CN114790665A - Carbonization-free diaphragm paper and preparation method and application thereof - Google Patents

Carbonization-free diaphragm paper and preparation method and application thereof Download PDF

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Publication number
CN114790665A
CN114790665A CN202210563229.0A CN202210563229A CN114790665A CN 114790665 A CN114790665 A CN 114790665A CN 202210563229 A CN202210563229 A CN 202210563229A CN 114790665 A CN114790665 A CN 114790665A
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China
Prior art keywords
fibers
fiber
nano
paper
carbonization
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CN202210563229.0A
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Chinese (zh)
Inventor
杨军
杨宇
宋欢
刘含茂
杨清
王进
吴东森
刘云路
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Zhuzhou Times Fiber Pioneer Material Technology Co ltd
Zhuzhou Times New Material Technology Co Ltd
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Zhuzhou Times Fiber Pioneer Material Technology Co ltd
Zhuzhou Times New Material Technology Co Ltd
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Priority to CN202210563229.0A priority Critical patent/CN114790665A/en
Publication of CN114790665A publication Critical patent/CN114790665A/en
Pending legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F11/00—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/02—Synthetic cellulose fibres
    • D21H13/08—Synthetic cellulose fibres from regenerated cellulose
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10—Organic non-cellulose fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10—Organic non-cellulose fibres
    • D21H13/12—Organic non-cellulose fibres from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/14—Polyalkenes, e.g. polystyrene polyethylene
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10—Organic non-cellulose fibres
    • D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10—Organic non-cellulose fibres
    • D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/24—Polyesters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10—Organic non-cellulose fibres
    • D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/26—Polyamides; Polyimides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10—Organic non-cellulose fibres
    • D21H13/28—Organic non-cellulose fibres from natural polymers
    • D21H13/34—Protein fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/38—Inorganic fibres or flakes siliceous
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/38—Inorganic fibres or flakes siliceous
    • D21H13/40—Inorganic fibres or flakes siliceous vitreous, e.g. mineral wool, glass fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/46—Non-siliceous fibres, e.g. from metal oxides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/46—Non-siliceous fibres, e.g. from metal oxides
    • D21H13/50—Carbon fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
    • D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/48—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances fibrous materials
    • H01B3/52—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances fibrous materials wood; paper; press board
    • 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
    • H01G9/02—Diaphragms; Separators

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Paper (AREA)

Abstract

A carbonization-free diaphragm paper is mainly prepared from 10-60% of nano fibers and 40-90% of synthetic fibers. The preparation method comprises the following steps: adding water into the nano-fibers, and then defibering and dispersing to obtain nano-fiber slurry; adding water into the synthetic fiber, pulping, defibering and grinding to obtain synthetic fiber pulp; uniformly mixing the nanofiber pulp and the synthetic fiber pulp to obtain mixed fiber pulp; and (3) carrying out net-feeding low-concentration forming on the mixed slurry, and then carrying out squeezing, drying, reeling, post-treatment and slitting to obtain the carbonization-free diaphragm paper. According to the invention, the carbonization-free diaphragm paper is prepared from the nano fibers and the synthetic fibers, the nano fibers and the synthetic fibers are mutually wound to form rich chemical bonds, the bonding force between the fibers is enhanced, and the mechanical strength of the diaphragm paper is improved; the fibers are lapped and wound to form a rich pore structure, the porosity is high and uniform, the absorption capacity of the conductive high polymer monomers is ensured, and the defects of the diaphragm are few.

Description

Carbonization-free diaphragm paper and preparation method and application thereof
Technical Field
The invention belongs to the field of diaphragm paper, and particularly relates to carbonization-free diaphragm paper and a preparation method and application thereof.
Background
The solid-state capacitor adopts a conductive high polymer material with high conductivity and good thermal stability to replace electrolyte, and compared with the common liquid-state aluminum electrolytic capacitor, the solid-state capacitor has the characteristics of high reliability, long service life, high frequency, low impedance and extra-large ripple current resistance, is favorable for integration and miniaturization of electronic products, and can overcome the defect of easy liquid leakage of the liquid-state aluminum electrolytic capacitor. The solid capacitor diaphragm is used as an adsorption carrier of a conductive high polymer material, forms a cathode of the aluminum electrolytic capacitor together with the conductive high polymer material, plays a role of isolating two electrode foils, determines the interface structure, internal resistance and the like of the solid capacitor by the performance of the solid capacitor diaphragm, directly influences the capacity, the cycle performance and the service life of the solid capacitor, and is an important component of the solid capacitor.
The diaphragm paper prepared by the common cellulose material has a compact structure and low porosity, so that the diaphragm paper has less and uneven adsorption to a high polymer monomer, and the diaphragm paper is often required to be carbonized through high-temperature treatment in the production process of the solid capacitor to improve the porosity and the liquid absorption capacity of the diaphragm paper, so that the structure of an aluminum foil of the capacitor is damaged, a large number of defects are generated in the capacitor, and a large amount of electric energy is wasted. Meanwhile, solid capacitors have a trend of miniaturization and light weight, so that thinner and lighter solid capacitor diaphragm paper is needed, but the diaphragm paper is low in quantitative quantity and thinner, so that mechanical strength is low, cracks are easy to generate when a capacitor core is wound, internal defects of the capacitor are caused, and performance of the capacitor is affected. Therefore, in order to save energy and simplify the capacitor production process, it is necessary to develop a solid electrolytic capacitor separator paper which has high mechanical strength even under the conditions of low ration, light weight and thinness, can be well adapted to the core winding process of the capacitor, and can be well combined with the conductive polymer monomer without carbonization treatment.
Disclosure of Invention
The invention aims to overcome the defects and defects in the background art and provide the carbonization-free diaphragm paper which has high mechanical strength, can well adsorb high-molecular conductive monomers and has low impedance, and the preparation method and the application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the carbonization-free diaphragm paper is mainly prepared from 10-60% by mass of nano fibers and 40-90% by mass of synthetic fibers, wherein the nano fibers comprise one or more of nano cellulose fibers, artificial spider silk fibers, nano bacteria cellulose fibers, nano carbon fibers, nano glass fibers, nano ceramic fibers and nano aluminum oxide fibers; the synthetic fiber comprises one or more of polyester fiber (PET), polyacrylonitrile fiber, polyethylene fiber, polypropylene fiber, polysulfonamide fiber, poly-p-phenylene benzobisoxazole fiber (PBO), aromatic polyoxadiazole fiber (POD), poly-m-phenylene isophthalamide fiber (aramid 1313), poly-p-phenylene terephthamide fiber (aramid 1414), aromatic nylon fiber and semi-aromatic nylon fiber.
Preferably, the diameter of the nanofiber is less than 1000nm, and the length of the nanofiber is greater than 300 um. Further preferably, the nanofiber is a linear material with the diameter less than 500nm and the length more than 800 um.
More preferably, the mass percentage of the nano fibers is 20-40%.
Preferably, the carbonization-free diaphragm paper has an initial length of 0.3 to 12mm and an initial fineness of 0.1 to 3 dtex.
Further preferably, the synthetic fibers have an initial length of 0.3 to 10mm and an initial fineness of 0.3 to 2 tex.
More preferably, the synthetic fiber has a mass content of 60 to 90%, an initial length of 0.3 to 8mm, and an initial fineness of 0.3 to 1.5 dtex.
Preferably, the total weight of the non-carbonized diaphragm paper is 12-20 g/m 2 The thickness is 30-60 um, the tensile strength of the diaphragm paper is not lower than 0.70kN/m, the air permeability is not lower than 210mm/s, and the porosity is not lower than 60%.
As a general inventive concept, the present invention also provides a method for preparing the above carbonization-free membrane paper, comprising the steps of:
(1) adding water into the nano-fibers, and then defibering and dispersing to obtain nano-fiber slurry;
adding water into the synthetic fiber, and then performing pulping and defibering to obtain synthetic fiber pulp;
(2) uniformly mixing the nanofiber pulp and the synthetic fiber pulp to obtain mixed fiber pulp;
(3) and (3) carrying out net-feeding low-concentration forming on the mixed slurry, and then carrying out squeezing, drying, reeling, post-treatment and slitting to obtain the carbonization-free diaphragm paper.
In the above-mentioned production method, the pulp fluffing is not particularly limited, and a known method and apparatus can be suitably used; the equipment used for refining can be one or the combination of a groove type refiner, a double-disc mill, a double-cone mill and a double-cylinder mill.
In the above preparation method, preferably, in the step (3), the concentration of the formed product on the net is 0.05-0.5%. A further preferred upper web forming consistency is 0.08%.
In the above preparation method, preferably, in the step (3), the forming is performed by using a long inclined wire for primary forming; the forming area of the long inclined wire is a single-layer wire, the length of the forming area is not less than 6m, and an adjustable inclination angle of 0-60% exists between the forming area and the paper machine direction, so that the requirements of high-beating-degree paper pulp on dehydration and the requirements of uniform dispersion of long fibers are met.
In the preparation method, preferably, in the step (3), the post-treatment is a combination of a high-temperature treatment and a cold-press polishing treatment, and the temperature of the high-temperature treatment is 100 to 300 ℃, and more preferably 100 to 200 ℃. The high-temperature treatment equipment is an electric heating stainless steel single roller, and the cold press polishing equipment is a double-cylinder pressure roller with the surface being a rubber surface.
The invention also provides application of the carbonization-free diaphragm paper or the carbonization-free diaphragm paper prepared by the preparation method in all-solid electrolytic capacitors, semi-solid electrolytic capacitors, base materials of printed circuit boards, motor insulation structures, base materials of biochemical-proof weapons or base materials of protective clothing.
The diaphragm paper is mainly used as an adsorption carrier of a conductive high polymer material in all-solid-state and semi-solid-state electrolytic capacitors and super capacitors, and the adsorption carrier and the conductive high polymer material jointly form a cathode of the electrolytic capacitor, and simultaneously play a role in isolating two electrode foils. The prepared capacitor can be applied to industries such as various servers, 5G communication base stations, notebook computers, high-power quick-charging chargers, industrial control mainboards, high-end display cards, mining machines, new energy sources and automobile electronics.
The printed wiring board is a plate-shaped insulating material which is made by impregnating paper with phenolic resin and then thermally pressing a plurality of layers together, and the surface of the insulating material is covered with copper foil. Papers used for printed wiring boards require good absorption and uniformity of the resin, which is the main source of insulation properties and phenolic resins. The diaphragm paper prepared by the invention has good absorptivity to conductive high molecular monomer and good absorptivity to resin, and the main material used by the diaphragm paper is synthetic fiber, so that the diaphragm paper has high dimensional stability, and meanwhile, the diaphragm paper prepared by the invention has higher mechanical strength under the conditions of low ration and thinness, so the diaphragm paper can be used as a base material of a printed circuit board.
The diaphragm paper disclosed by the invention has rich pores, the pore size can be adjusted by controlling the fiber form, the adsorption effect on a high-molecular conductive monomer is good, and the diaphragm paper also has a good adsorption effect on impregnating varnish, an adhesive and the like in a fluid form, so that the diaphragm paper can be used as a carrier of impregnating varnish in a motor insulation structure, and can be applied to motor structures in the fields of rail transit, automobiles, wind power generation and the like, especially in a thinning insulation structure of a motor.
The diaphragm paper disclosed by the invention is porous and provided with a membrane, can well control pores by adjusting the fiber ratio, can not only enable air to penetrate, has breathability, but also can block aerosol, block wind and filter fine particles, and can be used for preparing base materials of biochemical weapon prevention and high-grade protective clothing for toxic substances.
Compared with the prior art, the invention has the advantages that:
(1) the diaphragm paper is prepared from the nanofibers and the synthetic fibers, the nanofibers not only have higher length-diameter ratio and larger specific surface area, but also have the characteristics of high strength, high Young modulus, high crystallinity, high hydrophilicity, high transparency, low thermal expansion coefficient and the like, the nanofibers are easier to mutually wind with adjacent synthetic fibers to form rich chemical bonds, the bonding force among the fibers can be greatly enhanced, the mechanical strength of the diaphragm paper is greatly improved, and the toughness of the diaphragm is increased; meanwhile, the nano fibers and the synthetic fibers are lapped and wound to form a rich pore structure, the porosity is high and uniform, the absorption capacity of the conductive polymer monomers is ensured, and the defects of the diaphragm are few.
(2) The diaphragm paper has high mechanical strength, can reduce the defects of the capacitor core in the winding process, simultaneously uses synthetic fibers and has rich pore structures, and monomers can be well adsorbed in the paper and are uniformly distributed, so that the diaphragm paper does not need to be carbonized in the capacitor preparation process, and the prepared capacitor has extremely low ESR value, small impedance and low loss.
(3) In the preparation process, the synthetic fiber is modified in a way of mutually matching and combining the mill and the defibering, and the difference of the shearing effect and the fibrillation effect of the mill and the defibering on the fiber is fully utilized, so that the prepared fiber not only has high fibrillation degree, but also better retains the fiber length; the high degree of fiber fibrillation, the very large number of fibers, the very large number of hydrogen bonds formed by overlapping and winding fibers, the stronger the bonding force between fibers, and the more pores are formed.
(4) The long inclined net is adopted for forming in the preparation process, the respective advantages of the long net and the inclined net are comprehensively utilized, the phenomenon that synthetic fibers are not well dispersed and are tangled and conglobated due to the fact that the forming concentration of the pure long net cannot be too low can be reduced, the forming uniformity is good, needle holes and the like generated by fine fiber loss due to too large dewatering amount of the pure inclined net can be reduced, and the defect of preparing the diaphragm paper is small.
(5) The preparation process of the invention adopts a mode of combining high-temperature treatment and cold-press polishing treatment, which can effectively avoid the phenomenon of fluid fiber hole blocking caused by applying pressure while melting synthetic fibers when hot-press light is used in the prior art, firstly uses high-temperature treatment to soften and melt the synthetic fibers to generate cohesiveness, further enhances the combination among the fibers, further increases the strength, and then uses double-cylinder pressure rollers with double rubber surfaces to carry out cold-press polishing on the diaphragm, so that the surface of the diaphragm is smooth, compact and free from hair falling.
(6) The diaphragm paper prepared by the invention has high mechanical strength, high porosity, good liquid absorption and no hair falling, can be used as a carrier of fluid substances, and can be applied to the fields of power electronic elements such as solid capacitors, super capacitors, liquid/semi-solid batteries, printed circuits, motor insulation and the like.
Detailed Description
In order to facilitate an understanding of the invention, the invention will now be described more fully and in detail with reference to the preferred embodiments, but the scope of the invention is not limited to the specific embodiments described below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the carbonization-free diaphragm paper is mainly prepared from 40 percent of nano cellulose fiber and 60 percent of PET fiber, and the total weight of the carbonization-free diaphragm paper is 17g/m 2 And the thickness is 51.1 um.
The preparation method of the carbonization-free diaphragm paper comprises the following steps:
(1) carrying out low-concentration defibering and dispersing on the nano cellulose fibers with the diameter of 400nm and the length of 800um by using a defibering machine to prepare nano fiber slurry with the concentration of 2%;
carrying out hydraulic pulping on PET fibers with the fineness of 1.0dtex and the length of 5mm, and refining the PET fibers by a double disc grinder for 15 cycles to prepare PET fiber slurry;
(2) mixing the nano-cellulose fiber slurry and the PET fiber slurry, wherein the concentration of the mixed slurry is 0.8%, and the mass ratio of the nano-cellulose fibers to the PET fibers in the mixed slurry is 40: 60;
(3) diluting the mixed slurry obtained in the step (2), then adopting a long inclined net for one-step forming, carrying out ultra-low-concentration forming on the long inclined net with the single-layer net length of 9m and the inclination angle (the angle between the forming area and the paper machine direction) of 5 degrees in a forming area, wherein the forming concentration of the upper net is 0.12 percent, then carrying out squeezing, drying and coiling to obtain base paper, then carrying out high-temperature treatment on the base paper through an electric heating stainless steel single roller at 200 ℃, carrying out cold-press polishing treatment, and finally carrying out slitting to obtain the diaphragm paper.
Example 2:
the carbonization-free diaphragm paper is mainly prepared from 20 percent of nano cellulose fiber and 80 percent of PET fiber, and the total weight of the carbonization-free diaphragm paper is 17g/m 2 The design thickness is 50.6 um.
The preparation method of the carbonization-free diaphragm paper comprises the following steps:
(1) carrying out low-concentration defibering and dispersing on the nano cellulose fiber with the diameter of 400nm and the length of 800 mu m by using a defibering machine to prepare nano fiber slurry with the concentration of 2%;
carrying out hydraulic pulping on PET fibers with the fineness of 1.0dtex and the length of 5mm, and refining the PET fibers by a double disc grinder for 15 cycles to prepare PET fiber slurry;
(2) mixing the nano-cellulose fiber slurry and the PET fiber slurry, wherein the concentration of the mixed slurry is 0.8%, and the mass ratio of the nano-cellulose fibers to the PET fibers in the mixed slurry is 20: 80;
(3) and (3) diluting the mixed slurry obtained in the step (2), then adopting a long inclined net for one-step forming, carrying out ultra-low-concentration forming on the long inclined net with the single-layer net length of 9m and the inclination angle of 5 degrees in a forming area, wherein the net-feeding forming concentration is 0.08%, then carrying out squeezing, drying and coiling to obtain base paper, carrying out electric heating stainless steel single-roller high-temperature treatment on the base paper at 200 ℃, carrying out cold-press polishing treatment, and finally slitting to obtain the diaphragm paper.
Example 3:
the invention is free from carbonizationThe membrane paper is mainly prepared from 35% of nano cellulose fiber, 5% of nano ceramic fiber and 60% of PET fiber, and the total weight of the membrane paper is 17.1g/m 2 And the thickness is 50.5 um.
The preparation method of the carbonization-free diaphragm paper comprises the following steps:
(1) mixing nano cellulose fibers with the diameter of 400nm and the length of 800um with nano ceramic fibers with the diameter of 400nm and the length of 800um, and using a fluffer to defiber and disperse at low concentration to prepare mixed pulp of the nano cellulose fibers and the nano ceramic fibers with the concentration of 2 percent;
carrying out hydraulic pulping on PET fibers with the fineness of 1.0dtex and the length of 5mm, and refining the PET fibers by a double disc grinder for 15 cycles to prepare PET fiber slurry;
(2) mixing the mixed pulp of the nano cellulose fibers and the nano ceramic fibers with the PET fiber pulp to obtain mixed pulp, wherein the mass ratio of the nano cellulose fibers to the nano ceramic fibers to the PET fibers is 35:5: 60;
(3) diluting the mixed slurry obtained in the step (2), then adopting a long inclined wire for one-step forming, carrying out ultra-low-concentration forming on the long inclined wire with the single-layer wire length of 9m and the inclination angle of 5 degrees in a forming area, wherein the net-feeding forming concentration is 0.16%, then carrying out squeezing, drying and reeling to obtain base paper, then carrying out electric heating stainless steel single-roller high-temperature treatment on the base paper at 200 ℃, carrying out cold-pressing polishing treatment, and finally slitting to obtain the diaphragm paper.
Example 4:
the carbonization-free diaphragm paper is mainly prepared from 15 percent of nano cellulose fiber, 5 percent of nano ceramic fiber and 80 percent of PET fiber, and the total weight of the carbonization-free diaphragm paper is 17.1g/m 2 The thickness is 50.7 um.
The preparation method of the carbonization-free diaphragm paper comprises the following steps:
(1) mixing nano cellulose fibers with the diameter of 400nm and the length of 800um and nano ceramic fibers with the diameter of 400nm and the length of 800um, and using a fluffer to defiber and disperse at low concentration to prepare mixed pulp of the nano cellulose fibers and the nano ceramic fibers with the concentration of 2 percent;
carrying out hydraulic pulping on PET fibers with the fineness of 1.0dtex and the length of 5mm, and refining the PET fibers by a double disc grinder for 15 cycles to prepare PET fiber slurry;
(2) mixing the mixed slurry of the nano cellulose fibers and the nano ceramic fibers with the PET fiber slurry to obtain mixed slurry, wherein the mass ratio of the nano cellulose fibers to the nano ceramic fibers to the PET fibers is 15:5: 80;
(3) and (3) diluting the mixed slurry obtained in the step (2), then adopting a long inclined net for one-step forming, carrying out ultra-low-concentration forming on the long inclined net with the single-layer net length of 9m and the inclination angle of 5 degrees in a forming area, wherein the net-feeding forming concentration is 0.12%, then carrying out squeezing, drying and coiling to obtain base paper, carrying out electric heating stainless steel single-roller high-temperature treatment on the base paper at 200 ℃, carrying out cold-press polishing treatment, and finally slitting to obtain the diaphragm paper.
Example 5:
the carbonization-free diaphragm paper is mainly prepared from 40% of nano cellulose fibers, 35% of PET fibers and 25% of POD fibers, and the total weight of the carbonization-free diaphragm paper is 17g/m 2 The thickness of the film is 50.3 um.
The preparation method of the carbonization-free diaphragm paper comprises the following steps:
(1) carrying out low-concentration defibering and dispersing on the nano cellulose fibers with the diameter of 400nm and the length of 800um by using a defibering machine to prepare nano fiber slurry with the concentration of 2%;
carrying out hydraulic pulping and double disc grinding refining on PET fibers with the fineness of 1.0dtex and the length of 5mm and POD fibers with the fineness of 0.5dtex and the length of 4mm for 15 cycles to prepare mixed pulp of the PET fibers and the POD fibers;
(2) mixing the nano cellulose fiber slurry with a mixed slurry of PET fibers and POD fibers, wherein the mass ratio of the nano cellulose fibers to the PET fibers to the POD fibers in the prepared mixed slurry is 40:35: 25;
(3) diluting the mixed slurry obtained in the step (2), then adopting a long inclined wire for one-step forming, carrying out ultra-low-concentration forming on the long inclined wire with the single-layer wire length of 9m and the inclination angle of 5 degrees in a forming area, wherein the net-feeding forming concentration is 0.16%, then carrying out squeezing, drying and reeling to obtain base paper, then carrying out electric heating stainless steel single-roller high-temperature treatment on the base paper at 200 ℃, carrying out cold-pressing polishing treatment, and finally slitting to obtain the diaphragm paper.
Example 6:
the carbonization-free diaphragm paper is mainly prepared from 20% of nano cellulose fibers, 45% of PET fibers and 35% of POD fibers, and the total weight of the carbonization-free diaphragm paper is 17.2g/m 2 And the thickness is 51.2 um.
The preparation method of the carbonization-free diaphragm paper comprises the following steps:
(1) carrying out low-concentration defibering and dispersing on the nano cellulose fibers with the diameter of 400nm and the length of 800um by using a defibering machine to prepare nano fiber slurry with the concentration of 2%;
performing hydraulic pulping on PET fibers with the titer of 1.0dtex and the length of 5mm and POD fibers with the titer of 0.5dtex and the length of 4mm, and refining by a double disc grinder for 15 cycles to prepare mixed pulp of the PET fibers and the POD fibers;
(2) mixing the nano cellulose fiber pulp with PET fibers and POD fiber pulp, wherein the mass ratio of the nano cellulose fibers to the PET fibers to the POD fibers in the obtained mixed pulp is 20:45: 35;
(3) and (3) diluting the mixed slurry obtained in the step (2), then adopting a long inclined net for one-step forming, carrying out ultra-low-concentration forming on the long inclined net with the single-layer net length of 9m and the inclination angle of 5 degrees in a forming area, wherein the net-feeding forming concentration is 0.12%, then carrying out squeezing, drying and coiling to obtain base paper, carrying out electric heating stainless steel single-roller high-temperature treatment on the base paper at 200 ℃, carrying out cold-press polishing treatment, and finally slitting to obtain the diaphragm paper.
Example 7:
the carbonization-free diaphragm paper is mainly prepared from 15% of nano cellulose fibers, 25% of nano ceramic fibers, 40% of PET fibers and 20% of POD fibers, and the total weight of the carbonization-free diaphragm paper is 17.2g/m 2 Its thickness is 51.3 um.
The preparation method of the carbonization-free diaphragm paper comprises the following steps:
(1) mixing nano cellulose fibers with the diameter of 400nm and the length of 800um and nano ceramic fibers with the diameter of 400nm and the length of 800um, and using a fluffer to defiber and disperse at low concentration to prepare mixed pulp of the nano cellulose fibers and the nano ceramic fibers with the concentration of 2 percent;
mixing PET fibers with the fineness of 1.0dtex and the length of 5mm and POD fibers with the fineness of 0.5dtex and the length of 4mm, performing hydraulic repulping, and refining by a double disc grinder for at least 15 cycles to prepare mixed pulp of the PET fibers and the POD fibers;
(2) mixing the mixed slurry of the nano cellulose fibers and the nano ceramic fibers with the mixed slurry of the PET fibers and the POD fibers, wherein the mass ratio of the nano cellulose fibers, the nano ceramic fibers, the PET fibers and the POD fibers in the mixed slurry is 15:25:40: 20;
(3) and (3) diluting the mixed slurry obtained in the step (2), then adopting a long inclined net for one-step forming, carrying out ultra-low-concentration forming on the long inclined net with the single-layer net length of 9m and the inclination angle of 5 degrees in a forming area, wherein the net-feeding forming concentration is 0.2%, then carrying out squeezing, drying and coiling to obtain base paper, carrying out electric heating stainless steel single-roller high-temperature treatment on the base paper at 200 ℃, carrying out cold-press polishing treatment, and finally slitting to obtain the diaphragm paper.
Example 8:
the carbonization-free diaphragm paper is mainly prepared from 15% of nano cellulose fibers, 5% of nano ceramic fibers, 40% of PET fibers and 40% of POD fibers, and the total weight of the carbonization-free diaphragm paper is 17.1g/m 2 Its thickness is 51.0 um.
The preparation method of the carbonization-free diaphragm paper comprises the following steps:
(1) mixing nano cellulose fibers with the diameter of 400nm and the length of 800um with nano ceramic fibers with the diameter of 400nm and the length of 800um, and carrying out low-concentration defibering and dispersing by using a defibering machine to prepare mixed pulp of the nano cellulose fibers and the nano ceramic fibers with the concentration of 2 percent;
mixing PET fibers with the fineness of 1.0dtex and the length of 5mm and POD fibers with the fineness of 0.5dtex and the length of 4mm, performing hydraulic repulping, and refining by a double disc grinder for at least 15 cycles to prepare a mixed pulp of the PET fibers and the POD fibers;
(2) mixing the mixed pulp of the nano cellulose fibers and the nano ceramic fibers with the pulp of the PET fibers and the POD fibers, wherein the mass ratio of the nano cellulose fibers, the nano ceramic fibers, the PET fibers and the POD fibers in the mixed pulp is 15:5:40: 40;
(3) and (3) diluting the mixed slurry obtained in the step (2), then adopting a long inclined net for one-step forming, carrying out ultra-low-concentration forming on the long inclined net with the single-layer net length of 9m and the inclination angle of 5 degrees in a forming area, wherein the net-feeding forming concentration is 0.16%, then carrying out squeezing, drying and coiling to obtain base paper, carrying out electric heating stainless steel single-roller high-temperature treatment on the base paper at 200 ℃, carrying out cold-press polishing treatment, and finally slitting to obtain the diaphragm paper.
Comparative example 1:
the preparation method of the diaphragm paper of the comparative example comprises the following steps:
(1) carrying out hydraulic pulping on PET fibers with the fineness of 1.0dtex and the length of 5mm, and refining by a double-disc mill for 15 cycles to prepare PET fiber slurry;
(2) diluting the slurry prepared in the step (1), then adopting a long inclined net for one-step forming, carrying out ultra-low concentration forming on the long inclined net with the single-layer net length of 9m and the inclination angle of 5 degrees in a forming area, wherein the net-feeding forming concentration is 0.08%, then carrying out squeezing, drying and coiling to obtain base paper, carrying out high-temperature treatment on the base paper by an electric heating single stainless steel single roller at 200 ℃, carrying out cold-press polishing treatment, and finally slitting to obtain the diaphragm paper.
Comparative example 2:
the preparation method of the diaphragm paper of the comparative example comprises the following steps:
(1) PET fibers having a fineness of 1.0dtex and a length of 5mm and POD fibers having a fineness of 0.5dtex and a length of 4mm were spun in a ratio of 1: 1, mixing, performing hydraulic pulping, refining by a double-disc mill for at least 15 cycles, and preparing into PET fiber and POD fiber mixed pulp;
(2) diluting the mixed slurry of the PET fibers and POD fibers prepared in the step (1), then adopting a long inclined net for one-step forming, carrying out ultra-low-concentration forming on the long inclined net with the single-layer net length of 9m and the inclination angle of 5 degrees in a forming area, wherein the net-feeding forming concentration is 0.08%, then carrying out squeezing, drying and coiling to obtain base paper, carrying out high-temperature treatment on the base paper by an electric heating stainless steel single roller at 200 ℃, carrying out cold-press polishing treatment, and finally slitting to obtain the diaphragm paper.
The performance of the separator paper of each of the above examples and comparative examples was tested and is shown in table 1. As can be seen from the comparative examples in Table 1, the membranes prepared from homozygous fibers have low tensile strength, high thermal shrinkage and high air permeability, which indicates that the membranes prepared by the method have poor mechanical properties, uneven pores and poor thermal stability; the embodiment shows that the tensile strength, the liquid absorption height and the porosity of the diaphragm are obviously improved after the nano-fiber is added, and the thermal stability is better.
TABLE 1 Properties of separator papers of examples and comparative examples
Figure BDA0003652826400000091
The test methods or criteria for each property in table 1 include:
quantitative test method: GB/T451.2-. 2002;
thickness test method: GB/T451.3-. 2002;
tensile strength test method: GB/T12914-2008;
liquid absorption height test: GB/T461.1-2002;
and (3) testing air permeability: measuring the air permeability of GB/T5453 textile fabrics;
thermal shrinkage test method: after measuring points with the distance of 100mm are marked along the center line of the sample by a marking pen, the sample is hung in an oven with the temperature of 200 ℃ and is treated for 40min +/-1 min, and when the time is up, the sample is taken out, placed in a drier, cooled to room temperature for 4h, and then the length of each sample is measured again. If the sample is not flat, the sample can be measured by pressing the glass plate.
ESR measurement: the ESR (equivalent series resistance) was measured at a temperature of 20 ℃ and a frequency of 200kHz using an LCR meter.
And (3) porosity testing: the sample was cut into a test piece of 5cm long by 5cm wide, and the humidity and the thickness H of the test piece were measured after controlling the humidity in an atmosphere of 23 ℃ and 50% relative humidity for 24 hours, then, the test solution was immersed with ethylene glycol for 20 minutes, then the excessive ethylene glycol attached to the surface of the test piece was absorbed and removed with filter paper, and the weight was measured again. Then, the porosity (%) was 100 × [ weight of test piece after absorption (g) — weight of test piece before absorption (g) ]/density of ethylene glycol (g/cm 3) × 5cm (length) × 5cm (width) × h (cm) × porosity).

Claims (10)

1. The carbonization-free diaphragm paper is characterized by being mainly prepared from 10-60% by mass of nano fibers and 40-90% by mass of synthetic fibers, wherein the nano fibers comprise one or more of nano cellulose fibers, artificial spider silk fibers, nano bacteria cellulose fibers, nano carbon fibers, nano glass fibers, nano ceramic fibers and nano alumina fibers;
the synthetic fiber comprises one or more of polyester fiber, polyacrylonitrile fiber, polyethylene fiber, polypropylene fiber, polysulfonamide fiber, poly-p-phenylene benzobisoxazole fiber, aromatic polyoxadiazole fiber, poly-m-phenylene isophthalamide fiber, poly-p-phenylene terephthamide fiber, aromatic nylon fiber and semi-aromatic nylon fiber.
2. The non-carbonized separator paper of claim 1, wherein the nanofibers have a diameter less than 1000nm and a length greater than 300 um.
3. The non-carbonized separator paper of claim 1, wherein the synthetic fibers have an initial length of 0.3 to 12mm and an initial fineness of 0.1 to 3 dtex.
4. The non-carbonized separator paper as claimed in any one of claims 1 to 3, wherein the total basis weight of the separator paper is 12 to 20g/m 2 The thickness is 30-60 um, the tensile strength is not lower than 0.70kN/m, the air permeability is not lower than 210mm/s, and the porosity is not lower than 60%.
5. A method for preparing the non-carbonized separator paper according to any one of claims 1 to 4, comprising the steps of:
(1) adding water into the nano-fibers and then defibering to obtain nano-fiber slurry;
adding water into the synthetic fiber, pulping, defibering and grinding to obtain synthetic fiber pulp;
(2) uniformly mixing the nanofiber pulp and the synthetic fiber pulp to obtain mixed fiber pulp;
(3) and (3) carrying out net-feeding low-concentration forming on the mixed slurry, and then carrying out squeezing, drying, reeling, post-treatment and slitting to obtain the carbonization-free diaphragm paper.
6. The method according to claim 5, wherein in the step (3), the web forming concentration is 0.05 to 0.5%.
7. The preparation method according to claim 5, wherein in the step (3), the post-treatment is a combination of a high temperature treatment and a cold press light treatment, and the temperature of the high temperature treatment is 100-300 ℃.
8. The method according to claim 5, wherein in the step (3), the forming is performed in one pass using a long wire.
9. The process according to claim 8, wherein the forming zone of the fourdrinier wire is a single layer wire having a length of not less than 6m and an angle of 0 to 60 ° with respect to the machine direction.
10. Use of the non-carbonized separator paper as defined in any one of claims 1 to 4 or the non-carbonized separator paper prepared by the preparation method as defined in any one of claims 5 to 9 in all-solid electrolytic capacitors, semi-solid electrolytic capacitors, substrates for printed wiring boards, motor insulation structures, substrates for biochemical weapons or protective clothing.
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