 3 can be found: the capacitor prepared in examples 15-20 had a reduced impedance and leakage current and an increased capacitance, which indicated that the application diluted the electrolyte, reduced the viscosity of the electrolyte, improved the adsorption effect of the electrolyte on the electrolyte, and the diluent was able to volatilize rapidly and stably improved the loading effect of the electrolyte on the electrolyte in a vacuum environment. The doped acid is adopted to dope polyaniline, so that the interaction between polyaniline molecular chains can be reduced, the movement resistance of carriers is reduced, and the impedance of a capacitor is reduced. As can be seen from Table 4, the electrochemical properties of the capacitors prepared in examples 17 and 18 are better, which means that the polyaniline in example 17 is more suitable in proportion and the doping acid in example 18 is more suitable.
(6) The comparison of examples 21-22 and example 3 can be found: the capacitor prepared in examples 21-22 has reduced impedance and leakage current, and improved capacitance, which indicates that the application adopts aniline and sol electrolyte to cooperate, so that the retention of electrolyte by the electrolytic paper can be improved, namely, the transmission speed of charges in the capacitor is improved, and the impedance of the capacitor is improved. As can be seen from Table 4, the electrochemical properties of the capacitor obtained in example 22 were good, indicating that the ratio of the components in the electrolyte in example 22 was good.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.

Claims (7)

1. The low-impedance capacitor is characterized by comprising 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 asparagus fibers and 0.1-1 part of nanofibrillar cellulose, wherein the beating degree of the asparagus fibers is 30-50 DEG SR, and the softwood pulp fibers are the softwood pulp fibers with the beating degree of 70-90 DEG SR after high-concentration beating; the Chinese alpine rush fiber is Chinese alpine rush fiber modified by a modifier, and the modifier comprises one or two of sodium hydroxide and acrylamide; the softwood pulp fiber is a softwood pulp fiber pretreated by biological enzymes, wherein the biological enzymes comprise any one of cellulase and pulping enzyme.
2. A low impedance capacitor according to claim 1, wherein: the electrode plate comprises an aluminum-based composite material doped with graphene, and the aluminum-based composite material has a three-dimensional structure.
3. A low impedance capacitor according to claim 2, wherein: the aluminum-based composite material also comprises manganese dioxide, and the aluminum-based composite material has an open porous structure.
4. A low impedance capacitor according to claim 3, wherein the preparation of the aluminium-based composite material comprises the steps of:
pretreatment: immersing the aluminum foil in hydrochloric acid, etching, taking out to obtain etched aluminum foil, and immersing the etched aluminum foil in sodium hydroxide and nitric acid solution in sequence 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 an ionic aluminum foil, introducing carbon source gas, and performing deposition treatment to obtain an intermediate; and (3) placing the intermediate in a potassium permanganate solution, stirring and mixing, performing constant-temperature treatment, taking out the intermediate, washing and drying to obtain the aluminum-based composite material.
5. A low impedance capacitor according to claim 1, wherein: the electrolyte comprises one or two of polyaniline and sol electrolyte.
6. A low impedance capacitor according to claim 5, wherein: the polyaniline is polyaniline doped with doping acid, and the doping acid comprises any one of sulfuric acid, benzenesulfonic acid, D-camphor-10-sulfonic acid and dodecylbenzenesulfonic acid.
7. A method of manufacturing a low impedance capacitor according to any one of claims 1 to 6, comprising the steps of:
s1, dipping treatment: immersing the electrode sheet and diluted electrolytic paper in electrolyte, carrying out vacuum treatment under reduced pressure, repeatedly immersing and drying to obtain the immersed electrode sheet and electrolytic paper;
s2, preparing a capacitor: sequentially stacking and winding the electrode sheet and the electrolytic paper to obtain a winding core, immersing the winding core in the electrolyte, performing vacuum treatment under reduced pressure, repeatedly immersing and drying to obtain an immersed winding core; placing the impregnated winding core into an aluminum shell, and sealing and aging to obtain a capacitor; wherein the aging treatment adopts pulse voltage to perform aging at room temperature.
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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

Patent Citations (6)

* 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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