CN103700800A - Manufacturing method for lithium ion battery diaphragm - Google Patents

Manufacturing method for lithium ion battery diaphragm Download PDF

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Publication number
CN103700800A
CN103700800A CN201410010884.9A CN201410010884A CN103700800A CN 103700800 A CN103700800 A CN 103700800A CN 201410010884 A CN201410010884 A CN 201410010884A CN 103700800 A CN103700800 A CN 103700800A
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ion battery
lithium ion
battery separator
battery diaphragm
cotton fiber
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CN201410010884.9A
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CN103700800B (en
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张雄飞
陈启杰
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Changsha University of Science and Technology
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Changsha University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/02—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising animal or vegetable substances, e.g. cork, bamboo, starch
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/429—Natural polymers
    • H01M50/4295—Natural cotton, cellulose or wood
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/20—All layers being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0253—Polyolefin fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/06—Vegetal fibres
    • B32B2262/062—Cellulose fibres, e.g. cotton
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/308—Heat stability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Cell Separators (AREA)

Abstract

The invention relates to a lithium ion battery diaphragm and a preparation method of the lithium ion battery diaphragm. The lithium ion battery diaphragm provided by the invention is divided into three layers, wherein a core layer is a cotton fiber film layer; an upper layer and a lower layer are polypropylene fiber film layers; the core layer of the diaphragm is a film formed by pulping cotton fibers and then performing a wet manufacturing technology on the pulped cotton fibers by using an antioxidant, a fire retardant and the like; each surface layer is a film formed by performing hydrophilic modification on polypropylene fibers and then performing the wet manufacturing technology on the modified polypropylene fibers by using an adhesive; the cotton fiber film is used as the core layer, and the polypropylene fiber films are used as the upper surface layer and the lower surface layer, so that the lithium ion battery diaphragm is prepared by hot pressing by two hot pressing rollers under the condition of 110-150 DEG C. The porosity of the lithium ion battery diaphragm is 40-80 percent, and the aperture is 0.01-0.2 microns; the tensile strength of the lithium ion battery diaphragm in both the longitudinal direction and the transverse direction is basically the same, which is 120-300Mpa; the puncture strength is higher than 20kg.mm<-1>; under 90 DEG C, the shrinkage rate is less than 1 percent; the lithium ion battery diaphragm is 20-60 microns thick. The lithium ion battery diaphragm is uniform in porosity distribution, high in mechanical strength, low in shrinkage rate, high in thermal stability and high in hydrophilicity/liquid retaining performance and is easy to prepare, pollution-free and suitable for industrial production.

Description

A kind of lithium ion battery separator manufacture method
Technical field
The present invention relates to lithium ion battery material field, be specifically related to a kind of lithium-ion electric barrier film and preparation method thereof.
Background technology
Barrier film is one of critical material of lithium ion battery, is used for intercepting positive pole and negative pole, prevents battery internal short-circuit, just allows again ion to pass through, thereby completes the transmission of lithium ion between both positive and negative polarity in charge discharge process.The performance of barrier film has determined the internal resistance of battery, directly affect battery capacity, the characteristic such as discharge and recharge.As lithium ion battery separator, the mechanical strength that must possess is corrosive power, suitable porosity, higher lyophily and guarantor's fluidity energy of punctured resistance, electrolyte resistance especially.The barrier film of excellent properties has important function to improving the combination property of lithium ion battery.Existing lithium season, ion battery barrier film mainly adopted polyethylene and polypropylene as raw material, prepare the method for polyethylene film and polypropylene screen and mainly use dry method and wet method drawing process, main employing is dry production barrier film at present, be about to polyolefin melting, push, be blow molded into crystalline polymer film, through crystallization heat treatment, annealing, obtain height-oriented sandwich construction again, at high temperature further stretch, crystalizing interface is peeled off, formed the film of loose structure.It is simple that dry method has technique, just to porosity and aperture, can not well control.At present the polyalkene diaphragm of dry production has that pore-size distribution is inhomogeneous, mechanical strength is low, thermal stability is not good enough and close/protects the poor shortcoming of fluidity.
Summary of the invention
The object of the present invention is to provide a kind of even aperture distribution, mechanical strength and thermal stability be high and close/protect the well behaved lithium ion battery separator of liquid.
Meanwhile, the present invention also aims to provide a kind of preparation method who manages ion battery barrier film.
In order to realize above object, the technical solution adopted in the present invention is: a kind of lithium ion battery separator, the sandwich layer that this barrier film is prepared by cotton fiber and the top layer up and down of being prepared by polypropylene fibre totally three layers form.
The porosity of described lithium ion battery separator is 40%～80%, and aperture is 0.01 micron～0.2 micron; Vertical transverse tensile strength is basically identical, is 120～300Mpa; Puncture intensity >20kgmm -1; Shrinkage <2% at 90 ℃; Thickness is 20 microns～60 microns.
Described lithium ion battery separator, in its sandwich layer, the quality percentage composition of antioxidant is 0.01～1%, the quality percentage composition of fire retardant is 0.01～1%, all the other for beating degree be the cotton fiber of 50～75 °.
Described lithium ion battery separator, in its top layer, the quality percentage composition of bonding agent is 0.1～10%, all the other are modified polypropylene fiber.
Described lithium ion battery separator, in its modified polypropylene fiber, modifier percentage composition is 0.1～10%, additive percentage composition is 0.01～1%.
Described lithium ion battery separator, the density of its modified polypropylene fiber is 0.95～1.05gcm -3.
Described antioxidant is at least one of dibutyl hydroxy toluene, dibutyl BHA, dibutyl phthalate and dioctyl phthalate.
Described fire retardant is at least one of chloroethyl phosphate polymer, ammonium polyphosphate, aluminium hydroxide, magnesium hydroxide.
Described bonding agent is at least one of PVA, PVDF.
Described modifier is new system precipitated calcium carbonate, and additive is PAA.
A preparation method for lithium ion battery separator, comprises the following steps:
(1) cotton fiber is caused in water, being made into slurry dense is 2%～5% mixture, cause in beater, pull an oar to beating degree (or beating degree) be 50～75 °;
(2) by the cotton fiber slurry of 50～75 ° as in water, being made into slurry dense is 0.5%～2% suspension, adds antioxidant and fire retardant, after stirring on copper mesh dehydration forming, through squeezing, drying and forming-film, stand-by;
(3) by polypropylene fibre oil removing in boiling water, swollen, add modified and light calcium carbonate and additive PAA, stir, obtain and there is hydrophilic modified polypropylene fiber;
(4) by modified polypropylene fiber as in water, concentration is 1%～3%, adds adhesive, after mixing on copper mesh dehydration forming, drying and forming-film;
(5) cotton fiber film of two polypropylene screen folders is introduced to two hot-pressing rollers, 110 ℃～150 ℃ of temperature, pressure is 100-200kgfcm -2condition under, be hot pressed into the lithium ion battery separator with three-decker.
Lithium ion battery separator provided by the invention is divided into three layers, and its center core layer is cotton fiber thin layer, and upper and lower top layer is polypropylene fibre thin layer.It is raw material that each layer film directly adopts fiber, through wet method papermaking process manufacturing paper and forming, preparation method provided by the invention can make fibrous strands in rete arrange more regular, the mechanical strength of vertical, horizontal is uniformity more, possess the performances such as higher resistance toly pierce through, strain insulator is tight, high-temperature shrinkage rate that the more important thing is the lithium ion battery separator making significantly reduces (shrinkage < 1% under 90 0C), make the thermal stability of barrier film better, therefore improved greatly the security performance of the lithium ion battery that uses this barrier film.
Lithium ion battery separator sandwich layer provided by the invention really connects and adopts cotton fiber manufacturing paper and forming, due to the fabulous parent/guarantor fluidity energy of cotton fiber to electrolyte, make lithium ion can pass through fast barrier film, guarantee the conductivity that electrolyte/membrane system is high, effectively improved capacity and the charge-discharge performance of lithium ion battery.
The porosity of the lithium ion battery separator that the present invention makes is 40%～80%, and aperture is 0.01 micron～0.2 micron; Vertical transverse tensile strength is basically identical, is 120～300Mpa; Puncture intensity >20kgmm -1; Shrinkage <1% at 90 ℃; Thickness is 20 microns～60 microns.This barrier film has even pore distribution, and mechanical strength is high, and shrinkage is low, and thermal stability is high, and parent/guarantor's liquid is functional, and preparation is simple, pollution-free, is applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention.
Wherein: the cotton fiber sandwich layer of 1-barrier film, the polypropylene top layer of 2-barrier film
Embodiment
Embodiment 1
The original bucket formula of the reason ion battery barrier film of the present embodiment is in Table shown in 1.
The preparation method of the lithium ion battery separator of the present embodiment, comprises the following steps:
(1) by the raw material proportioning shown in table 1, take each raw material, cotton fiber and water are made into mixture with the ratio of 4:100, be placed in beater, make beating degree and be the cotton pulp of 60 °, dehydration, measures its moisture;
(2) step (1) gained cotton pulp and water are made into mixture with the ratio of 1:100, add antioxidant and fire retardant, after dispersed with stirring on copper mesh dehydration forming, then through squeezing, 90 ℃ of drying and forming-films, stand-by;
(3) modified polypropylene fiber and water are made into suspension with the ratio of 1:100, add adhesive, stir, dispersed after on copper mesh dehydration forming, 110 ℃ of drying and forming-films;
(4) repeating step (3);
(5) using step (3) and step (4) gained polypropylene screen as upper and lower top layer, step (2) institute row cotton fiber film, as the two hot-pressing rollers of the compound introducing of sandwich layer, is 110 ℃ in temperature, and pressure is 100kgfcm -2condition under hot pressing, must there is the lithium ion battery separator of three-decker.
 
Embodiment 2
The original bucket formula of the reason ion battery barrier film of the present embodiment is in Table shown in 1.
The preparation method of the lithium ion battery separator of the present embodiment, comprises the following steps:
(1) by the raw material proportioning shown in table 1, take each raw material, cotton fiber and water are made into mixture with the ratio of 4:100, be placed in beater, make beating degree and be the cotton pulp of 60 °, dehydration, measures its moisture;
(2) step (1) gained cotton pulp and water are made into mixture with the ratio of 1:100, add antioxidant and fire retardant, after dispersed with stirring on copper mesh dehydration forming, then through squeezing, 110 ℃ of drying and forming-films, stand-by;
(3) modified polypropylene fiber and water are made into suspension with the ratio of 1:100, add adhesive, stir, dispersed after on copper mesh dehydration forming, 90 ℃ of drying and forming-films;
(4) repeating step (3);
(5) using step (3) and step (4) gained polypropylene screen as upper and lower top layer, step (2) institute row cotton fiber film, as the two hot-pressing rollers of the compound introducing of sandwich layer, is 130 ℃ in temperature, and pressure is 160kgfcm -2condition under hot pressing, must there is the lithium ion battery separator of three-decker.
 
Embodiment 3
The original bucket formula of the reason ion battery barrier film of the present embodiment is in Table shown in 1.
The preparation method of the lithium ion battery separator of the present embodiment, comprises the following steps:
(1) by the raw material proportioning shown in table 1, take each raw material, cotton fiber and water are made into mixture with the ratio of 4:100, be placed in beater, make beating degree and be the cotton pulp of 60 °, dehydration, measures its moisture;
(2) step (1) gained cotton pulp and water are made into mixture with the ratio of 1:100, add antioxidant and fire retardant, after dispersed with stirring on copper mesh dehydration forming, then through squeezing, 110 ℃ of drying and forming-films, stand-by;
(3) modified polypropylene fiber and water are made into suspension with the ratio of 1:100, add adhesive, stir, dispersed after on copper mesh dehydration forming, 90 ℃ of drying and forming-films;
(4) repeating step (3);
(5) using step (3) and step (4) gained polypropylene screen as upper and lower top layer, step (2) institute row cotton fiber film, as the two hot-pressing rollers of the compound introducing of sandwich layer, is 150 ℃ in temperature, and pressure is 200kgfcm -2condition under hot pressing, must there is the lithium ion battery separator of three-decker.
 
Embodiment 4
The original bucket formula of the reason ion battery barrier film of the present embodiment is in Table shown in 1.
The preparation method of the lithium ion battery separator of the present embodiment, comprises the following steps:
(1) by the raw material proportioning shown in table 1, take each raw material, cotton fiber and water are made into mixture with the ratio of 4:100, be placed in beater, make beating degree and be the cotton pulp of 65 °, dehydration, measures its moisture;
(2) step (1) gained cotton pulp and water are made into mixture with the ratio of 1:100, add antioxidant and fire retardant, after dispersed with stirring on copper mesh dehydration forming, then through squeezing, 110 ℃ of drying and forming-films, stand-by;
(3) modified polypropylene fiber and water are made into suspension with the ratio of 1:100, add adhesive, stir, dispersed after on copper mesh dehydration forming, 90 ℃ of drying and forming-films;
(4) repeating step (3);
(5) using step (3) and step (4) gained polypropylene screen as upper and lower top layer, step (2) institute row cotton fiber film, as the two hot-pressing rollers of the compound introducing of sandwich layer, is 110 ℃ in temperature, and pressure is 130kgfcm -2condition under hot pressing, must there is the lithium ion battery separator of three-decker.
 
Embodiment 5
The original bucket formula of the reason ion battery barrier film of the present embodiment is in Table shown in 1.
The preparation method of the lithium ion battery separator of the present embodiment, comprises the following steps:
(1) by the raw material proportioning shown in table 1, take each raw material, cotton fiber and water are made into mixture with the ratio of 4:100, be placed in beater, make beating degree and be the cotton pulp of 65 °, dehydration, measures its moisture;
(2) step (1) gained cotton pulp and water are made into mixture with the ratio of 1:100, add antioxidant and fire retardant, after dispersed with stirring on copper mesh dehydration forming, then through squeezing, 110 ℃ of drying and forming-films, stand-by;
(3) modified polypropylene fiber and water are made into suspension with the ratio of 1:100, add adhesive, stir, dispersed after on copper mesh dehydration forming, 90 ℃ of drying and forming-films;
(4) repeating step (3);
(5) using step (3) and step (4) gained polypropylene screen as upper and lower top layer, step (2) institute row cotton fiber film, as the two hot-pressing rollers of the compound introducing of sandwich layer, is 130 ℃ in temperature, and pressure is 200kgfcm -2condition under hot pressing, must there is the lithium ion battery separator of three-decker.
 
Embodiment 6
The original bucket formula of the reason ion battery barrier film of the present embodiment is in Table shown in 1.
The preparation method of the lithium ion battery separator of the present embodiment, comprises the following steps:
(1) by the raw material proportioning shown in table 1, take each raw material, cotton fiber and water are made into mixture with the ratio of 4:100, be placed in beater, make beating degree and be the cotton pulp of 70 °, dehydration, measures its moisture;
(2) step (1) gained cotton pulp and water are made into mixture with the ratio of 1:100, add antioxidant and fire retardant, after dispersed with stirring on copper mesh dehydration forming, then through squeezing, 110 ℃ of drying and forming-films, stand-by;
(3) modified polypropylene fiber and water are made into suspension with the ratio of 1:100, add adhesive, stir, dispersed after on copper mesh dehydration forming, 90 ℃ of drying and forming-films;
(4) repeating step (3);
(5) using step (3) and step (4) gained polypropylene screen as upper and lower top layer, step (2) institute row cotton fiber film, as the two hot-pressing rollers of the compound introducing of sandwich layer, is 110 ℃ in temperature, and pressure is 160kgfcm -2condition under hot pressing, must there is the lithium ion battery separator of three-decker.
 
Embodiment 7
The original bucket formula of the reason ion battery barrier film of the present embodiment is in Table shown in 1.
The preparation method of the lithium ion battery separator of the present embodiment, comprises the following steps:
(1) by the raw material proportioning shown in table 1, take each raw material, cotton fiber and water are made into mixture with the ratio of 4:100, be placed in beater, make beating degree and be the cotton pulp of 70 °, dehydration, measures its moisture;
(2) step (1) gained cotton pulp and water are made into mixture with the ratio of 1:100, add antioxidant and fire retardant, after dispersed with stirring on copper mesh dehydration forming, then through squeezing, 110 ℃ of drying and forming-films, stand-by;
(3) modified polypropylene fiber and water are made into suspension with the ratio of 1:100, add adhesive, stir, dispersed after on copper mesh dehydration forming, 90 ℃ of drying and forming-films;
(4) repeating step (3);
(5) using step (3) and step (4) gained polypropylene screen as upper and lower top layer, step (2) institute row cotton fiber film, as the two hot-pressing rollers of the compound introducing of sandwich layer, is 130 ℃ in temperature, and pressure is 110kgfcm -2condition under hot pressing, must there is the lithium ion battery separator of three-decker.
 
Embodiment 8
The original bucket formula of the reason ion battery barrier film of the present embodiment is in Table shown in 1.
The preparation method of the lithium ion battery separator of the present embodiment, comprises the following steps:
(1) by the raw material proportioning shown in table 1, take each raw material, cotton fiber and water are made into mixture with the ratio of 4:100, be placed in beater, make beating degree and be the cotton pulp of 70 °, dehydration, measures its moisture;
(2) step (1) gained cotton pulp and water are made into mixture with the ratio of 1:100, add antioxidant and fire retardant, after dispersed with stirring on copper mesh dehydration forming, then through squeezing, 110 ℃ of drying and forming-films, stand-by;
(3) modified polypropylene fiber and water are made into suspension with the ratio of 1:100, add adhesive, stir, dispersed after on copper mesh dehydration forming, 90 ℃ of drying and forming-films;
(4) repeating step (3);
(5) using step (3) and step (4) gained polypropylene screen as upper and lower top layer, step (2) institute row cotton fiber film, as the two hot-pressing rollers of the compound introducing of sandwich layer, is 120 ℃ in temperature, and pressure is 160kgfcm -2condition under hot pressing, must there is the lithium ion battery separator of three-decker.
 
Embodiment 9
The original bucket formula of the reason ion battery barrier film of the present embodiment is in Table shown in 1.
The preparation method of the lithium ion battery separator of the present embodiment, comprises the following steps:
(1) by the raw material proportioning shown in table 1, take each raw material, cotton fiber and water are made into mixture with the ratio of 4:100, be placed in beater, make beating degree and be the cotton pulp of 75 °, dehydration, measures its moisture;
(2) step (1) gained cotton pulp and water are made into mixture with the ratio of 1:100, add antioxidant and fire retardant, after dispersed with stirring on copper mesh dehydration forming, then through squeezing, 110 ℃ of drying and forming-films, stand-by;
(3) modified polypropylene fiber and water are made into suspension with the ratio of 1:100, add adhesive, stir, dispersed after on copper mesh dehydration forming, 90 ℃ of drying and forming-films;
(4) repeating step (3)
(5) using step (3) and step (4) gained polypropylene screen as upper and lower top layer, step (2) institute row cotton fiber film, as the two hot-pressing rollers of the compound introducing of sandwich layer, is 130 ℃ in temperature, and pressure is 130kgfcm -2condition under hot pressing, must there is the lithium ion battery separator of three-decker.
 
Embodiment 10
The original bucket formula of the reason ion battery barrier film of the present embodiment is in Table shown in 1.
The preparation method of the lithium ion battery separator of the present embodiment, comprises the following steps:
(1) by the raw material proportioning shown in table 1, take each raw material, cotton fiber and water are made into mixture with the ratio of 4:100, be placed in beater, make beating degree and be the cotton pulp of 75 °, dehydration, measures its moisture;
(2) step (1) gained cotton pulp and water are made into mixture with the ratio of 1:100, add antioxidant and fire retardant, after dispersed with stirring on copper mesh dehydration forming, then through squeezing, 110 ℃ of drying and forming-films, stand-by;
(3) modified polypropylene fiber and water are made into suspension with the ratio of 1:100, add adhesive, stir, dispersed after on copper mesh dehydration forming, 90 ℃ of drying and forming-films;
(4) repeating step (3);
(5) using step (3) and step (4) gained polypropylene screen as upper and lower top layer, step (2) institute row cotton fiber film, as the two hot-pressing rollers of the compound introducing of sandwich layer, is 130 ℃ in temperature, and pressure is 200kgfcm -2condition under hot pressing, must there is the lithium ion battery separator of three-decker.
 
Each embodiment of table 1 manages the raw material proportioning of ion battery barrier film
Figure 691174DEST_PATH_IMAGE001
The detection data of the reason ion battery barrier film that each embodiment of table 2 makes
Figure 567863DEST_PATH_IMAGE002

Claims (10)

1. a lithium ion battery separator, is characterized in that: the sandwich layer that this barrier film is prepared by cotton fiber and the top layer up and down of being prepared by polypropylene fibre totally three layers form.
2. lithium ion battery separator as claimed in claim 1, is characterized in that: the porosity of described lithium ion battery separator is 40%～80%, and aperture is 0.01 micron～0.2 micron; Vertical transverse tensile strength is basically identical, is 120～300Mpa; Puncture intensity >20kgmm -1; Shrinkage <1% at 90 ℃; Thickness is 20 microns～60 microns.
3. lithium ion battery separator as claimed in claim 1, is characterized in that: in sandwich layer, the quality percentage composition of antioxidant is 0.01～1%, and the quality percentage composition of fire retardant is 0.01～1%, all the other for beating degree be the cotton fiber of 50～75 °.
4. lithium ion battery separator as claimed in claim 1, is characterized in that: in top layer, the quality percentage composition of bonding agent is 0.1～10%, and all the other are modified polypropylene fiber.
5. lithium ion battery separator as claimed in claim 3, is characterized in that: in modified polypropylene fiber, modifier percentage composition is 0.1～10%, and additive percentage composition is 0.01～1%.
6. lithium ion battery separator as claimed in claim 3, is characterized in that: antioxidant is dibutyl hydroxy toluene, want fourth to want at least one of BHA, dibutyl phthalate and dioctyl phthalate.
7. lithium ion battery separator as claimed in claim 3, is characterized in that: fire retardant is at least one of chloroethyl phosphate polymer, ammonium polyphosphate, aluminium hydroxide, magnesium hydroxide.
8. the lithium ion battery separator of stating as claim 4, is characterized in that: bonding agent is at least one of PVA, PVDF.
9. lithium ion battery separator as claimed in claim 5, is characterized in that: modifier is new system modified and light calcium carbonate.
10. the preparation method of lithium ion battery separator as claimed in claim 1, is characterized in that: comprise the following steps:
(1) cotton fiber is caused in water, being made into slurry dense is 2%～5% mixture, cause in beater, pull an oar to beating degree (or beating degree) be 50～75 °;
(2) the cotton fiber slurry of 50～75 ° is put as in water, being made into slurry dense is 0.5%～2% suspension, adds antioxidant and fire retardant, after stirring on copper mesh dehydration forming, through squeezing, drying and forming-film, stand-by;
(3) by polypropylene fibre oil removing in boiling water, swollen, add modified and light calcium carbonate and additive PAA, stir, obtain and there is hydrophilic modified polypropylene fiber;
(4) modified polypropylene fiber is placed in to water, concentration is 1%～3%, adds adhesive, after mixing on copper mesh dehydration forming, drying and forming-film;
(5) cotton fiber film of two polypropylene screen folders is introduced to two hot-pressing rollers, 110 ℃～150 ℃ of temperature, pressure is 100-200kgfcm -2condition under, be hot pressed into the lithium ion battery separator with three-decker.
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CN109065813A (en) * 2018-08-07 2018-12-21 长沙理工大学 A kind of lithium ion battery separator and preparation method and application with hot closure function
CN111933867A (en) * 2020-10-13 2020-11-13 河南银金达新材料股份有限公司 Film without grease residue and preparation method thereof
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CN105355818A (en) * 2015-12-15 2016-02-24 上海洁晟环保科技有限公司 Compound nanofiber lithium battery diaphragm and preparation method thereof
CN109065813A (en) * 2018-08-07 2018-12-21 长沙理工大学 A kind of lithium ion battery separator and preparation method and application with hot closure function
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CN112787038A (en) * 2021-02-20 2021-05-11 天津谦同新能源科技有限公司 Post-treatment method of lithium ion battery spinning diaphragm and spinning diaphragm

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