WO2017113275A1 - Composite nanofiber membrane for electrochemical element, preparation method and energy storage device - Google Patents

Composite nanofiber membrane for electrochemical element, preparation method and energy storage device Download PDF

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WO2017113275A1
WO2017113275A1 PCT/CN2015/100075 CN2015100075W WO2017113275A1 WO 2017113275 A1 WO2017113275 A1 WO 2017113275A1 CN 2015100075 W CN2015100075 W CN 2015100075W WO 2017113275 A1 WO2017113275 A1 WO 2017113275A1
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flame retardant
composite nanofiber
separator
nanofibers
slurry
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PCT/CN2015/100075
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French (fr)
Chinese (zh)
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张宣宣
解明
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宁波艾特米克锂电科技有限公司
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Priority to PCT/CN2015/100075 priority Critical patent/WO2017113275A1/en
Priority to CN201610087816.1A priority patent/CN105655526A/en
Publication of WO2017113275A1 publication Critical patent/WO2017113275A1/en

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    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/44Fibrous material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403Manufacturing processes of separators, membranes or diaphragms
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403Manufacturing processes of separators, membranes or diaphragms
    • H01M50/406Moulding; Embossing; Cutting
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/411Organic material
    • H01M50/414Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417Polyolefins
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/411Organic material
    • H01M50/414Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/42Acrylic resins
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/411Organic material
    • H01M50/414Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/426Fluorocarbon polymers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/411Organic material
    • H01M50/429Natural polymers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/443Particulate material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491Porosity
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/494Tensile strength
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Definitions

  • the invention belongs to the technical field of separators for electrochemical components, and particularly relates to a flame retardant membrane with high temperature resistance and a preparation method thereof.
  • the invention also relates to energy storage devices for the production of such separators, including lithium ion batteries, supercapacitors, lead acid batteries, zinc air batteries, sodium ion batteries.
  • Lithium batteries have many advantages such as high energy density, high power density and long cycle life, and have received great attention in the fields of portable electronic devices, power batteries and energy storage batteries. Over-charging, short-circuit, thermal shock and mechanical shock of lithium-ion batteries may cause lithium-ion batteries to ignite and explode, posing a safety hazard to people's lives and property.
  • the main function of the separator is to isolate the positive and negative electrodes and prevent electrons from passing freely, and at the same time allow ions to pass freely.
  • the performance determines the interface structure and internal resistance of the battery, directly affecting the capacity of the battery. Cyclic performance, etc., and is a key part of the safety performance of lithium-ion batteries. Therefore, whether the performance of the battery separator is excellent is one of the key steps to improve the safety of the battery.
  • the lithium ion battery separator is mainly a polyolefin separator, which has a sufficiently small pore size to effectively prevent internal short circuit of the battery, and has good uniformity, and can effectively ensure the charge and discharge performance of the battery.
  • the internal temperature of the battery rises rapidly, and the polyolefin film cannot guarantee its integrity at high temperature (above 170 ° C), so that the positive and negative materials are A large area of contact occurs, causing the battery to explode, posing a threat to the safety of the battery.
  • the design of large capacity and high power charge and discharge requires better high temperature resistance of the diaphragm.
  • the polyolefin membrane has poor gas permeability, which can not meet the needs of rapid battery charge and discharge, affecting the cycle life of the battery; in addition, the polyolefin membrane electrolyte has poor wettability and liquid absorption capacity, affecting the lithium battery rate performance and Long cycle performance; synthesize the above content, send It is necessary to have a battery separator having high temperature dimensional stability, good gas permeability, good electrolyte wettability and liquid absorption capability.
  • the technical problem to be solved by the present invention is to improve the thermal stability and flame retardancy of the battery separator, and at the same time improve the electrolyte wetting property, liquid absorbing ability, gas permeability and electrochemical performance of the separator, and provide a high temperature resistance for the electrochemical component. Flame-retardant composite nanofiber membrane and preparation method thereof.
  • the present invention firstly provides a high temperature flame retardant composite nanofiber separator for electrochemical components, having a thickness of 10-80 ⁇ m, a porosity of 40-90%, and a gas permeability index of Gurley of 5-300 s/100 cc.
  • the electrolyte absorption rate is 150-500%
  • the mechanical tensile strength is 10-100 MPa
  • the thermal stability is excellent.
  • the dimensional shrinkage is 0-5%
  • the flame retardancy is good
  • the LOI (limit oxygen index) ) is 20-65%.
  • the raw materials of the present invention are based on the mass percentage content: 20-78% of cellulose nanofibers, 20-65% of low melting polymer nanofibers, and 2-35% of flame retardant materials.
  • the cellulose nanofibers are at least one of cellulose nanofibers separated from nanosized wood materials, seaweed cellulose nanofibers, and bacterial cellulose nanofibers obtained by culturing strains.
  • the cellulose nanofibers have a diameter of 10 to 1000 nm and a length of 10 to 3000 ⁇ m.
  • the low melting point polymer nanofibers are polymethyl methacrylate, vinylidene fluoride polymer, polyurethane, polyvinyl chloride, polyvinyl alcohol, polyolefin, polyacrylonitrile, polyethylene-vinyl acetate copolymer, One or more combinations of polyethylene succinate.
  • the low melting point fiber has a diameter of 10 to 1000 nm.
  • the flame retardant material comprises flame retardant fiber fluorocarbon, phenolic fiber, partial fluorinated fiber, chlorinated fiber, urethane fiber, nitrile chlorinated fiber, PBI, aramid fiber (1414), flame retardant polyester fiber, flame retardant acrylic fiber, flame retardant polypropylene fiber , polyarylsulfone amide, etc.; and flame retardant phosphate, phosphite, tetramethylolphosphonium chloride, organic phosphorus salt, phosphorus oxide, phosphorus-containing polyol, phosphorus-nitrogen compound, melamine, melamine cyanurate, three ( One or more of 2,3-dibromopropyl)isocyanurate, monocyanamide, dicyandiamide, cyanuric acid, thiourea, decabromodiphenyl ether.
  • the flame retardant fiber has a diameter of 10 to 1000 nm; and the flame retardant has a particle diameter of less than 1 ⁇ m.
  • Another object of the present invention is to provide a preparation method for a low-cost, simple production process, convenient transfer, and suitable for large-scale production of the above-mentioned high-temperature-resistant flame-retardant composite nanofiber separator, characterized in that the specific steps include:
  • the dispersing agent includes one or more of deionized water, ethanol, isopropanol and glycerol;
  • the additive comprises acetic acid, starch acetate, methylol starch, sodium carboxymethylcellulose, hydroxymethylcellulose, gelatin, carrageenan, chitosan, chitin Or one or more of polyethylene oxide, water-soluble polyurethane, polyacrylamide, polyvinylpyrrolidone or water-soluble polyurethane; the mass of the additive is 0.1-10% of the cellulose nanofiber;
  • step III the slurry after step II is diluted to a mass percentage concentration of 0.01-0.05%;
  • the diluted slurry is subjected to dehydration molding, pressing, drying and hot rolling forming on the Internet to obtain the high temperature resistant flame-retardant composite nanofiber separator; the press line pressure is 60-120 kg/cm, The drying temperature is 70-100 ° C, the hot rolling forming temperature is 100-300 ° C, and the line pressure is 95-300 kg/cm.
  • the dispersing agent comprises one or more of deionized water, ethanol, isopropanol and glycerin; the additive comprises acetic acid, starch acetate, methylol starch, sodium carboxymethyl cellulose, hydroxyl group Cellulose, gelatin, carrageenan, chitosan, chitin, polyethylene oxide, water soluble polyurethane, polypropylene One or more of an enamide, a polyvinylpyrrolidone or a water-soluble polyurethane; the mass percentage of the additive is from 0.1 to 10% of the absolute dry weight of the nanocellulose fiber.
  • the present invention adopts a wet-laid method to prepare a flame-retardant composite nanofiber membrane with high temperature resistance by self-assembly cross-linking between high-temperature resistant nanofibers, low melting point polymer nanofibers and flame retardant materials.
  • the cellulose nanofibers are mainly combined by hydrogen bonding and intermolecular force, and the cellulose nanofibers are combined with the low melting point polymer nanofibers and the long diameter of the flame retardant fibers by crosslinking.
  • Another aspect of the present invention is to provide an energy storage device comprising a closed cell composite using a fibrillated cellulose nanofiber obtained by the above method, such as a lithium ion battery, a supercapacitor, a lead acid battery, a zinc air battery, a sodium ion battery, or the like. Diaphragm.
  • the invention adopts high-temperature resistant nanofibers, low melting point polymer nanofibers and flame retardant materials to self-assemble and prepare composite nanofiber membranes with high temperature resistance and excellent flame retardant performance.
  • the beneficial effects of the invention are:
  • the diaphragm can prevent leakage and excessive conduction and undesired ion transport blocking current conduction through the closed hole to prevent explosion.
  • the high temperature resistance of the diaphragm can ensure the stability of the diaphragm at high temperature and prevent the positive and negative electrodes from being short-circuited and fired.
  • the manufacturing process is simple and low cost.
  • 1 is a comparison diagram of combustion properties of (a) a polyolefin separator, (b) a pure nanocellulose separator, and (c) a heat-resistant flame-retardant composite nanofiber separator.
  • Fig. 3 is a graph showing the dimensional measurement after baking of the heat-resistant flame-retardant composite nanofiber membrane of the specific example 1.
  • the composite nanofiber membrane for preparing an electrochemical component comprises the following steps:
  • Step 1 The mass ratio is 20-78% of cellulose nanofibers, 20-65% of low melting polymer nanofibers and 2-35% of flame retardant materials, and the dispersing agent is deionized water, ethanol and isopropyl. One or more of an alcohol and glycerol are rapidly agitated to form an overall uniform slurry.
  • the cellulose nanofiber is at least one of fibrillated cellulose nanofibers separated from nanosized wood materials, seaweed cellulose nanofibers, and bacterial cellulose nanofibers obtained by culturing the strain; cellulose nanofibers
  • the diameter is 10-1000 nm and the length is 10-3000 ⁇ m.
  • the low melting point polymer nanofibers are polymethyl methacrylate, vinylidene fluoride polymer, polyurethane, polyvinyl chloride, polyvinyl alcohol, polyolefin, polyacrylonitrile, polyethylene-vinyl acetate copolymer, polybutylene
  • One or more combinations of acid glycol esters, the low melting point polymer nanofibers have a diameter of from 10 to 1000 nm.
  • Flame retardant materials include flame retardant fiber fluorocarbon, phenolic fiber, vinylidene fluoride, polyvinyl chloride, vinyl chloride, nitrile chloride, PBI, aramid (1414), flame retardant polyester, flame retardant acrylic, flame retardant polypropylene, polyfang Sulfonamide; and flame retardant phosphate, phosphite, tetramethylolphosphonium chloride, organic phosphorus salt, phosphorus oxide, phosphorus-containing polyol, phosphorus-nitrogen compound, melamine, melamine cyanurate, tris(2,3- One or more of dibromopropyl)isocyanate, monocyanamide, dicyandiamide, cyanuric acid, thiourea, decabromodiphenyl ether; flame retardant materials, flame retardant fibers The diameter is 10-1000 nm; the flame retardant particle size is less than 1 ⁇ m.
  • Step 2 adding an additive to the slurry, the additive is acetic acid, starch acetate, methylol starch, One or more of sodium carboxymethyl cellulose, hydroxymethyl cellulose, gelatin, carrageenan, chitosan, chitin, polyethylene oxide, water-soluble polyurethane, polyacrylamide, polyvinylpyrrolidone or water-soluble polyurethane
  • the quality of the additive is 0.1-10% of the dry amount of the cellulose nano-nanose cellulose fiber in the slurry;
  • Step 3 the slurry water is diluted to a mass percentage concentration of 0.01-0.05%
  • Step 4 The diluted slurry is dehydrated by the Internet, and is pressed at a roller line pressure of 60-120 kg/cm. After drying at a temperature of 70-100 ° C, the temperature is 100-300 ° C and the line pressure is 100- The hot-rolling forming composite nanofiber separator of the present invention is obtained by hot-rolling at 300 kg/cm.
  • the obtained separator has a thickness of 10-80 ⁇ m; the porosity is 40-90%, which facilitates the passage of electrolyte ions; the dimensional shrinkage is 0-5% at a temperature of 200 ° C for 30 min; and the limiting oxygen index LOI is 20-65. %; gas permeability index Gurley value is 5-300s/100cc; electrolyte absorption rate is 150%-500%, mechanical tensile strength is 10-100MPa.
  • Cellulose nanofibers, polypropylene fibers (low melting point polymer nanofibers), and aramid fibers (flame retardant materials) separated from nanosized wood materials are put into dispersing agent deionized water at a mass ratio of 75%, 20%, and 5%. Then, the slurry is prepared by high-speed mechanical stirring to achieve uniformity of the whole, and the additive acetic acid is added to the slurry, and the acetic acid mass content accounts for 0.1% of the absolute dry weight of the nanocellulose fiber.
  • the slurry is diluted to a mass concentration of 0.01% by adding water, and the diluted slurry is dehydrated by the Internet; pressed and dried; hot-rolled at a molding temperature of 120 ° C and a line pressure of 120 kg/cm, and then subjected to hot rolling.
  • the composite nanofiber membrane has a thickness of 20 ⁇ m, a porosity of 45%, an LOI of 30%, a dimensional shrinkage of 0.05% at a temperature of 200 ° C for 30 minutes, an electrolyte absorption rate of 356%, and a gas permeability Gurley value of 15 s/100 cc.
  • the mechanical tensile strength is 80 MPa, showing excellent properties.
  • the seaweed cellulose nanofiber, the polyethylene-vinyl acetate copolymer (low melting point polymer nanofiber), and the phenolic fiber (flame retardant material) are put into the dispersing agent isopropanol at a mass ratio of 20%, 65%, and 15%. Then, the slurry was prepared by high-speed mechanical stirring to achieve uniformity of the solution, and the additive hydroxymethylcellulose was added to the slurry, and the content of hydroxymethylcellulose was 10% of the absolute amount of the nanocellulose fiber.
  • the slurry is diluted to a mass concentration of 0.01% by adding water, and the diluted slurry is dehydrated by the Internet; pressed and dried; hot-rolled at a molding temperature of 110 ° C and a line pressure of 120 kg/cm, and then subjected to hot rolling.
  • the composite nanofiber membrane has a thickness of 50 ⁇ m, a porosity of 40%, and an LOI of 65%; a dimensional shrinkage of 5% at a temperature of 200 ° C for 30 minutes; an electrolyte absorption rate of 480%; and a gas permeability Gurley value of 260 s/100 cc,
  • the mechanical tensile strength is 10 MPa, showing excellent properties.
  • the slurry was prepared by adding the dispersant to deionized water at a mass ratio of 75%, 20%, 5%, and then the solution was uniformly homogenized by high-speed mechanical stirring, and the additive chitosan, chitosan was added to the slurry.
  • the mass content accounts for 10% of the absolute dryness of the cellulose nano-nanocellulose fibers.
  • the slurry was diluted to a mass concentration of 0.05% by adding an alcohol-water mixture, and the diluted slurry was dehydrated by the Internet; pressed and dried; and hot-rolled at a molding temperature of 110 ° C and a line pressure of 120 kg/cm. Then, through the roll paper, rewinding, slitting and packaging, a composite nanofiber separator for the battery is obtained.
  • the composite nanofiber membrane has a thickness of 80 ⁇ m, a porosity of 90%, an LOI of 20%, a dimensional shrinkage of 2% at a temperature of 200 ° C for 30 minutes, an electrolyte absorption rate of 150%, and a gas permeability Gurley value of 150 s/100 cc.
  • the mechanical tensile strength is 65 MPa, showing excellent properties.
  • Cellulose nanofibers Polyvinyl chloride (low melting point polymerization) separated from nanosized wood materials Nanofiber
  • flame retardant polypropylene fiber flame retardant material
  • the slurry is prepared, and an additive water-soluble polyurethane is added to the slurry, and the water-soluble polyurethane has a mass content of 0.5% of the absolute dry weight of the nanocellulose fiber.
  • the slurry is diluted to a mass concentration of 0.04% by adding water, and the diluted slurry is dehydrated by the Internet; pressed and dried; hot-rolled at a molding temperature of 120 ° C and a line pressure of 150 kg/cm, and then subjected to hot rolling.
  • the composite nanofiber membrane has a thickness of 30 ⁇ m, a porosity of 78%, and an LOI of 28%; a dimensional shrinkage of 5% at a temperature of 200 ° C for 30 minutes; an electrolyte absorption rate of 500%; and a gas permeability Gurley value of 150 s/100 cc,
  • the mechanical tensile strength is 100 MPa, showing excellent properties.
  • Cellulose nanofibers, polymethyl methacrylate fibers (low melting point polymer nanofibers), and tetramethylolphosphonium chloride (flame retardant materials) separated from nanosized wood materials by mass ratio of 35%, 30%, 35% is put into the dispersing agent in deionized water, and then the solution is prepared by high-speed mechanical stirring to make the solution uniform.
  • the additive carrageenan is added to the slurry.
  • the carrageenan mass content accounts for 4% of the absolute dry weight of the nanocellulose fiber. .
  • the slurry was diluted to a mass concentration of 0.03% by adding an alcohol-water mixture, and the diluted slurry was dehydrated by the Internet; pressed and dried; and hot-rolled at a molding temperature of 100 ° C and a line pressure of 120 kg/cm. Then, through the roll paper, rewinding, slitting and packaging, a composite nanofiber separator for the battery is obtained.
  • the composite nanofiber membrane has a thickness of 40 ⁇ m, a porosity of 85%, and an LOI of 20%; a dimensional shrinkage of 0.35% at a temperature of 200 ° C for 30 minutes; an electrolyte absorption rate of 328%; and a gas permeability Gurley value of 156 s/100 cc,
  • the mechanical tensile strength is 80 MPa, showing excellent properties.
  • Bacterial cellulose nanofibers, polyolefin fibers (low melting point polymer nanofibers), fluorocarbon (flame retardant materials) are put into dispersing agent deionized water at a mass ratio of 60%, 30%, and 10%, and The slurry is prepared by high-speed mechanical stirring to achieve uniformity of the solution, and the additive acetic acid is added to the slurry, and the acetic acid mass content accounts for 3% of the absolute dry weight of the nanocellulose fiber.
  • the solvent is diluted to a mass concentration of 0.05%, and the diluted slurry is dehydrated by the Internet; pressed and dried; hot-rolled at a molding temperature of 100 ° C and a line pressure of 110 kg/cm, and then subjected to hot rolling.
  • the composite nanofiber membrane has a thickness of 60 ⁇ m, a porosity of 58%, and an LOI of 47%; a dimensional shrinkage of 0.15% at a temperature of 200 ° C for 30 minutes; an electrolyte absorption rate of 296%; and a gas permeability Gurley value of 165 s/100 cc,
  • the mechanical tensile strength was 58 MPa, showing excellent properties.
  • the seaweed cellulose nanofiber, polyethylene succinate (low melting point polymer nanofiber), flame retardant polyester, flame retardant acrylic, flame retardant polypropylene (flame retardant material) by mass ratio of 45%, 25%, 30 % is put into the dispersant deionized water and glycerol, and then the slurry is prepared by high-speed mechanical stirring to achieve the overall uniformity.
  • the additive is added with starch starch and methylol starch, starch acetate and methylol acetate. The quality and content of starch accounted for 8% of the absolute dry weight of nanocellulose fibers.
  • the slurry is diluted to a mass concentration of 0.02% by adding water, and the diluted slurry is dehydrated by the net; pressed and dried; hot-rolled at a molding temperature of 100 ° C and a line pressure of 105 kg/cm, and then subjected to hot rolling.
  • the composite nanofiber membrane has a thickness of 25 ⁇ m, a porosity of 85%, an LOI of 50%, a dimensional shrinkage of 4% at a temperature of 200 ° C for 30 minutes, an electrolyte absorption rate of 180%, and a gas permeability Gurley value of 80 s/100 cc.
  • the mechanical tensile strength is 35 MPa, showing excellent properties.
  • Chlorinated fiber flame retardant material
  • the additive is acetic acid, and the acetic acid content accounts for 2% of the absolute dry weight of the nanocellulose fiber.
  • the slurry was diluted to a mass concentration of 0.04% by adding an alcohol-water mixture, and the diluted slurry was dehydrated by the Internet; pressed and dried; and hot-rolled at a molding temperature of 100 ° C and a line pressure of 150 kg/cm. Then, through the roll paper, rewinding, slitting and packaging, a composite nanofiber separator for the battery is obtained.
  • the composite nanofiber membrane has a thickness of 50 ⁇ m, a porosity of 55%, and an LOI of 46%; a dimensional shrinkage of 0.2% at a temperature of 200 ° C for 30 minutes; an electrolyte absorption rate of 433%; and a gas permeability Gurley value of 230 s/100 cc,
  • the mechanical tensile strength is 68 MPa, showing excellent properties.
  • a prior art polyolefin separator of the same size, a prior art pure nanocellulose separator, and a heat-resistant flame-retardant composite nanofiber membrane of the present invention are respectively fired by a lighter.
  • the polyolefin membrane of Fig. 1(a) has a large shrinkage deformation and the pure nanocellulose membrane of Fig. 1(b) is spontaneously burned.
  • the heat-resistant flame-retardant composite nanofiber membrane of the present invention has almost no dimensional shrinkage deformation and is less burned.
  • the present invention is a heat-resistant flame-retardant composite nanofiber membrane excellent in performance.
  • FIGS. 2 and 3 are comparative diagrams of thermal dimensional stability of the heat-resistant flame-retardant composite nanofiber separator prepared in the specific example 1.
  • the initial length of the separator before baking was 12 cm, and it was measured after baking at a temperature of 200 ° C for 30 minutes.
  • the length of the separator was still 12 cm, and there was almost no dimensional shrinkage.

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Abstract

Disclosed are a composite nanofiber membrane for an electrochemical element, a preparation method and an energy storage device. The membrane is prepared by self-assembly crosslinking of high-temperature resistant nanofibers, low melting point polymer nanofibers and a flame-retardant material through a wet-process papermaking method. The membrane has a thickness of 10-80 μm, a porosity of 40%-90%, a dimensional shrinkage of 0%-5% when the membrane is at the temperature of 200°C for 30 min, a limit oxygen index (LOI) of 20%-65%, a breathability index Gurley value of 5-300 s/100cc, an electrolyte absorptivity of 150%-500%, and a mechanical stretching strength of 10-100 MPa. The membrane has excellent high-temperature resistance and flame resistance, and the preparation process is simple, and low in cost.

Description

电化学元件用复合纳米纤维隔膜、制备方法及储能器件Composite nanofiber separator for electrochemical component, preparation method and energy storage device 技术领域Technical field
本发明属于电化学元件用隔膜技术领域,具体涉及一种具有耐高温的阻燃隔膜及其制备方法。本发明还涉及应用这种隔膜的生产的储能器件,包括锂离子电池,超级电容器,铅酸电池,锌空气电池,钠离子电池。The invention belongs to the technical field of separators for electrochemical components, and particularly relates to a flame retardant membrane with high temperature resistance and a preparation method thereof. The invention also relates to energy storage devices for the production of such separators, including lithium ion batteries, supercapacitors, lead acid batteries, zinc air batteries, sodium ion batteries.
背景技术Background technique
锂电池所具有高能量密度、高功率密度和循环寿命长等诸多优点,因而在便携式电子设备、动力电池和储能电池等领域得到了极大地关注。锂离子电池在应用过程中的过充电、短路、热冲击和机械冲击等都可能使锂离子电池发生着火、爆炸,给人们的生命和财产带来安全隐患。在锂电池的构成中,隔膜的主要作用是隔离正负极并使电子不能自由穿过,同时能让离子自由通过,其性能决定了电池的界面结构、内阻等,直接影响电池的容量、循环性能等,而且是关乎锂离子电池安全性能的关键部分。因此,电池隔膜性能是否优良,是提高电池安全性的关键环节之一。Lithium batteries have many advantages such as high energy density, high power density and long cycle life, and have received great attention in the fields of portable electronic devices, power batteries and energy storage batteries. Over-charging, short-circuit, thermal shock and mechanical shock of lithium-ion batteries may cause lithium-ion batteries to ignite and explode, posing a safety hazard to people's lives and property. In the composition of the lithium battery, the main function of the separator is to isolate the positive and negative electrodes and prevent electrons from passing freely, and at the same time allow ions to pass freely. The performance determines the interface structure and internal resistance of the battery, directly affecting the capacity of the battery. Cyclic performance, etc., and is a key part of the safety performance of lithium-ion batteries. Therefore, whether the performance of the battery separator is excellent is one of the key steps to improve the safety of the battery.
目前,锂离子电池隔膜主要为聚烯烃隔膜,其具有足够小的孔径能够有效防止电池内部短路,且具有较好的均匀性,能有效保证电池的充放电性能。但在应用过程中,如果电池由于内部短路或者过充等导致发生热失控,电池内部温度迅速升高,聚烯烃膜在高温下(高于170℃)无法保证其完整性,使正、负极材料发生大面积接触,导致电池发生爆炸,对电池的安全性构成威胁。特别是在锂离子动力电池中,大容量大功率充放电的设计要求隔膜具有更好的耐高温性能。其次,聚烯烃隔膜透气性较差,无法很好地满足电池快速充放电的需要,影响电池的循环使用寿命;另外,聚烯烃隔膜电解液浸润性和吸液能力差,影响锂电池倍率性能和长循环性能;综合上述内容,发 明一种具有高温尺寸稳定、良好透气性、良好的电解液浸润性和吸液能力的电池隔膜是很有必要的。At present, the lithium ion battery separator is mainly a polyolefin separator, which has a sufficiently small pore size to effectively prevent internal short circuit of the battery, and has good uniformity, and can effectively ensure the charge and discharge performance of the battery. However, in the application process, if the battery is thermally out of control due to internal short circuit or overcharge, the internal temperature of the battery rises rapidly, and the polyolefin film cannot guarantee its integrity at high temperature (above 170 ° C), so that the positive and negative materials are A large area of contact occurs, causing the battery to explode, posing a threat to the safety of the battery. Especially in lithium ion power batteries, the design of large capacity and high power charge and discharge requires better high temperature resistance of the diaphragm. Secondly, the polyolefin membrane has poor gas permeability, which can not meet the needs of rapid battery charge and discharge, affecting the cycle life of the battery; in addition, the polyolefin membrane electrolyte has poor wettability and liquid absorption capacity, affecting the lithium battery rate performance and Long cycle performance; synthesize the above content, send It is necessary to have a battery separator having high temperature dimensional stability, good gas permeability, good electrolyte wettability and liquid absorption capability.
为了进一步提高锂电池的安全性,抑制电解液的燃烧,目前已采用在电解液中添加阻燃剂的方法,当阻燃剂达到一定浓度后可以完全抑制电解液的燃烧,或者采用本身具有不燃性质的氟代酯类做电解液的溶剂。在隔膜领域,将隔膜进行阻燃改性,对提高锂电池的安全性也有着重要的作用。In order to further improve the safety of the lithium battery and inhibit the combustion of the electrolyte, a method of adding a flame retardant to the electrolyte has been adopted, and when the flame retardant reaches a certain concentration, the combustion of the electrolyte can be completely suppressed, or the flame retardant itself is incombustible. The nature of the fluoroesters as a solvent for the electrolyte. In the field of separators, the flame retardant modification of the separator also plays an important role in improving the safety of the lithium battery.
发明内容Summary of the invention
本发明所要解决的技术问题是为了提高电池隔膜的热稳定性能和阻燃性能,同时改善隔膜电解液浸润性能、吸液能力、透气性及电化学性能等,提供一种电化学元件用耐高温阻燃型复合纳米纤维隔膜及其制备方法。The technical problem to be solved by the present invention is to improve the thermal stability and flame retardancy of the battery separator, and at the same time improve the electrolyte wetting property, liquid absorbing ability, gas permeability and electrochemical performance of the separator, and provide a high temperature resistance for the electrochemical component. Flame-retardant composite nanofiber membrane and preparation method thereof.
为解决上述技术问题,本发明首先提供一种电化学元件用耐高温阻燃型复合纳米纤维隔膜,厚度为10-80μm,孔隙率为40-90%,透气性指标Gurley值5-300s/100cc,电解液吸收率为150-500%,机械拉伸强度为10-100MPa,热稳定性能优异,在200℃,30min,尺寸收缩率为0-5%,阻燃性能好,LOI(极限氧指数)为20-65%。In order to solve the above technical problems, the present invention firstly provides a high temperature flame retardant composite nanofiber separator for electrochemical components, having a thickness of 10-80 μm, a porosity of 40-90%, and a gas permeability index of Gurley of 5-300 s/100 cc. The electrolyte absorption rate is 150-500%, the mechanical tensile strength is 10-100 MPa, and the thermal stability is excellent. At 200 ° C, 30 min, the dimensional shrinkage is 0-5%, the flame retardancy is good, and the LOI (limit oxygen index) ) is 20-65%.
本发明原料以质量百分比含量计:包括纤维素纳米纤维20-78%、低熔点聚合物纳米纤维20-65%及阻燃材料2-35%。The raw materials of the present invention are based on the mass percentage content: 20-78% of cellulose nanofibers, 20-65% of low melting polymer nanofibers, and 2-35% of flame retardant materials.
所述的纤维素纳米纤维为从纳米尺寸木质材料分离的纤维素纳米纤维,海藻纤维素纳米纤维,以及通过培养菌株获得的细菌纤维素纳米纤维中的至少其中一种。The cellulose nanofibers are at least one of cellulose nanofibers separated from nanosized wood materials, seaweed cellulose nanofibers, and bacterial cellulose nanofibers obtained by culturing strains.
所述的纤维素纳米纤维的直径为10-1000nm,长度为10-3000μm。The cellulose nanofibers have a diameter of 10 to 1000 nm and a length of 10 to 3000 μm.
所述的低熔点聚合物纳米纤维为聚甲基丙烯酸甲酯、偏氟乙烯基聚合物、聚氨酯、聚氯乙烯,聚乙烯醇、聚烯烃、聚丙烯腈、聚乙烯-醋酸乙烯酯共聚物、聚丁二酸乙二醇酯的一种或者多种组合。The low melting point polymer nanofibers are polymethyl methacrylate, vinylidene fluoride polymer, polyurethane, polyvinyl chloride, polyvinyl alcohol, polyolefin, polyacrylonitrile, polyethylene-vinyl acetate copolymer, One or more combinations of polyethylene succinate.
所述的低熔点纤维的直径为10-1000nm。 The low melting point fiber has a diameter of 10 to 1000 nm.
所述的阻燃材料包括阻燃纤维氟纶、酚醛纤维、偏氟纶、氯纶、维氯纶、腈氯纶、PBI、芳纶(1414)、阻燃涤纶、阻燃腈纶、阻燃丙纶,聚芳砜酰胺等;以及阻燃剂磷酸酯、亚磷酸酯、四羟甲基氯化磷、有机磷盐、氧化磷、含磷多元醇、磷氮化合物、三聚氰胺、氰尿酸三聚氰胺、三(2,3-二溴丙基)异三聚氰酸酯、单氰铵、双氰铵、三聚氰酸、硫脲、十溴二苯醚中的一种或多种。The flame retardant material comprises flame retardant fiber fluorocarbon, phenolic fiber, partial fluorinated fiber, chlorinated fiber, urethane fiber, nitrile chlorinated fiber, PBI, aramid fiber (1414), flame retardant polyester fiber, flame retardant acrylic fiber, flame retardant polypropylene fiber , polyarylsulfone amide, etc.; and flame retardant phosphate, phosphite, tetramethylolphosphonium chloride, organic phosphorus salt, phosphorus oxide, phosphorus-containing polyol, phosphorus-nitrogen compound, melamine, melamine cyanurate, three ( One or more of 2,3-dibromopropyl)isocyanurate, monocyanamide, dicyandiamide, cyanuric acid, thiourea, decabromodiphenyl ether.
所述的阻燃材料中,阻燃纤维的直径为10-1000nm;阻燃剂粒径小于1μm。In the flame retardant material, the flame retardant fiber has a diameter of 10 to 1000 nm; and the flame retardant has a particle diameter of less than 1 μm.
本发明的另一目的在于提供一种成本低、生产工序简单、方便转移并且适宜大规模生产上述耐高温阻燃型复合纳米纤维隔膜的制备方法,其特征在于,具体步骤包括:Another object of the present invention is to provide a preparation method for a low-cost, simple production process, convenient transfer, and suitable for large-scale production of the above-mentioned high-temperature-resistant flame-retardant composite nanofiber separator, characterized in that the specific steps include:
I、以质量百分比含量计称取纤维素纳米纤维20-78%、低熔点聚合物纳米纤维20-65%及阻燃材料2-35%投入分散剂中,快速搅拌形成整体均匀的浆料;所述的分散剂包括去离子水、乙醇、异丙醇和丙三醇中的一种或多种;I. Weigh 20-78% of cellulose nanofibers, 20-65% of low melting polymer nanofibers and 2-35% of flame retardant materials into the dispersant by mass percentage content, and rapidly stir to form a whole uniform slurry; The dispersing agent includes one or more of deionized water, ethanol, isopropanol and glycerol;
II、向步骤I的浆料中加入添加剂;所述添加剂包括醋酸、醋酸淀粉、羟甲基淀粉、羧甲基纤维素钠、羟甲基纤维素、明胶、卡拉胶、壳聚糖、甲壳素、聚氧化乙烯,水溶性聚氨酯、聚丙烯酰胺、聚乙烯吡咯烷酮或水溶性聚氨酯中的一种或多种;所述添加剂的质量为纤维素纳米纤维的0.1-10%;II. Adding an additive to the slurry of step I; the additive comprises acetic acid, starch acetate, methylol starch, sodium carboxymethylcellulose, hydroxymethylcellulose, gelatin, carrageenan, chitosan, chitin Or one or more of polyethylene oxide, water-soluble polyurethane, polyacrylamide, polyvinylpyrrolidone or water-soluble polyurethane; the mass of the additive is 0.1-10% of the cellulose nanofiber;
III、将步骤II后的浆料稀释至质量百分比浓度为0.01-0.05%;III, the slurry after step II is diluted to a mass percentage concentration of 0.01-0.05%;
IV、稀释后的浆料经上网脱水成型、压榨、干燥、热轧成型,即得到所述的耐高温阻燃型复合纳米纤维隔膜;所述的压榨线压力为60-120kg/cm,所述的干燥温度为70-100℃,所述的热轧成型温度为100-300℃,线压力为95-300kg/cm条件下进行热轧成型。IV. The diluted slurry is subjected to dehydration molding, pressing, drying and hot rolling forming on the Internet to obtain the high temperature resistant flame-retardant composite nanofiber separator; the press line pressure is 60-120 kg/cm, The drying temperature is 70-100 ° C, the hot rolling forming temperature is 100-300 ° C, and the line pressure is 95-300 kg/cm.
所述的分散剂包括去离子水、乙醇、异丙醇和丙三醇中的一种或多种;所述的添加剂包括醋酸、醋酸淀粉、羟甲基淀粉、羧甲基纤维素钠、羟甲基纤维素、明胶、卡拉胶、壳聚糖、甲壳素、聚氧化乙烯,水溶性聚氨酯、聚丙 烯酰胺、聚乙烯吡咯烷酮或水溶性聚氨酯中的一种或多种;所述添加剂的质量百分比为纳米纤维素纤维绝干量的0.1-10%。The dispersing agent comprises one or more of deionized water, ethanol, isopropanol and glycerin; the additive comprises acetic acid, starch acetate, methylol starch, sodium carboxymethyl cellulose, hydroxyl group Cellulose, gelatin, carrageenan, chitosan, chitin, polyethylene oxide, water soluble polyurethane, polypropylene One or more of an enamide, a polyvinylpyrrolidone or a water-soluble polyurethane; the mass percentage of the additive is from 0.1 to 10% of the absolute dry weight of the nanocellulose fiber.
综上,本发明采用湿法抄造的方法,通过耐高温的纳米纤维,低熔点的聚合物纳米纤维以及阻燃材料的之间自组装交联制备成具有耐高温的阻燃型复合纳米纤维隔膜。所述纤维素纳米纤维之间主要通过氢键、分子间作用力结合,纤维素纳米纤维与低熔点聚合物纳米纤维及阻燃纤维长径间通过交联作用结合。In summary, the present invention adopts a wet-laid method to prepare a flame-retardant composite nanofiber membrane with high temperature resistance by self-assembly cross-linking between high-temperature resistant nanofibers, low melting point polymer nanofibers and flame retardant materials. . The cellulose nanofibers are mainly combined by hydrogen bonding and intermolecular force, and the cellulose nanofibers are combined with the low melting point polymer nanofibers and the long diameter of the flame retardant fibers by crosslinking.
本发明的另一方面在于提供储能器件,包括锂离子电池,超级电容器,铅酸电池,锌空气电池,钠离子电池等使用由上述方法制得的原纤化纤维素纳米纤维的闭孔复合隔膜。Another aspect of the present invention is to provide an energy storage device comprising a closed cell composite using a fibrillated cellulose nanofiber obtained by the above method, such as a lithium ion battery, a supercapacitor, a lead acid battery, a zinc air battery, a sodium ion battery, or the like. Diaphragm.
本发明采用耐高温的纳米纤维、低熔点的聚合物纳米纤维及阻燃材料自组装制备了具有耐高温性、阻燃性能优异的复合纳米纤维隔膜。本发明有益效果在于:The invention adopts high-temperature resistant nanofibers, low melting point polymer nanofibers and flame retardant materials to self-assemble and prepare composite nanofiber membranes with high temperature resistance and excellent flame retardant performance. The beneficial effects of the invention are:
1)隔膜一旦暴露于高温环境,隔膜可通过闭孔来防止电池损害后的过量和不期望的离子输送阻隔电流的传导,防止爆炸。2)隔膜的耐高温性又能够保证隔膜在高温尺寸稳定性,防止正负极大面积短接而发生着火燃烧。3)阻燃性能,即使发生短路散发大量的热量达到燃点,隔膜的阻燃性能又能抑制起火燃烧。4)制造工艺简单、低成本。1) Once the diaphragm is exposed to a high temperature environment, the diaphragm can prevent leakage and excessive conduction and undesired ion transport blocking current conduction through the closed hole to prevent explosion. 2) The high temperature resistance of the diaphragm can ensure the stability of the diaphragm at high temperature and prevent the positive and negative electrodes from being short-circuited and fired. 3) Flame retardant performance, even if a short circuit emits a large amount of heat to reach the ignition point, the flame retardant performance of the diaphragm can inhibit the ignition. 4) The manufacturing process is simple and low cost.
附图说明DRAWINGS
下面结合附图和具体实施方式对本发明的技术方案作进一步具体说明。The technical solutions of the present invention are further described in detail below with reference to the accompanying drawings and specific embodiments.
图1为(a)聚烯烃隔膜、(b)纯纳米纤维素隔膜和(c)耐热阻燃型复合纳米纤维隔膜的燃烧性能对比图。1 is a comparison diagram of combustion properties of (a) a polyolefin separator, (b) a pure nanocellulose separator, and (c) a heat-resistant flame-retardant composite nanofiber separator.
图2为具体实施例1中耐热阻燃型复合纳米纤维隔膜的烘烤前尺寸测量图。 2 is a pre-bake size measurement chart of the heat-resistant flame-retardant composite nanofiber separator in Specific Example 1.
图3为具体实施例1中耐热阻燃型复合纳米纤维隔膜的烘烤后尺寸测量图。Fig. 3 is a graph showing the dimensional measurement after baking of the heat-resistant flame-retardant composite nanofiber membrane of the specific example 1.
具体实施方式detailed description
以上是对本发明的一般性描述,下面我们将通过具体实施例对本发明的权利要求作进一步的解释。但本发明并非受限于以下讨论的实施例,可以以不同的形式来实施。The above is a general description of the invention, and the claims of the invention are further explained below by way of specific examples. However, the invention is not limited to the embodiments discussed below, and may be embodied in different forms.
制备电化学元件用复合纳米纤维隔膜,包括以下步骤:The composite nanofiber membrane for preparing an electrochemical component comprises the following steps:
步骤一、将质量比为纤维素纳米纤维20-78%、低熔点聚合物纳米纤维20-65%及阻燃材料2-35%投入分散剂中,分散剂为去离子水、乙醇、异丙醇和丙三醇中的一种或多种,快速搅拌形成整体均匀的浆料。Step 1. The mass ratio is 20-78% of cellulose nanofibers, 20-65% of low melting polymer nanofibers and 2-35% of flame retardant materials, and the dispersing agent is deionized water, ethanol and isopropyl. One or more of an alcohol and glycerol are rapidly agitated to form an overall uniform slurry.
其中,纤维素纳米纤维为从纳米尺寸木质材料分离的原纤化纤维素纳米纤维,海藻纤维素纳米纤维,以及通过培养菌株获得的细菌纤维素纳米纤维中的至少其中一种;纤维素纳米纤维的直径为10-1000nm,长度为10-3000μm。Wherein the cellulose nanofiber is at least one of fibrillated cellulose nanofibers separated from nanosized wood materials, seaweed cellulose nanofibers, and bacterial cellulose nanofibers obtained by culturing the strain; cellulose nanofibers The diameter is 10-1000 nm and the length is 10-3000 μm.
低熔点聚合物纳米纤维为聚甲基丙烯酸甲酯、偏氟乙烯基聚合物、聚氨酯、聚氯乙烯,聚乙烯醇、聚烯烃、聚丙烯腈、聚乙烯-醋酸乙烯酯共聚物、聚丁二酸乙二醇酯的一种或者多种组合,低熔点聚合物纳米纤维的直径为10-1000nm。The low melting point polymer nanofibers are polymethyl methacrylate, vinylidene fluoride polymer, polyurethane, polyvinyl chloride, polyvinyl alcohol, polyolefin, polyacrylonitrile, polyethylene-vinyl acetate copolymer, polybutylene One or more combinations of acid glycol esters, the low melting point polymer nanofibers have a diameter of from 10 to 1000 nm.
阻燃材料包括阻燃纤维氟纶、酚醛纤维、偏氟纶、氯纶、维氯纶、腈氯纶、PBI、芳纶(1414)、阻燃涤纶、阻燃腈纶、阻燃丙纶,聚芳砜酰胺;以及阻燃剂磷酸酯、亚磷酸酯、四羟甲基氯化磷、有机磷盐、氧化磷、含磷多元醇、磷氮化合物、三聚氰胺、氰尿酸三聚氰胺、三(2,3-二溴丙基)异三聚氰酸酯、单氰铵、双氰铵、三聚氰酸、硫脲、十溴二苯醚中的一种或多种;阻燃材料中,阻燃纤维的直径为10-1000nm;阻燃剂粒径小于1μm。Flame retardant materials include flame retardant fiber fluorocarbon, phenolic fiber, vinylidene fluoride, polyvinyl chloride, vinyl chloride, nitrile chloride, PBI, aramid (1414), flame retardant polyester, flame retardant acrylic, flame retardant polypropylene, polyfang Sulfonamide; and flame retardant phosphate, phosphite, tetramethylolphosphonium chloride, organic phosphorus salt, phosphorus oxide, phosphorus-containing polyol, phosphorus-nitrogen compound, melamine, melamine cyanurate, tris(2,3- One or more of dibromopropyl)isocyanate, monocyanamide, dicyandiamide, cyanuric acid, thiourea, decabromodiphenyl ether; flame retardant materials, flame retardant fibers The diameter is 10-1000 nm; the flame retardant particle size is less than 1 μm.
步骤二、向浆料中加入添加剂,添加剂为醋酸、醋酸淀粉、羟甲基淀粉、 羧甲基纤维素钠、羟甲基纤维素、明胶、卡拉胶、壳聚糖、甲壳素、聚氧化乙烯,水溶性聚氨酯、聚丙烯酰胺、聚乙烯吡咯烷酮或水溶性聚氨酯中的一种或多种;添加剂的质量为浆料中纤维素纳米纳米纤维素纤维绝干量的0.1-10%;Step 2, adding an additive to the slurry, the additive is acetic acid, starch acetate, methylol starch, One or more of sodium carboxymethyl cellulose, hydroxymethyl cellulose, gelatin, carrageenan, chitosan, chitin, polyethylene oxide, water-soluble polyurethane, polyacrylamide, polyvinylpyrrolidone or water-soluble polyurethane The quality of the additive is 0.1-10% of the dry amount of the cellulose nano-nanose cellulose fiber in the slurry;
步骤三、将浆料水稀释至质量百分比浓度为0.01-0.05%;Step 3, the slurry water is diluted to a mass percentage concentration of 0.01-0.05%;
步骤四、稀释后的浆料经上网脱水成型、在辊线压力为60-120kg/cm下压榨,烘缸温度为70-100℃干燥后,在温度为100-300℃,线压力为100-300kg/cm条件下进行热轧成型,即得到本发明的耐高温阻燃型复合纳米纤维隔膜。Step 4: The diluted slurry is dehydrated by the Internet, and is pressed at a roller line pressure of 60-120 kg/cm. After drying at a temperature of 70-100 ° C, the temperature is 100-300 ° C and the line pressure is 100- The hot-rolling forming composite nanofiber separator of the present invention is obtained by hot-rolling at 300 kg/cm.
得到的隔膜厚度为10-80μm;孔隙率为40-90%,便于电解液离子的穿过;在200℃的温度下30min,尺寸收缩率为0-5%;极限氧指数LOI为20-65%;透气性指标Gurley值为5-300s/100cc;电解液吸收率为150%-500%,机械拉伸强度为10-100MPa。The obtained separator has a thickness of 10-80 μm; the porosity is 40-90%, which facilitates the passage of electrolyte ions; the dimensional shrinkage is 0-5% at a temperature of 200 ° C for 30 min; and the limiting oxygen index LOI is 20-65. %; gas permeability index Gurley value is 5-300s/100cc; electrolyte absorption rate is 150%-500%, mechanical tensile strength is 10-100MPa.
实施例1Example 1
将从纳米尺寸木质材料分离的纤维素纳米纤维、聚丙烯纤维(低熔点聚合物纳米纤维)、芳纶纤维(阻燃材料)按质量比75%、20%、5%投入分散剂去离子水中,并随后通过高速机械搅拌使溶液达到整体的均匀来制备浆料,向浆料中加入添加剂醋酸,醋酸质量含量占纳米纤维素纤维绝干量的0.1%。加入水将浆料稀释至质量浓度为0.01%,将稀释好的浆料经上网脱水成型;压榨、干燥;在成型温度为120℃,线压力为120kg/cm条件下进行热轧成型,再经卷纸、复卷、分切和包装,制得电池用复合纳米纤维隔膜。Cellulose nanofibers, polypropylene fibers (low melting point polymer nanofibers), and aramid fibers (flame retardant materials) separated from nanosized wood materials are put into dispersing agent deionized water at a mass ratio of 75%, 20%, and 5%. Then, the slurry is prepared by high-speed mechanical stirring to achieve uniformity of the whole, and the additive acetic acid is added to the slurry, and the acetic acid mass content accounts for 0.1% of the absolute dry weight of the nanocellulose fiber. The slurry is diluted to a mass concentration of 0.01% by adding water, and the diluted slurry is dehydrated by the Internet; pressed and dried; hot-rolled at a molding temperature of 120 ° C and a line pressure of 120 kg/cm, and then subjected to hot rolling. Rolled paper, rewinding, slitting and packaging to produce a composite nanofiber separator for batteries.
复合纳米纤维隔膜厚度为20μm,孔隙率为45%,LOI为30%;在200℃温度下30min的尺寸收缩率为0.05%;电解液吸收率为356%;透气性Gurley值为15s/100cc,机械拉伸强度为80MPa,展示出优良的特性。 The composite nanofiber membrane has a thickness of 20 μm, a porosity of 45%, an LOI of 30%, a dimensional shrinkage of 0.05% at a temperature of 200 ° C for 30 minutes, an electrolyte absorption rate of 356%, and a gas permeability Gurley value of 15 s/100 cc. The mechanical tensile strength is 80 MPa, showing excellent properties.
实施例2Example 2
将海藻纤维素纳米纤维、聚乙烯-醋酸乙烯酯共聚物(低熔点聚合物纳米纤维)、酚醛纤维(阻燃材料)按质量比20%、65%、15%投入分散剂异丙醇中,并随后通过高速机械搅拌使溶液达到整体的均匀来制备浆料,向浆料中加入添加剂羟甲基纤维素,羟甲基纤维素质量含量占纳米纤维素纤维绝干量的10%。加入水将浆料稀释至质量浓度为0.01%,将稀释好的浆料经上网脱水成型;压榨、干燥;在成型温度为110℃,线压力为120kg/cm条件下进行热轧成型,再经卷纸、复卷、分切和包装,制得电池用复合纳米纤维隔膜。The seaweed cellulose nanofiber, the polyethylene-vinyl acetate copolymer (low melting point polymer nanofiber), and the phenolic fiber (flame retardant material) are put into the dispersing agent isopropanol at a mass ratio of 20%, 65%, and 15%. Then, the slurry was prepared by high-speed mechanical stirring to achieve uniformity of the solution, and the additive hydroxymethylcellulose was added to the slurry, and the content of hydroxymethylcellulose was 10% of the absolute amount of the nanocellulose fiber. The slurry is diluted to a mass concentration of 0.01% by adding water, and the diluted slurry is dehydrated by the Internet; pressed and dried; hot-rolled at a molding temperature of 110 ° C and a line pressure of 120 kg/cm, and then subjected to hot rolling. Rolled paper, rewinding, slitting and packaging to produce a composite nanofiber separator for batteries.
复合纳米纤维隔膜厚度为50μm,孔隙率为40%,LOI为65%;在200℃温度下30min的尺寸收缩率为5%;电解液吸收率为480%;透气性Gurley值为260s/100cc,机械拉伸强度为10MPa,展示出优良的特性。The composite nanofiber membrane has a thickness of 50 μm, a porosity of 40%, and an LOI of 65%; a dimensional shrinkage of 5% at a temperature of 200 ° C for 30 minutes; an electrolyte absorption rate of 480%; and a gas permeability Gurley value of 260 s/100 cc, The mechanical tensile strength is 10 MPa, showing excellent properties.
实施例3Example 3
将通过培养菌株获得的细菌纤维素纳米纤维、聚乙烯醇(低熔点聚合物纳米纤维)、三(2,3-二溴丙基)异三聚氰酸酯和单氰铵的混合物(阻燃材料)按质量比75%、20%、5%投入分散剂去离子水中,并随后通过高速机械搅拌使溶液达到整体的均匀来制备浆料,向浆料中加入添加剂壳聚糖,壳聚糖质量含量占纤维素纳米纳米纤维素纤维绝干量的10%。加入醇水混合液将浆料稀释至质量浓度为0.05%,将稀释好的浆料经上网脱水成型;压榨、干燥;在成型温度为110℃,线压力为120kg/cm条件下进行热轧成型,再经卷纸、复卷、分切和包装,制得电池用复合纳米纤维隔膜。a mixture of bacterial cellulose nanofibers, polyvinyl alcohol (low melting point polymer nanofibers), tris(2,3-dibromopropyl)isocyanurate and monocyanamide obtained by culturing the strain (flame retardant) Material) The slurry was prepared by adding the dispersant to deionized water at a mass ratio of 75%, 20%, 5%, and then the solution was uniformly homogenized by high-speed mechanical stirring, and the additive chitosan, chitosan was added to the slurry. The mass content accounts for 10% of the absolute dryness of the cellulose nano-nanocellulose fibers. The slurry was diluted to a mass concentration of 0.05% by adding an alcohol-water mixture, and the diluted slurry was dehydrated by the Internet; pressed and dried; and hot-rolled at a molding temperature of 110 ° C and a line pressure of 120 kg/cm. Then, through the roll paper, rewinding, slitting and packaging, a composite nanofiber separator for the battery is obtained.
复合纳米纤维隔膜厚度为80μm,孔隙率为90%,LOI为20%;在200℃温度下30min的尺寸收缩率为2%;电解液吸收率为150%;透气性Gurley值为150s/100cc,机械拉伸强度为65MPa,展示出优良的特性。The composite nanofiber membrane has a thickness of 80 μm, a porosity of 90%, an LOI of 20%, a dimensional shrinkage of 2% at a temperature of 200 ° C for 30 minutes, an electrolyte absorption rate of 150%, and a gas permeability Gurley value of 150 s/100 cc. The mechanical tensile strength is 65 MPa, showing excellent properties.
实施例4Example 4
将从纳米尺寸木质材料分离的纤维素纳米纤维、聚氯乙烯(低熔点聚合 物纳米纤维)、阻燃丙纶纤维(阻燃材料)按质量比45%、53%、2%投入分散剂乙醇与异丙醇的混合物中,并随后通过高速机械搅拌使溶液达到整体的均匀来制备浆料,向浆料中加入添加剂水溶性聚氨酯,水溶性聚氨酯质量含量占纳米纤维素纤维绝干量的0.5%。加入水将浆料稀释至质量浓度为0.04%,将稀释好的浆料经上网脱水成型;压榨、干燥;在成型温度为120℃,线压力为150kg/cm条件下进行热轧成型,再经卷纸、复卷、分切和包装,制得电池用复合纳米纤维隔膜。Cellulose nanofibers, polyvinyl chloride (low melting point polymerization) separated from nanosized wood materials Nanofiber), flame retardant polypropylene fiber (flame retardant material) was put into a mixture of dispersant ethanol and isopropanol at a mass ratio of 45%, 53%, 2%, and then the solution was uniformly uniformed by high-speed mechanical stirring. The slurry is prepared, and an additive water-soluble polyurethane is added to the slurry, and the water-soluble polyurethane has a mass content of 0.5% of the absolute dry weight of the nanocellulose fiber. The slurry is diluted to a mass concentration of 0.04% by adding water, and the diluted slurry is dehydrated by the Internet; pressed and dried; hot-rolled at a molding temperature of 120 ° C and a line pressure of 150 kg/cm, and then subjected to hot rolling. Rolled paper, rewinding, slitting and packaging to produce a composite nanofiber separator for batteries.
复合纳米纤维隔膜厚度为30μm,孔隙率为78%,LOI为28%;在200℃温度下30min的尺寸收缩率为5%;电解液吸收率为500%;透气性Gurley值为150s/100cc,机械拉伸强度为100MPa,展示出优良的特性。The composite nanofiber membrane has a thickness of 30 μm, a porosity of 78%, and an LOI of 28%; a dimensional shrinkage of 5% at a temperature of 200 ° C for 30 minutes; an electrolyte absorption rate of 500%; and a gas permeability Gurley value of 150 s/100 cc, The mechanical tensile strength is 100 MPa, showing excellent properties.
实施例5Example 5
将从纳米尺寸木质材料分离的纤维素纳米纤维、聚甲基丙烯酸甲酯纤维(低熔点聚合物纳米纤维)、四羟甲基氯化磷(阻燃材料)按质量比35%、30%、35%投入分散剂去离子水中,并随后通过高速机械搅拌使溶液达到整体的均匀来制备浆料,向浆料中加入添加剂卡拉胶,卡拉胶质量含量占纳米纤维素纤维绝干量的4%。加入醇水混合液将浆料稀释至质量浓度为0.03%,将稀释好的浆料经上网脱水成型;压榨、干燥;在成型温度为100℃,线压力为120kg/cm条件下进行热轧成型,再经卷纸、复卷、分切和包装,制得电池用复合纳米纤维隔膜。Cellulose nanofibers, polymethyl methacrylate fibers (low melting point polymer nanofibers), and tetramethylolphosphonium chloride (flame retardant materials) separated from nanosized wood materials by mass ratio of 35%, 30%, 35% is put into the dispersing agent in deionized water, and then the solution is prepared by high-speed mechanical stirring to make the solution uniform. The additive carrageenan is added to the slurry. The carrageenan mass content accounts for 4% of the absolute dry weight of the nanocellulose fiber. . The slurry was diluted to a mass concentration of 0.03% by adding an alcohol-water mixture, and the diluted slurry was dehydrated by the Internet; pressed and dried; and hot-rolled at a molding temperature of 100 ° C and a line pressure of 120 kg/cm. Then, through the roll paper, rewinding, slitting and packaging, a composite nanofiber separator for the battery is obtained.
复合纳米纤维隔膜厚度为40μm,孔隙率为85%,LOI为20%;在200℃温度下30min的尺寸收缩率为0.35%;电解液吸收率为328%;透气性Gurley值为156s/100cc,机械拉伸强度为80MPa,展示出优良的特性。The composite nanofiber membrane has a thickness of 40 μm, a porosity of 85%, and an LOI of 20%; a dimensional shrinkage of 0.35% at a temperature of 200 ° C for 30 minutes; an electrolyte absorption rate of 328%; and a gas permeability Gurley value of 156 s/100 cc, The mechanical tensile strength is 80 MPa, showing excellent properties.
实施例6Example 6
将细菌纤维素纳米纤维、聚烯烃纤维(低熔点聚合物纳米纤维)、氟纶(阻燃材料)按质量比60%、30%、10%投入分散剂去离子水中,并随 后通过高速机械搅拌使溶液达到整体的均匀来制备浆料,向浆料中加入添加剂醋酸,醋酸质量含量占纳米纤维素纤维绝干量的3%。加入溶剂将浆料稀释至质量浓度为0.05%,将稀释好的浆料经上网脱水成型;压榨、干燥;在成型温度为100℃,线压力为110kg/cm条件下进行热轧成型,再经卷纸、复卷、分切和包装,制得电池用复合纳米纤维隔膜。Bacterial cellulose nanofibers, polyolefin fibers (low melting point polymer nanofibers), fluorocarbon (flame retardant materials) are put into dispersing agent deionized water at a mass ratio of 60%, 30%, and 10%, and The slurry is prepared by high-speed mechanical stirring to achieve uniformity of the solution, and the additive acetic acid is added to the slurry, and the acetic acid mass content accounts for 3% of the absolute dry weight of the nanocellulose fiber. The solvent is diluted to a mass concentration of 0.05%, and the diluted slurry is dehydrated by the Internet; pressed and dried; hot-rolled at a molding temperature of 100 ° C and a line pressure of 110 kg/cm, and then subjected to hot rolling. Rolled paper, rewinding, slitting and packaging to produce a composite nanofiber separator for batteries.
复合纳米纤维隔膜厚度为60μm,孔隙率为58%,LOI为47%;在200℃温度下30min的尺寸收缩率为0.15%;电解液吸收率为296%;透气性Gurley值为165s/100cc,机械拉伸强度为58MPa,展示出优良的特性。The composite nanofiber membrane has a thickness of 60 μm, a porosity of 58%, and an LOI of 47%; a dimensional shrinkage of 0.15% at a temperature of 200 ° C for 30 minutes; an electrolyte absorption rate of 296%; and a gas permeability Gurley value of 165 s/100 cc, The mechanical tensile strength was 58 MPa, showing excellent properties.
实施例7Example 7
将海藻纤维素纳米纤维、聚丁二酸乙二醇酯(低熔点聚合物纳米纤维)、阻燃涤纶、阻燃腈纶、阻燃丙纶(阻燃材料)按质量比45%、25%、30%投入分散剂去离子水与丙三醇中,并随后通过高速机械搅拌使溶液达到整体的均匀来制备浆料,向浆料中加入添加剂醋酸淀粉和羟甲基淀粉,醋酸淀粉和羟甲基淀粉的质量和含量占纳米纤维素纤维绝干量的8%。加入水将浆料稀释至质量浓度为0.02%,将稀释好的浆料经上网脱水成型;压榨、干燥;在成型温度为100℃,线压力为105kg/cm条件下进行热轧成型,再经卷纸、复卷、分切和包装,制得电池用复合纳米纤维隔膜。The seaweed cellulose nanofiber, polyethylene succinate (low melting point polymer nanofiber), flame retardant polyester, flame retardant acrylic, flame retardant polypropylene (flame retardant material) by mass ratio of 45%, 25%, 30 % is put into the dispersant deionized water and glycerol, and then the slurry is prepared by high-speed mechanical stirring to achieve the overall uniformity. The additive is added with starch starch and methylol starch, starch acetate and methylol acetate. The quality and content of starch accounted for 8% of the absolute dry weight of nanocellulose fibers. The slurry is diluted to a mass concentration of 0.02% by adding water, and the diluted slurry is dehydrated by the net; pressed and dried; hot-rolled at a molding temperature of 100 ° C and a line pressure of 105 kg/cm, and then subjected to hot rolling. Rolled paper, rewinding, slitting and packaging to produce a composite nanofiber separator for batteries.
复合纳米纤维隔膜厚度为25μm,孔隙率为85%,LOI为50%;在200℃温度下30min的尺寸收缩率为4%;电解液吸收率为180%;透气性Gurley值为80s/100cc,机械拉伸强度为35MPa,展示出优良的特性。The composite nanofiber membrane has a thickness of 25 μm, a porosity of 85%, an LOI of 50%, a dimensional shrinkage of 4% at a temperature of 200 ° C for 30 minutes, an electrolyte absorption rate of 180%, and a gas permeability Gurley value of 80 s/100 cc. The mechanical tensile strength is 35 MPa, showing excellent properties.
实施例8Example 8
将从纳米尺寸木质材料分离的纤维素纳米纤维、偏氟乙烯基聚合物与聚丁二酸乙二醇酯(低熔点聚合物纳米纤维)、聚芳砜酰胺与偏氟纶、氯纶、维氯纶(阻燃材料)按质量比35%、50%、15%投入分散剂去离子水中,并随后通过高速机械搅拌使溶液达到整体的均匀来制备浆料,向浆料中加 入添加剂醋酸,醋酸质量含量占纳米纤维素纤维绝干量的2%。加入醇水混合液将浆料稀释至质量浓度为0.04%,将稀释好的浆料经上网脱水成型;压榨、干燥;在成型温度为100℃,线压力为150kg/cm条件下进行热轧成型,再经卷纸、复卷、分切和包装,制得电池用复合纳米纤维隔膜。Cellulose nanofibers, vinylidene fluoride polymers and polybutylene succinate (low melting point polymer nanofibers), polyarylsulfone amides and perfluoropolyethers, polyvinyl chlorides, oligos, which are separated from nanosized wood materials Chlorinated fiber (flame retardant material) is put into dispersing agent deionized water at a mass ratio of 35%, 50%, 15%, and then the slurry is uniformly homogenized by high-speed mechanical stirring to prepare a slurry, which is added to the slurry. The additive is acetic acid, and the acetic acid content accounts for 2% of the absolute dry weight of the nanocellulose fiber. The slurry was diluted to a mass concentration of 0.04% by adding an alcohol-water mixture, and the diluted slurry was dehydrated by the Internet; pressed and dried; and hot-rolled at a molding temperature of 100 ° C and a line pressure of 150 kg/cm. Then, through the roll paper, rewinding, slitting and packaging, a composite nanofiber separator for the battery is obtained.
复合纳米纤维隔膜厚度为50μm,孔隙率为55%,LOI为46%;在200℃温度下30min的尺寸收缩率为0.2%;电解液吸收率为434%;透气性Gurley值为230s/100cc,机械拉伸强度为68MPa,展示出优良的特性。The composite nanofiber membrane has a thickness of 50 μm, a porosity of 55%, and an LOI of 46%; a dimensional shrinkage of 0.2% at a temperature of 200 ° C for 30 minutes; an electrolyte absorption rate of 433%; and a gas permeability Gurley value of 230 s/100 cc, The mechanical tensile strength is 68 MPa, showing excellent properties.
对比试验:Comparative Test:
如图1所示的对比图,用打火机分别烧灼同样尺寸大小的现有技术的聚烯烃隔膜、现有技术的纯纳米纤维素隔膜和本发明的耐热阻燃型复合纳米纤维隔膜,从图1看出,图1(a)中聚烯烃隔膜尺寸收缩变形严重、图1(b)中纯纳米纤维素隔膜自身起火燃烧。而图1(c)中本发明的耐热阻燃型复合纳米纤维隔膜几乎没有尺寸收缩变形,更没有燃烧。说明本发明的是一种性能优异的耐热阻燃型复合纳米纤维隔膜。As shown in the comparative diagram of FIG. 1, a prior art polyolefin separator of the same size, a prior art pure nanocellulose separator, and a heat-resistant flame-retardant composite nanofiber membrane of the present invention are respectively fired by a lighter. It can be seen that the polyolefin membrane of Fig. 1(a) has a large shrinkage deformation and the pure nanocellulose membrane of Fig. 1(b) is spontaneously burned. On the other hand, in Fig. 1(c), the heat-resistant flame-retardant composite nanofiber membrane of the present invention has almost no dimensional shrinkage deformation and is less burned. DESCRIPTION OF THE INVENTION The present invention is a heat-resistant flame-retardant composite nanofiber membrane excellent in performance.
图2、图3为对具体实施例1制备的耐热阻燃型复合纳米纤维隔膜的热尺寸稳定性能对比图。烘烤前隔膜初始长度为12cm,在200℃的温度下烘烤30min后测量,隔膜长度仍为12cm,几乎没有尺寸收缩。2 and 3 are comparative diagrams of thermal dimensional stability of the heat-resistant flame-retardant composite nanofiber separator prepared in the specific example 1. The initial length of the separator before baking was 12 cm, and it was measured after baking at a temperature of 200 ° C for 30 minutes. The length of the separator was still 12 cm, and there was almost no dimensional shrinkage.
最后所应说明的是,以上具体实施方式仅用以说明本发明的技术方案而非限制,尽管参照较佳实施例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的精神和范围,其均应涵盖在本发明的权利要求范围当中。 It should be understood that the above specific embodiments are only illustrative of the technical solutions of the present invention, and are not to be construed as limiting. The technical solutions are modified or equivalent, without departing from the spirit and scope of the invention, and are intended to be included within the scope of the appended claims.

Claims (10)

  1. 一种电化学元件用复合纳米纤维隔膜,其特征在于,所述的隔膜厚度为10-80μm;孔隙率为40-90%,便于电解液离子的穿过;在200℃的温度下30min,尺寸收缩率为0-5%;极限氧指数LOI为20-65%;透气性指标Gurley值为5-300s/100cc;电解液吸收率为150-500%,机械拉伸强度为10MPa-100MPa。A composite nanofiber separator for electrochemical components, characterized in that the separator has a thickness of 10-80 μm; a porosity of 40-90%, which facilitates the passage of electrolyte ions; at a temperature of 200 ° C for 30 minutes, the size The shrinkage rate is 0-5%; the limiting oxygen index LOI is 20-65%; the gas permeability index Gurley value is 5-300 s/100 cc; the electrolyte absorption rate is 150-500%, and the mechanical tensile strength is 10 MPa-100 MPa.
  2. 根据权利要求1所述的电化学元件用复合纳米纤维隔膜,其特征在于,原料以质量百分比含量计:包括纤维素纳米纤维20-78%、低熔点聚合物纳米纤维20-65%及阻燃材料2-35%。The composite nanofiber separator for electrochemical components according to claim 1, wherein the raw materials are in mass percentage content: 20-78% of cellulose nanofibers, 20-65% of low melting point polymer nanofibers, and flame retardant. Material 2-35%.
  3. 根据权利要求3所述的电化学元件用复合纳米纤维隔膜,其特征在于,所述的纤维素纳米纤维为从纳米尺寸木质材料分离的纤维素纳米纤维,海藻纤维素纳米纤维,以及通过培养菌株获得的细菌纤维素纳米纤维中的至少其中一种。The composite nanofiber separator for electrochemical components according to claim 3, wherein the cellulose nanofibers are cellulose nanofibers separated from nanosized wood materials, seaweed cellulose nanofibers, and cultured strains. At least one of the obtained bacterial cellulose nanofibers.
  4. 根据权利要求2所述的电化学元件用复合纳米纤维隔膜,其特征在于,所述的纤维素纳米纤维的直径为10-1000nm,长度为10-3000μm。The composite nanofiber separator for electrochemical devices according to claim 2, wherein the cellulose nanofibers have a diameter of 10 to 1000 nm and a length of 10 to 3000 μm.
  5. 根据权利要求2所述的电化学元件用复合纳米纤维隔膜,其特征在于,所述的低熔点聚合物纳米纤维为聚甲基丙烯酸甲酯、偏氟乙烯基聚合物、聚氨酯、聚氯乙烯,聚乙烯醇、聚烯烃、聚丙烯腈、聚乙烯-醋酸乙烯酯共聚物、聚丁二酸乙二醇酯的一种或者多种组合。The composite nanofiber separator for electrochemical components according to claim 2, wherein the low melting point polymer nanofibers are polymethyl methacrylate, vinylidene fluoride polymer, polyurethane, polyvinyl chloride, One or more combinations of polyvinyl alcohol, polyolefin, polyacrylonitrile, polyethylene-vinyl acetate copolymer, polyethylene succinate.
  6. 根据权利要求5所述的方法,其特征在于所述的低熔点聚合物纳米纤维的直径为10-1000nm。The method of claim 5 wherein said low melting point polymer nanofibers have a diameter of from 10 to 1000 nm.
  7. 根据权利要求2所述的电化学元件用复合纳米纤维隔膜,其特征在于,所述的阻燃材料包括阻燃纤维氟纶、酚醛纤维、偏氟纶、氯纶、维氯纶、腈氯纶、PBI、芳纶(1414)、阻燃涤纶、阻燃腈纶、阻燃丙纶,聚芳砜酰胺等;以及阻燃剂磷酸酯、亚磷酸酯、四羟甲基氯化磷、有机磷盐、氧化磷、含磷多元醇、磷氮化合物、三聚氰胺、氰尿酸三聚氰胺、三(2,3-二溴丙基)异 三聚氰酸酯、单氰铵、双氰铵、三聚氰酸、硫脲、十溴二苯醚中的一种或多种。The composite nanofiber separator for electrochemical components according to claim 2, wherein the flame retardant material comprises flame retardant fiber fluorocarbon, phenolic fiber, partial fluorocarbon, polyvinyl chloride, vinyl chloride, and nitrile chloride. , PBI, aramid (1414), flame retardant polyester, flame retardant acrylic, flame retardant polypropylene, polyarylsulfone amide, etc.; and flame retardant phosphate, phosphite, tetramethylolphosphonium chloride, organic phosphorus salt, Phosphorus oxide, phosphorus-containing polyol, phosphorus-nitrogen compound, melamine, melamine cyanurate, tris(2,3-dibromopropyl) One or more of cyanuric acid ester, monocyanamide, dicyandiamide, cyanuric acid, thiourea, decabromodiphenyl ether.
  8. 根据权利要求2所述的电化学元件用复合纳米纤维隔膜,其特征在于所述的阻燃材料中,阻燃纤维的直径为10-1000nm;阻燃剂粒径小于1μm。The composite nanofiber separator for electrochemical components according to claim 2, wherein the flame retardant material has a diameter of 10 to 1000 nm and a flame retardant particle diameter of less than 1 μm.
  9. 一种电化学元件用复合纳米纤维隔膜的制备方法,其特征在于,包括以下具体步骤:A method for preparing a composite nanofiber membrane for an electrochemical component, comprising the following specific steps:
    I、以质量百分比含量计称取纤维素纳米纤维20-78%、低熔点聚合物纳米纤维20-65%及阻燃材料2-35%投入分散剂中,快速搅拌形成整体均匀的浆料;所述的分散剂包括去离子水、乙醇、异丙醇和丙三醇中的一种或多种;I. Weigh 20-78% of cellulose nanofibers, 20-65% of low melting polymer nanofibers and 2-35% of flame retardant materials into the dispersant by mass percentage content, and rapidly stir to form a whole uniform slurry; The dispersing agent includes one or more of deionized water, ethanol, isopropanol and glycerol;
    II、向步骤I的浆料中加入添加剂;所述添加剂包括醋酸、醋酸淀粉、羟甲基淀粉、羧甲基纤维素钠、羟甲基纤维素、明胶、卡拉胶、壳聚糖、甲壳素、聚氧化乙烯,水溶性聚氨酯、聚丙烯酰胺、聚乙烯吡咯烷酮或水溶性聚氨酯中的一种或多种;所述添加剂的质量为纤维素纳米纤维的0.1-10%;II. Adding an additive to the slurry of step I; the additive comprises acetic acid, starch acetate, methylol starch, sodium carboxymethylcellulose, hydroxymethylcellulose, gelatin, carrageenan, chitosan, chitin Or one or more of polyethylene oxide, water-soluble polyurethane, polyacrylamide, polyvinylpyrrolidone or water-soluble polyurethane; the mass of the additive is 0.1-10% of the cellulose nanofiber;
    III、将步骤II后的浆料稀释至质量百分比浓度为0.01-0.05%;III, the slurry after step II is diluted to a mass percentage concentration of 0.01-0.05%;
    IV、稀释后的浆料经上网脱水成型、压榨、干燥、热轧成型,即得到所述的耐高温阻燃型复合纳米纤维隔膜;所述的压榨线压力为60-120kg/cm,所述的干燥温度为70-100℃,所述的热轧成型温度为100-300℃,线压力为95-300kg/cm条件下进行热轧成型。IV. The diluted slurry is subjected to dehydration molding, pressing, drying and hot rolling forming on the Internet to obtain the high temperature resistant flame-retardant composite nanofiber separator; the press line pressure is 60-120 kg/cm, The drying temperature is 70-100 ° C, the hot rolling forming temperature is 100-300 ° C, and the line pressure is 95-300 kg/cm.
  10. 一种应用所述电化学元件用复合纳米纤维隔膜的储能器件,包括锂离子电池,锂硫电池,碱性电池,超级电容器,铅酸电池,锌空气电池,钠离子电池。 An energy storage device using the composite nanofiber separator for the electrochemical component, including a lithium ion battery, a lithium sulfur battery, an alkaline battery, a super capacitor, a lead acid battery, a zinc air battery, and a sodium ion battery.
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