CN108565383A - A kind of high tenacity lithium battery diaphragm and preparation method thereof - Google Patents
A kind of high tenacity lithium battery diaphragm and preparation method thereof Download PDFInfo
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- CN108565383A CN108565383A CN201810413767.5A CN201810413767A CN108565383A CN 108565383 A CN108565383 A CN 108565383A CN 201810413767 A CN201810413767 A CN 201810413767A CN 108565383 A CN108565383 A CN 108565383A
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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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- H01M50/411—Organic material
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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
- H01M50/411—Organic material
- H01M50/429—Natural polymers
- H01M50/4295—Natural cotton, cellulose or wood
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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
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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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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Abstract
The invention discloses a kind of high tenacity lithium battery diaphragm and preparation method thereof, which is that sandwich diaphragm is compounded with high tenacity layer using nucleopore membranes as base material in nucleopore membranes, hot closed layer is compounded on high tenacity layer, high tenacity layer includes following raw material：Polyester resin, Lauxite, epoxy resin, phenolic resin, microcrystalline cellulose, nanometer silicon carbide, ramee, blanc fixe, chlorinated paraffin, stearic acid, toughness enhancing modified additive, toughening filler, surface modifier；The high tenacity lithium battery diaphragm is by preparing base-material, surface modifying stuffing, modified additive will be enhanced with toughness after base-material and polyester resin heating and toughening filler mixes, blend melt is obtained in double screw extruder, then by melt conveying to die head, is cooled and solidified in rapidly chilling roller, obtain sheet material, then biaxial tension is carried out, extracts, lithium battery diaphragm is obtained after thermal finalization.The lithium battery diaphragm of the present invention has excellent toughness.
Description
Technical field
The invention belongs to battery material preparing technical fields, and in particular to a kind of high tenacity lithium battery diaphragm and its preparation side
Method.
Background technology
In recent years, with the fast development of portable electronic device, electric vehicle, power grid energy storage technology, people are to high energy
The demand of metric density, the battery of high security and energy-storage system is more and more urgent, in commercialized electrochemical energy storage device
In, lithium ion battery becomes the optimal selection of people because energy density is high, has extended cycle life.
Chinese patent application document " polyvinyl formal-nanocrystal cellulose preparing lithium ion battery membrane（Application is public
Cloth number：CN102746522B）" a kind of polyvinyl formal-nanocrystal cellulose lithium ion battery separator is disclosed, due to
The softening temperature of polyvinyl formal is higher, while having very high mechanical strength, high-wearing feature and good caking property, tall and erect
Electrical property more is production high tenacity, the important source material of wearability and high dielectric strength film, PVFM is dissolved in formic acid, acetic acid etc.
After solvent, nanocrystal cellulose is added with it after evenly mixing, removes solvent, obtain the PVFM films containing NCC, then with sulfuric acid water
Solution removal NCC obtains the films of PVFM containing nano aperture, which can make lithium-ion membrane or other battery diaphragms, but its toughness can not
The needs of meeting in actual use.
A kind of Chinese patent literature " lithium battery diaphragm and preparation method thereof（Authorization Notice No.：CN103378331B）" open
A kind of lithium battery diaphragm and preparation method thereof, which is sandwich diaphragm, using nucleopore membranes as base material, nucleopore
It is compounded with high-temperature-resistant layer on film, hot closed layer is compounded on high-temperature-resistant layer, the high-temperature-resistant layer is resistant to 200 DEG C or more of high temperature,
The fusing point of the hot closed layer scratches heat-resisting material at 100-120 DEG C in nucleopore membranes, stands, and heat is then closed material
It is quickly applied to outside heat-resisting material in the molten state, continues room temperature curing, obtain lithium battery diaphragm, composite membrane is warming up to 200
DEG C, nucleopore film layer melts substantially, and high-temperature-resistant layer can still form a film, and has higher thermal stability, and in charge and discharge process, even if
The transmitting fusing of organic matter counterdie, prevents the appearance of large area positive/negative short circuit phenomenon, improves the safety of battery, but its is tough
Property cannot be satisfied demand in actual use.
Invention content
The object of the present invention is to provide a kind of high tenacity lithium battery diaphragms and preparation method thereof, to solve in Chinese patent Shen
It please document " polyvinyl formal-nanocrystal cellulose preparing lithium ion battery membrane（Application publication number：
CN102746522B）" and a kind of patent document " lithium battery diaphragm and preparation method thereof（Authorization Notice No.：CN103378331B）”
The problem of on the basis of disclosed lithium battery diaphragm, how optimizing component, dosage, method etc., improving the lithium battery diaphragm toughness.
In order to solve the above technical problems, the present invention uses following technical scheme：
A kind of high tenacity lithium battery diaphragm, which is sandwich diaphragm, compound in nucleopore membranes using nucleopore membranes as base material
There is high tenacity layer, hot closed layer is compounded on the high tenacity layer, the high tenacity layer includes following raw material：Polyester resin, urea
It is urea formaldehyde, epoxy resin, phenolic resin, microcrystalline cellulose, nanometer silicon carbide, ramee, blanc fixe, chlorinated paraffin, hard
Resin acid, toughness enhancing modified additive, toughening filler, surface modifier；
The toughness enhances modified additive, as unit of parts by weight, including following raw material：15-25 parts of corn flour, distilled water 10-
20 parts, it is 4-8 parts of maleic anhydride, 2-5 parts of ammonium persulfate, 1-5 parts of styrene, 4-8 parts of wood fiber powder, 3-6 parts of tossa, empty
2-8 parts of heart glass microballoon, 4-6 parts of multi-walled carbon nanotube, 2-5 parts of dichloroethanes, 1-5 parts of silane coupling agent KH-560, peroxidating
2-6 parts of diisopropylbenzene (DIPB), 4-8 parts of hydroxy silicon oil；
The toughening filler, as unit of parts by weight, including following raw material：18-36 parts of neopelex, deionized water
5-15 parts, 4-8 parts of hydroxymethyl cellulose, 3-9 parts of butyl acrylate, 2-5 parts of potassium peroxydisulfate, mass fraction be 5-15% sulfuric acid
1-5 parts of aluminum water solution, 2-5 parts of 4-6 parts of hydrochloric acid solution, silane resin acceptor kh-550, the carbamic acid that mass percent is 4-6%
1-4 parts of ester, 3-6 parts of isopropyl acrylate, 4-8 parts of polyparaphenylene's benzo dioxazole fiber；
The polyester resin, nanometer silicon carbide, ramee, blanc fixe, toughness enhancing modified additive, increases microcrystalline cellulose
The weight ratio of tough filler and surface modifier is（40-60）：（3-9）：（2-6）：（1-5）：（4-8）：（22-26）：（16-32）：
（1-3）.
Further, the polyester resin, microcrystalline cellulose, nanometer silicon carbide, ramee, blanc fixe, toughness increase
The weight ratio of strong modified additive, toughening filler and surface modifier is 50：6：4：3：6：24：24：2.
Further, as unit of parts by weight, including following raw material：40-60 parts of polyester resin, 25-45 parts of Lauxite,
18-36 parts of epoxy resin, 4-8 parts of phenolic resin, 3-9 parts of microcrystalline cellulose, 2-6 parts of nanometer silicon carbide, 1-5 parts of ramee,
4-8 parts of blanc fixe, 3-6 parts of chlorinated paraffin, 2-5 parts of stearic acid, 22-26 parts of modified additive of toughness enhancing, toughening filler 16-32
Part, 1-3 parts of surface modifier.
Further, the toughness enhancing modified additive is prepared by following technique：Under nitrogen protection, by corn
Powder, distilled water and maleic anhydride are uniformly mixed, and then heat to 80-90 DEG C, keep the temperature 10-30min, and it is mixed that ammonium persulfate is then added
It closes uniformly, addition styrene is uniformly mixed after stirring 5-15min, then stirs 50-70min in 850-1250r/min rotating speeds, so
After be warming up to 85-95 DEG C, extract 40-50h, then in vacuum drying oven, 65-75 DEG C dries to constant weight, and is cooled to room temperature to obtain object
Expect a；Wood fiber powder, tossa, hollow glass micropearl, multi-walled carbon nanotube and dichloroethanes are uniformly mixed, at ultrasound
1-3h is managed, material a, silane coupling agent KH-560, cumyl peroxide and hydroxy silicon oil is subsequently added into and is uniformly mixed, in 650-
850r/min rotating speeds stir 20-40min, are then warming up to 80-90 DEG C, and flow back 20-30h, are cooled to room temperature to obtain toughness enhancing
Modified additive.
Further, the toughening filler is prepared by following technique：By neopelex and deionized water
It is uniformly mixed, stirs 2-4min, hydroxymethyl cellulose is then added and is uniformly mixed, 20- is stirred in 1500-2500r/min rotating speeds
30min is then heated to 65-75 DEG C, keeps the temperature 5-15min, is subsequently added into butyl acrylate and potassium peroxydisulfate is uniformly mixed, reaction
Then 1-3h is added dropwise the aluminum sulfate aqueous solution that mass fraction is 5-15%, is demulsified, filtering, in 45-55 DEG C of vacuum drying oven after washing
Middle dry 5-7h, is cooled to room temperature, and then calcines 2-5h at 820-920 DEG C in calcining furnace, cooling, is put into mass percent
To impregnate 1-3h in the hydrochloric acid solution of 4-6%, filtering is taken out, and cleans drying with clear water, silane coupling agent KH- is added after crushing
550, carbamate, isopropyl acrylate and polyparaphenylene's benzo dioxazole fiber are uniformly mixed, and are warming up to 110-130 DEG C,
10-30min is kept the temperature, 20-30min is stirred in 650-850r/min rotating speeds, is cooled to room temperature up to toughening filler.
Further, the surface modifier is three ethoxy of 1,3-BDO, Silane coupling reagent KH-570 and anilinomethyl
One or more of base silane mixture.
The present invention also provides a kind of preparation methods of high tenacity lithium battery diaphragm, include the following steps：
S1：Liquid sizing material will be obtained after the heating melting of Lauxite, epoxy resin and phenolic resin, then by chlorinated paraffin and firmly
Resin acid is added in liquid sizing material, is continued heating stirring, is cooled to room temperature to obtain base-material；
S2：Microcrystalline cellulose, nanometer silicon carbide, ramee and blanc fixe are uniformly mixed, stirred after continuing heating, is added
Surface modifier is uniformly mixed, and is stirred after heating, is cooled to room temperature to obtain surface modifying stuffing；
S3：It will be stirred after base-material and polyester resin heating, toughness enhancing modified additive be then added and toughening filler is uniformly mixed,
It is stirred after heating, then in double screw extruder, shear at high temperature is plasticized, and is stirred, and is plasticized, and is blended, is obtained blend melt, so
It in consequent melt conveying to die head, is cooled and solidified in rapidly chilling roller, obtains sheet material, then carry out biaxial tension, extracted, heat is fixed
Lithium battery diaphragm is obtained after type.
Further, in S1, after being melted after Lauxite, epoxy resin and phenolic resin are warming up to 120-140 DEG C
To liquid sizing material, then chlorinated paraffin and stearic acid are added in liquid sizing material, are continuously heating to 160-180 DEG C, in 1100-
1300r/min rotating speeds stir 1-2h, are cooled to room temperature to obtain base-material.
Further, in S2, microcrystalline cellulose, nanometer silicon carbide, ramee and blanc fixe are uniformly mixed, heated up
After stir, be added surface modifier be uniformly mixed, after being warming up to 90-110 DEG C in 650-850r/min rotating speeds stir 20-30min,
It is cooled to room temperature to obtain surface modifying stuffing.
Further, it in S3, is stirred in 550-650r/min rotating speeds after base-material and polyester resin are warming up to 90-110 DEG C
1-2h, is then added toughness enhancing modified additive and toughening filler is uniformly mixed, in 850-1050r/ after being warming up to 130-150 DEG C
Min rotating speeds stir 20-40min, and then in double screw extruder, shear at high temperature is plasticized 5-15mi in 125-145 DEG C, stirs,
Be blended, obtain blend melt, then in part melt conveying to die head, cooled and solidified in rapidly chilling roller, obtain sheet material, then into
Row biaxial tension, extraction, lithium battery diaphragm is obtained after thermal finalization.
The invention has the advantages that：
（1）By embodiment 1-3 and the data of comparative example 10 and comparative example 11 as it can be seen that high tenacity lithium electricity made from embodiment 1-3
Toughness, porosity, puncture strength and the ventilative value of pond diaphragm are all remarkably higher than lithium made from comparative example 10 and comparative example 11
Toughness, porosity, puncture strength and the ventilative value of battery diaphragm；Simultaneously by the data of embodiment 1-3 as it can be seen that embodiment 1 is
Optimum embodiment, by embodiment 1 and the data of comparative example 1-9 as it can be seen that polyester resin, microcrystalline cellulose, nanometer silicon carbide, ramie
Fiber, blanc fixe, toughness enhancing modified additive, toughening filler and surface modifier rise in preparing high tenacity lithium battery diaphragm
Synergistic effect is arrived, collaboration improves the toughness of the lithium battery diaphragm.
（2）Polyester resin, microcrystalline cellulose, nanometer silicon carbide, ramee, blanc fixe, toughness enhancing modified additive,
Toughening filler and surface modifier are as reinforcement system, and wherein polyester resin is major ingredient, and assigning reinforcement system enhances toughness properties,
Microcrystalline cellulose, nanometer silicon carbide, ramee, blanc fixe act on the melting of polyester resin as toughness reinforced filling
In processing procedure, the toughness of polyester resin is improved, addition surface modifier is realized as graft modification agent and changes toughness enhancing
Property auxiliary agent and toughening filler toughness reinforcement apply in the base-material of the lithium battery diaphragm, realize toughness enhancing modified additive and
The hydroxyl on toughening filler surface is realized under the grafting effect of surface modifier and is combined with base-material, effectively increases lithium of the present invention
The toughness of battery diaphragm.
（3）Toughness enhances modified additive by under nitrogen protection, corn flour, distilled water and maleic anhydride being mixed equal
Even, then heating and heat preservation, is then added ammonium persulfate and is uniformly mixed, styrene is added after stirring and is uniformly mixed, is followed by stirring for, so
After heat up, extract, then in vacuum drying oven, dry to constant weight, be cooled to room temperature to obtain material a；Wood fiber powder, jute is fine
Dimension, hollow glass micropearl, multi-walled carbon nanotube and dichloroethanes are uniformly mixed, and are ultrasonically treated, and it is even to be subsequently added into material a, silane
Join agent KH-560, cumyl peroxide and hydroxy silicon oil to be uniformly mixed, stirring then heats up, and flows back, is cooled to room temperature
It arrives, wherein using corn flour as stickiness base-material, using maleic anhydride as grafted monomers, with ammonium persulfate, styrene and peroxidating two
Isopropylbenzene is initiator, with wood fiber powder, tossa, hollow glass micropearl, multi-walled carbon nanotube for toughened and reinforced filler,
Using hydroxy silicon oil as solvent, with silane coupling agent KH-560 graft modification agent, by will be with wood fiber powder, tossa, sky
Heart glass microballoon, multi-walled carbon nanotube carry out surface modification, obtain modified filler and are combined with maleic anhydride, and will obtain
In the preparation for the lithium battery diaphragm that toughness enhancing modified additive applies to the present invention, obtained lithium battery diaphragm has excellent tough
Property.
（4）Toughening filler stirs by the way that neopelex and deionized water to be uniformly mixed, hydroxyl first is then added
Base cellulose is uniformly mixed, and then stirring is heated, keep the temperature, and is subsequently added into butyl acrylate and potassium peroxydisulfate is uniformly mixed, instead
It answers, aluminum sulfate aqueous solution is then added dropwise, be demulsified, filtering is dry in vacuum drying oven after washing, is cooled to room temperature, then in forging
It burns in stove and calcines, it is cooling, it is put into hydrochloric acid solution and impregnates, filtering is taken out, and is cleaned drying with clear water, is added after crushing silane coupled
Agent KH-550, carbamate, isopropyl acrylate and polyparaphenylene's benzo dioxazole fiber are uniformly mixed, and are heated up, and heat preservation is stirred
It mixes, is cooled to room temperature and obtains, wherein using neopelex as surfactant, using hydroxymethyl cellulose as tough
Property reinforcement material, with butyl acrylate, carbamate, isopropyl acrylate and for monomer, using potassium peroxydisulfate as initiator, with sulphur
Sour aluminum water solution and polyparaphenylene's benzo dioxazole fiber are used as by silane resin acceptor kh-550 and are connect as toughened and reinforced material
Branch modified additive carries out surface modification to toughened and reinforced material, is combined with the unsaturated bond of monomer surface, obtained toughening is filled out
Material applies to the preparation of the lithium battery diaphragm of the present invention, effectively increases the toughness of lithium battery diaphragm of the present invention.
（5）By the data of comparative example 12-14 as it can be seen that polyester resin, microcrystalline cellulose, nanometer silicon carbide, ramee, again
The weight ratio that spar powder, toughness enhance modified additive, toughening filler and surface modifier does not exist（40-60）：（3-9）：（2-6）：
（1-5）：（4-8）：（22-26）：（16-32）：（1-3）When in range, the corresponding numerical value of toughness of lithium battery diaphragm obtained
It is very different with the numerical value of embodiment 1-3, the numerical value of embodiment 1-3 is much smaller than, with the prior art（Comparative example 10 and comparative example
11）Numerical value it is suitable.Polyester resin of the present invention, microcrystalline cellulose, nanometer silicon carbide, ramee, blanc fixe, toughness enhancing
Modified additive, toughening filler and surface modifier are as reinforcement system, when embodiment 1-3 controls prepare high tenacity lithium battery diaphragm
Enhance modified additive by adding polyester resin, microcrystalline cellulose, nanometer silicon carbide, ramee, blanc fixe, toughness, increase
The weight ratio of tough filler and surface modifier is（40-60）：（3-9）：（2-6）：（1-5）：（4-8）：（22-26）：（16-32）：
（1-3）, realize using the toughness that polyester resin is excellent in reinforcement system, and fine in microcrystalline cellulose, nanometer silicon carbide, ramie
Dimension, blanc fixe are as toughened and reinforced filler, using polyester resin as reinforcement system as major ingredient, realize less toughened and reinforced fill out
Material acts on polyester resin, improves the intensity of polyester resin, and under the grafting of surface modifier effect, toughness increasing is utilized
The toughness strengthening action of strong modified additive effectively increases the toughness of the lithium battery diaphragm, while coordinating with toughening filler, in table
It is applied in base-material under the action of the modifying agent of face, effectively increases the toughness of the lithium battery diaphragm, as a result, polyester resin, crystallite
Cellulose, nanometer silicon carbide, ramee, blanc fixe, toughness enhancing modified additive, toughening filler and surface modifier conduct
Reinforcement system applies in the preparation of the lithium battery diaphragm, effectively increases the toughness of the lithium battery diaphragm.
（6）Surfactant is in 1,3 butylene glycol, Silane coupling reagent KH-570 and anilinomethyl triethoxysilane
Base-material is utilized using the combination of the surface graft modification realization and base-material of surfactant in one or more kinds of mixtures
The unsaturated bond on surface is combined with reinforcement material surface hydroxyl, to improve the toughness of battery diaphragm of the present invention.
（7）The present invention obtains base-material by using resin refining glue material, then by microcrystalline cellulose, nanometer silicon carbide, ramie
Fiber and blanc fixe carry out surface modifying agent, realize microcrystalline cellulose, nanometer silicon carbide, ramee and barite
The modification of powder surface hydroxyl, and by after base-material and polyester resin mixing, under the action of surface modifier, realize toughness enhancing
Modified additive and toughening filler are grafted on base-material and polyester resin mixture, are realized to base-material and toughness reinforcement, are most passed through afterwards
It crosses in double screw extruder, by shear at high temperature, is plasticized, stirs, be plasticized, be blended, blend melt obtained, then by melt conveying
It into die head, is cooled and solidified in rapidly chilling roller, obtains sheet material, then carry out biaxial tension, extracted, lithium electricity is obtained after thermal finalization
Pond diaphragm, this method is easy to operate, efficient, and the obtained lithium ion battery separator of preparation has excellent toughness.
Specific implementation mode
For ease of more fully understanding the present invention, it is illustrated by the following examples, these examples belong to the protection of the present invention
Range, but do not limit the scope of the invention.
In embodiment, the high tenacity lithium battery diaphragm, as unit of parts by weight, including following raw material：Polyester resin
40-60 parts, 25-45 parts of Lauxite, 18-36 parts of epoxy resin, 4-8 parts of phenolic resin, 3-9 parts of microcrystalline cellulose, nano-sized carbon
2-6 parts of SiClx, 1-5 parts of ramee, 4-8 parts of blanc fixe, 3-6 parts of chlorinated paraffin, 2-5 parts of stearic acid, toughness enhancing are modified
22-26 parts of auxiliary agent, 16-32 parts of toughening filler, 1-3 parts of surface modifier.
The toughness enhancing modified additive is prepared by following technique：Under nitrogen protection, by weight by 15-25 parts
Corn flour, 10-20 part distilled water and 4-8 parts of maleic anhydrides are uniformly mixed, and are then heated to 80-90 DEG C, are kept the temperature 10-30min, so
2-5 parts of ammonium persulfates are added afterwards to be uniformly mixed, 1-5 parts of styrene of addition are uniformly mixed after stirring 5-15min, then in 850-
1250r/min rotating speeds stir 50-70min, then heat to 85-95 DEG C, extract 40-50h, then in vacuum drying oven, 65-75
It DEG C dries to constant weight, is cooled to room temperature to obtain material a；By 4-8 parts of wood fiber powders, 3-6 parts of tossas, 2-8 parts of hollow glass
Microballon, 4-6 part multi-walled carbon nanotube and 2-5 parts of dichloroethanes are uniformly mixed, and are ultrasonically treated 1-3h, are subsequently added into material a, 1-5
Part KH-560,2-6 parts of cumyl peroxides of silane coupling agent and 4-8 parts of hydroxy silicon oils are uniformly mixed, in 650-850r/min
Rotating speed stirs 20-40min, is then warming up to 80-90 DEG C, and flow back 20-30h, is cooled to room temperature to obtain toughness enhancing modified additive.
The toughening filler is prepared by following technique：By weight by 18-36 parts of neopelexes and 5-
15 parts of deionized waters are uniformly mixed, and stir 2-4min, and 4-8 parts of hydroxymethyl celluloses are then added and are uniformly mixed, in 1500-
2500r/min rotating speeds stir 20-30min, are then heated to 65-75 DEG C, keep the temperature 5-15min, are subsequently added into 3-9 parts of acrylic acid fourths
Ester and 2-5 parts of potassium peroxydisulfates are uniformly mixed, and react 1-3h, and it is water-soluble that the aluminum sulfate that 1-5 parts of mass fractions are 5-15% is then added dropwise
Liquid is demulsified, filtering, after washing in 45-55 DEG C of vacuum drying oven dry 5-7h, be cooled to room temperature, then in calcining furnace
2-5h is calcined at 820-920 DEG C, it is cooling, it is put into the hydrochloric acid solution that 4-6 parts of mass percents are 4-6% and impregnates 1-3h, filter to take
Go out, cleans drying with clear water, 2-5 parts of silane resin acceptor kh-550s, 1-4 parts of carbamates, 3-6 parts of acrylic acid are added after crushing
Isopropyl ester and 4-8 parts of polyparaphenylene's benzo dioxazole fibers are uniformly mixed, and are warming up to 110-130 DEG C, are kept the temperature 10-30min, in
650-850r/min rotating speeds stir 20-30min, are cooled to room temperature up to toughening filler.
The surface modifier is in 1,3 butylene glycol, Silane coupling reagent KH-570 and anilinomethyl triethoxysilane
One or more kinds of mixtures.
The preparation method of the high tenacity lithium battery diaphragm, includes the following steps：
S1：Liquid sizing material is obtained after being melted after Lauxite, epoxy resin and phenolic resin are warming up to 120-140 DEG C, then
Chlorinated paraffin and stearic acid are added in liquid sizing material, are continuously heating to 160-180 DEG C, is stirred in 1100-1300r/min rotating speeds
1-2h is mixed, is cooled to room temperature to obtain base-material；
S2：Microcrystalline cellulose, nanometer silicon carbide, ramee and blanc fixe are uniformly mixed, stirred after heating, surface is added
Modifying agent is uniformly mixed, and is stirred 20-30min in 650-850r/min rotating speeds after being warming up to 90-110 DEG C, is cooled to room temperature to obtain
Surface modifying stuffing；
S3：1-2h is stirred in 550-650r/min rotating speeds after base-material and polyester resin are warming up to 90-110 DEG C, is then added tough
Property enhancing modified additive and toughening filler be uniformly mixed, after being warming up to 130-150 DEG C in 850-1050r/min rotating speeds stir 20-
40min, then in double screw extruder, shear at high temperature is plasticized 5-15mi in 125-145 DEG C, stirs, is blended, mixed
Melt cools and solidifies then in part melt conveying to die head in rapidly chilling roller, obtains sheet material, then carries out biaxial tension, extraction
It takes, lithium battery diaphragm is obtained after thermal finalization.
Embodiment 1
A kind of high tenacity lithium battery diaphragm, as unit of parts by weight, including following raw material：50 parts of polyester resin, Lauxite 35
Part, 27 parts of epoxy resin, 6 parts of phenolic resin, 6 parts of microcrystalline cellulose, 4 parts of nanometer silicon carbide, 3 parts of ramee, blanc fixe 6
Part, 24 parts of modified additive of 4.5 parts of chlorinated paraffin, 3.5 parts of stearic acid, toughness enhancing, 24 parts of toughening filler, 2 parts of surface modifier.
The toughness enhancing modified additive is prepared by following technique：Under nitrogen protection, by weight by 20 parts of jade
Rice flour, 15 parts of distilled water and 6 parts of maleic anhydrides are uniformly mixed, and are then heated to 85 DEG C, are kept the temperature 20min, 3.5 parts of mistakes are then added
Ammonium sulfate is uniformly mixed, and 3 parts of styrene of addition are uniformly mixed after stirring 10min, then stir 60min in 1050r/min rotating speeds,
90 DEG C are then heated to, extracts 45h, then in vacuum drying oven, 70 DEG C dry to constant weight, and are cooled to room temperature to obtain material a；By 6
Part wood fiber powder, 4.5 parts of tossas, 5 parts of hollow glass micropearls, 5 parts of multi-walled carbon nanotubes and 3.5 parts of dichloroethanes mixing
Uniformly, it is ultrasonically treated 2h, is subsequently added into material a, 3 parts of silane coupling agent KH-560,4 parts of cumyl peroxides and 6 parts of hydroxyls
Silicone oil is uniformly mixed, and is stirred 30min in 750r/min rotating speeds, is then warming up to 85 DEG C, and flow back 25h, is cooled to room temperature to obtain tough
Property enhancing modified additive.
The toughening filler is prepared by following technique：22 parts of neopelexes and 10 parts are gone by weight
Ionized water is uniformly mixed, and stirs 3min, and 6 parts of hydroxymethyl celluloses are then added and are uniformly mixed, are stirred in 2000r/min rotating speeds
25min is then heated to 70 DEG C, keeps the temperature 10min, is subsequently added into 6 parts of butyl acrylates and 3.5 parts of potassium peroxydisulfates are uniformly mixed,
2h is reacted, the aluminum sulfate aqueous solution that 3 parts of mass fractions are 10% is then added dropwise, is demulsified, filtering, in 50 DEG C of vacuum drying ovens after washing
Middle dry 6h, is cooled to room temperature, and then calcines 3.5h at 870 DEG C in calcining furnace, and cooling, being put into 5 parts of mass percents is
Impregnate 2h in 5% hydrochloric acid solution, filtering is taken out, and drying is cleaned with clear water, be added after crushing 3.5 parts of silane resin acceptor kh-550s,
2.5 parts of carbamates, 4.5 parts of isopropyl acrylates and 6 parts of polyparaphenylene's benzo dioxazole fibers are uniformly mixed, and are warming up to
120 DEG C, 20min is kept the temperature, 25min is stirred in 750r/min rotating speeds, is cooled to room temperature up to toughening filler.
The surface modifier is in 1,3 butylene glycol, Silane coupling reagent KH-570 and anilinomethyl triethoxysilane
One or more kinds of mixtures.
The preparation method of the high tenacity lithium battery diaphragm, includes the following steps：
S1：Liquid sizing material is obtained after being melted after Lauxite, epoxy resin and phenolic resin are warming up to 130 DEG C, then by chlorine
Fossil waxes and stearic acid are added in liquid sizing material, are continuously heating to 170 DEG C, are stirred 1.5h in 1200r/min rotating speeds, are cooled to
Room temperature obtains base-material；
S2：Microcrystalline cellulose, nanometer silicon carbide, ramee and blanc fixe are uniformly mixed, stirred after heating, surface is added
Modifying agent is uniformly mixed, and 25min is stirred in 750r/min rotating speeds after being warming up to 100 DEG C, is cooled to room temperature to obtain surface and is modified and fills out
Material；
S3：1.5h is stirred in 600r/min rotating speeds after base-material and polyester resin are warming up to 100 DEG C, toughness enhancing is then added and changes
Property auxiliary agent and toughening filler be uniformly mixed, after being warming up to 140 DEG C in 950r/min rotating speeds stir 30min, then in twin-screw squeeze
Go out in machine, shear at high temperature, is plasticized 10mi in 135 DEG C, stirs, be blended, obtain blend melt, then part melt conveying to die head
In, cooled and solidified in rapidly chilling roller, obtain sheet material, then carry out biaxial tension, extract, obtained after thermal finalization lithium battery every
Film.
Embodiment 2
A kind of high tenacity lithium battery diaphragm, as unit of parts by weight, including following raw material：40 parts of polyester resin, Lauxite 45
Part, 18 parts of epoxy resin, 8 parts of phenolic resin, 3 parts of microcrystalline cellulose, 6 parts of nanometer silicon carbide, 1 part of ramee, blanc fixe 8
Part, 22 parts of modified additive of 3 parts of chlorinated paraffin, 5 parts of stearic acid, toughness enhancing, 32 parts of toughening filler, 1 part of surface modifier.
The toughness enhancing modified additive is prepared by following technique：Under nitrogen protection, by weight by 15 parts of jade
Rice flour, 20 parts of distilled water and 4 parts of maleic anhydrides are uniformly mixed, and are then heated to 90 DEG C, are kept the temperature 10min, 5 parts of over cures are then added
Sour ammonium is uniformly mixed, and 5 parts of styrene of addition are uniformly mixed after stirring 5min, then stir 70min in 850r/min rotating speeds, then
85 DEG C are warming up to, extracts 50h, then in vacuum drying oven, 65 DEG C dry to constant weight, and are cooled to room temperature to obtain material a；By 8 parts of wood
Matter fiber powder, 3 parts of tossas, 8 parts of hollow glass micropearls, 4 parts of multi-walled carbon nanotubes and 5 parts of dichloroethanes are uniformly mixed, and are surpassed
Sonication 1h is subsequently added into material a, 5 parts of silane coupling agent KH-560,2 parts of cumyl peroxides and 8 parts of hydroxy silicon oil mixing
Uniformly, 40min is stirred in 650r/min rotating speeds, is then warming up to 80 DEG C, flow back 30h, is cooled to room temperature to obtain toughness enhancing and changes
Property auxiliary agent.
The toughening filler is prepared by following technique：18 parts of neopelexes and 15 parts are gone by weight
Ionized water is uniformly mixed, and stirs 2min, and 8 parts of hydroxymethyl celluloses are then added and are uniformly mixed, are stirred in 1500r/min rotating speeds
30min is then heated to 65 DEG C, keeps the temperature 15min, is subsequently added into 3 parts of butyl acrylates and 5 parts of potassium peroxydisulfates are uniformly mixed, instead
1h is answered, the aluminum sulfate aqueous solution that 5 parts of mass fractions are 5% is then added dropwise, is demulsified, filtering is done after washing in 55 DEG C of vacuum drying ovens
Dry 5h, is cooled to room temperature, and then calcines 2h at 920 DEG C in calcining furnace, cooling, is put into the salt that 6 parts of mass percents are 4%
3h is impregnated in acid solution, filtering is taken out, and cleans drying with clear water, 2 parts of silane resin acceptor kh-550s, 4 parts of amino are added after crushing
Formic acid esters, 3 parts of isopropyl acrylates and 8 parts of polyparaphenylene's benzo dioxazole fibers are uniformly mixed, and are warming up to 110 DEG C, heat preservation
30min stirs 30min in 650r/min rotating speeds, is cooled to room temperature up to toughening filler.
The surface modifier is in 1,3 butylene glycol, Silane coupling reagent KH-570 and anilinomethyl triethoxysilane
One or more kinds of mixtures.
The preparation method of the high tenacity lithium battery diaphragm, includes the following steps：
S1：Liquid sizing material is obtained after being melted after Lauxite, epoxy resin and phenolic resin are warming up to 120 DEG C, then by chlorine
Fossil waxes and stearic acid are added in liquid sizing material, are continuously heating to 180 DEG C, are stirred 2h in 1100r/min rotating speeds, are cooled to room
Temperature obtains base-material；
S2：Microcrystalline cellulose, nanometer silicon carbide, ramee and blanc fixe are uniformly mixed, stirred after heating, surface is added
Modifying agent is uniformly mixed, and 20min is stirred in 850r/min rotating speeds after being warming up to 90 DEG C, is cooled to room temperature to obtain surface and is modified and fills out
Material；
S3：2h is stirred in 550r/min rotating speeds after base-material and polyester resin are warming up to 110 DEG C, toughness enhancing is then added and is modified
Auxiliary agent and toughening filler are uniformly mixed, and 20min are stirred in 1050r/min rotating speeds after being warming up to 130 DEG C, then in twin-screw extrusion
In machine, shear at high temperature is plasticized 5mi in 145 DEG C, stirs, is blended, obtains blend melt, then in part melt conveying to die head,
It is rapidly cooled and solidified in chilling roller, obtains sheet material, then carry out biaxial tension, extracted, lithium battery diaphragm is obtained after thermal finalization.
Embodiment 3
A kind of high tenacity lithium battery diaphragm, as unit of parts by weight, including following raw material：60 parts of polyester resin, Lauxite 25
Part, 36 parts of epoxy resin, 4 parts of phenolic resin, 9 parts of microcrystalline cellulose, 2 parts of nanometer silicon carbide, 5 parts of ramee, blanc fixe 4
Part, 26 parts of modified additive of 6 parts of chlorinated paraffin, 2 parts of stearic acid, toughness enhancing, 16 parts of toughening filler, 3 parts of surface modifier.
The toughness enhancing modified additive is prepared by following technique：Under nitrogen protection, by weight by 25 parts of jade
Rice flour, 10 parts of distilled water and 8 parts of maleic anhydrides are uniformly mixed, and are then heated to 80 DEG C, are kept the temperature 30min, 2 parts of over cures are then added
Sour ammonium is uniformly mixed, and 1 part of styrene of addition is uniformly mixed after stirring 15min, then stirs 50min in 1250r/min rotating speeds, so
After be warming up to 95 DEG C, extract 40h, then in vacuum drying oven, 75 DEG C dry to constant weight, and are cooled to room temperature to obtain material a；By 4 parts
Wood fiber powder, 6 parts of tossas, 2 parts of hollow glass micropearls, 6 parts of multi-walled carbon nanotubes and 2 parts of dichloroethanes are uniformly mixed,
It is ultrasonically treated 3h, it is mixed to be subsequently added into material a, 1 part of silane coupling agent KH-560,6 parts of cumyl peroxides and 4 parts of hydroxy silicon oils
It closes uniformly, stirs 20min in 850r/min rotating speeds, be then warming up to 90 DEG C, flow back 20h, is cooled to room temperature to obtain toughness enhancing
Modified additive.
The toughening filler is prepared by following technique：36 parts of neopelexes and 5 parts are gone by weight
Ionized water is uniformly mixed, and stirs 4min, and 4 parts of hydroxymethyl celluloses are then added and are uniformly mixed, are stirred in 2500r/min rotating speeds
20min is then heated to 75 DEG C, keeps the temperature 5min, is subsequently added into 9 parts of butyl acrylates and 2 parts of potassium peroxydisulfates are uniformly mixed, reaction
3h, is then added dropwise the aluminum sulfate aqueous solution that 1 part of mass fraction is 15%, is demulsified, and filtering is done after washing in 45 DEG C of vacuum drying ovens
Dry 7h, is cooled to room temperature, and then calcines 5h at 820 DEG C in calcining furnace, cooling, is put into the salt that 4 parts of mass percents are 6%
1h is impregnated in acid solution, filtering is taken out, and cleans drying with clear water, 5 parts of silane resin acceptor kh-550s, 1 part of amino are added after crushing
Formic acid esters, 6 parts of isopropyl acrylates and 4 parts of polyparaphenylene's benzo dioxazole fibers are uniformly mixed, and are warming up to 130 DEG C, heat preservation
10min stirs 20min in 850r/min rotating speeds, is cooled to room temperature up to toughening filler.
The surface modifier is in 1,3 butylene glycol, Silane coupling reagent KH-570 and anilinomethyl triethoxysilane
One or more kinds of mixtures.
The preparation method of the high tenacity lithium battery diaphragm, includes the following steps：
S1：Liquid sizing material is obtained after being melted after Lauxite, epoxy resin and phenolic resin are warming up to 140 DEG C, then by chlorine
Fossil waxes and stearic acid are added in liquid sizing material, are continuously heating to 160 DEG C, are stirred 1h in 1300r/min rotating speeds, are cooled to room
Temperature obtains base-material；
S2：Microcrystalline cellulose, nanometer silicon carbide, ramee and blanc fixe are uniformly mixed, stirred after heating, surface is added
Modifying agent is uniformly mixed, and 30min is stirred in 650r/min rotating speeds after being warming up to 110 DEG C, is cooled to room temperature to obtain surface and is modified and fills out
Material；
S3：1h is stirred in 650r/min rotating speeds after base-material and polyester resin are warming up to 90 DEG C, toughness enhancing is then added and is modified
Auxiliary agent and toughening filler are uniformly mixed, and 40min are stirred in 850r/min rotating speeds after being warming up to 150 DEG C, then in twin-screw extrusion
In machine, shear at high temperature is plasticized 15mi in 125 DEG C, stirs, is blended, obtains blend melt, then in part melt conveying to die head,
It is cooled and solidified in rapidly chilling roller, obtains sheet material, then carry out biaxial tension, extracted, lithium battery diaphragm is obtained after thermal finalization.
Comparative example 1
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that lacking in the raw material of preparation high tenacity lithium battery diaphragm
Polyester resin, microcrystalline cellulose, nanometer silicon carbide, ramee, blanc fixe, toughness enhancing modified additive, toughening filler and
Surface modifier.
Comparative example 2
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that lacking in the raw material of preparation high tenacity lithium battery diaphragm
Polyester resin.
Comparative example 3
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that lacking in the raw material of preparation high tenacity lithium battery diaphragm
Microcrystalline cellulose.
Comparative example 4
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that lacking in the raw material of preparation high tenacity lithium battery diaphragm
Nanometer silicon carbide.
Comparative example 5
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that lacking in the raw material of preparation high tenacity lithium battery diaphragm
Ramee.
Comparative example 6
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that lacking in the raw material of preparation high tenacity lithium battery diaphragm
Blanc fixe.
Comparative example 7
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that lacking in the raw material of preparation high tenacity lithium battery diaphragm
Toughness enhances modified additive.
Comparative example 8
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that lacking in the raw material of preparation high tenacity lithium battery diaphragm
Toughening filler.
Comparative example 9
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that lacking in the raw material of preparation high tenacity lithium battery diaphragm
Surface modifier.
Comparative example 10
Using Chinese patent application document " polyvinyl formal-nanocrystal cellulose preparing lithium ion battery membrane（Application is public
Cloth number：CN102746522B）" in method described in specific embodiment 1-3 prepare lithium battery diaphragm.
Comparative example 11
Using a kind of Chinese patent literature " lithium battery diaphragm and preparation method thereof（Authorization Notice No.：CN103378331B）" in tool
Method described in body embodiment 1-2 prepares lithium battery diaphragm.
Comparative example 12
It is essentially identical with the preparation process of embodiment 1, have only unlike prepare high tenacity lithium battery diaphragm raw material in polyester
Resin is 38 parts, microcrystalline cellulose is 10 parts, nanometer silicon carbide is 1 part, ramee is 6 parts, blanc fixe is 3 parts, toughness
Enhancing modified additive is 27 parts, toughening filler is 15 parts, surface modifier is 4 parts.
Comparative example 13
It is essentially identical with the preparation process of embodiment 1, have only unlike prepare high tenacity lithium battery diaphragm raw material in polyester
Resin is 62 parts, microcrystalline cellulose is 2 parts, nanometer silicon carbide is 7 parts, ramee is 6 parts, blanc fixe is 3 parts, toughness increases
Strong modified additive is 27 parts, toughening filler is 15 parts, surface modifier is 0.9 part.
Comparative example 14
It is essentially identical with the preparation process of embodiment 1, have only unlike prepare high tenacity lithium battery diaphragm raw material in polyester
Resin is 39 parts, microcrystalline cellulose is 2 parts, nanometer silicon carbide is 7 parts, ramee is 0.6 part, blanc fixe is 9 parts, toughness
Enhancing modified additive is 20 parts, toughening filler is 34 parts, surface modifier is 0.8 part.
Toughness properties test is carried out to product made from embodiment 1-3 and comparative example 1-14, the results are shown in table below.
As seen from the above table：（1）By embodiment 1-3 and the data of comparative example 10 and comparative example 11 as it can be seen that embodiment 1-3 systems
The toughness of high tenacity lithium battery diaphragm, porosity, puncture strength and ventilative value be all remarkably higher than comparative example 10 and right
The toughness, porosity of lithium battery diaphragm made from ratio 11, puncture strength and ventilative value；Simultaneously by the data of embodiment 1-3
As it can be seen that embodiment 1 is optimum embodiment.
（2）By embodiment 1 and the data of comparative example 1-9 as it can be seen that polyester resin, microcrystalline cellulose, nanometer silicon carbide, ramie
Fiber, blanc fixe, toughness enhancing modified additive, toughening filler and surface modifier rise in preparing high tenacity lithium battery diaphragm
Synergistic effect is arrived, collaboration improves the toughness of the lithium battery diaphragm；This is：Polyester resin, microcrystalline cellulose, nano silicon carbide
Silicon, ramee, blanc fixe, toughness enhancing modified additive, toughening filler and surface modifier are as reinforcement system, wherein poly-
Ester resin is major ingredient, and assigning reinforcement system enhances toughness properties, microcrystalline cellulose, nanometer silicon carbide, ramee, blanc fixe
It as toughness reinforced filling, acts on during the melt process of polyester resin, improves the toughness of polyester resin, add surface
Modifying agent realizes that the toughness reinforcement that toughness is enhanced to modified additive and toughening filler applies to the lithium battery as graft modification agent
In the base-material of diaphragm, the hydroxyl for realizing toughness enhancing modified additive and toughening filler surface is acted in the grafting of surface modifier
Under realize and combined with base-material, effectively increase the toughness of lithium battery diaphragm of the present invention.Wherein, toughness enhancing modified additive passes through
Under nitrogen protection, corn flour, distilled water and maleic anhydride are uniformly mixed, then heating and heat preservation, ammonium persulfate is then added
It is uniformly mixed, styrene is added after stirring and is uniformly mixed, is followed by stirring for, then heats up, extracts, then in vacuum drying oven, dry
To constant weight, it is cooled to room temperature to obtain material a；By wood fiber powder, tossa, hollow glass micropearl, multi-walled carbon nanotube and
Dichloroethanes is uniformly mixed, and is ultrasonically treated, is subsequently added into material a, silane coupling agent KH-560, cumyl peroxide and hydroxyl
Silicone oil is uniformly mixed, and stirring then heats up, and flows back, is cooled to room temperature to obtain, wherein using corn flour as stickiness base-material, with horse
It is grafted monomers to carry out acid anhydrides, using ammonium persulfate, styrene and cumyl peroxide as initiator, with wood fiber powder, jute
Fiber, hollow glass micropearl, multi-walled carbon nanotube are toughened and reinforced filler, using hydroxy silicon oil as solvent, with silane coupling agent KH-
560 graft modification agent are changed by that will carry out surface with wood fiber powder, tossa, hollow glass micropearl, multi-walled carbon nanotube
Property, obtain modified filler is combined with maleic anhydride, and obtained toughness enhancing modified additive is applied to the lithium of the present invention
In the preparation of battery diaphragm, obtained lithium battery diaphragm has excellent toughness.Wherein, toughening filler is by by detergent alkylate
Sodium sulfonate and deionized water are uniformly mixed, stirring, and hydroxymethyl cellulose is then added and is uniformly mixed, and then stirring is heated, protect
Temperature, is subsequently added into butyl acrylate and potassium peroxydisulfate is uniformly mixed, and then aluminum sulfate aqueous solution is added dropwise in reaction, be demulsified, filtering,
It is dry in vacuum drying oven after washing, it is cooled to room temperature, is then calcined in calcining furnace, it is cooling, it is put into hydrochloric acid solution and impregnates,
Filtering take out, with clear water clean drying, after crushing be added silane resin acceptor kh-550, carbamate, isopropyl acrylate and
Polyparaphenylene's benzo dioxazole fiber is uniformly mixed, and is heated up, and is kept the temperature, and stirring is cooled to room temperature and obtains, wherein with dodecane
Base benzene sulfonic acid sodium salt be surfactant, using hydroxymethyl cellulose as toughness reinforcement material, with butyl acrylate, carbamate,
Isopropyl acrylate and be monomer, it is fine with aluminum sulfate aqueous solution and polyparaphenylene's benzo dioxazole using potassium peroxydisulfate as initiator
Dimension is used as toughened and reinforced material, and is used as graft modification auxiliary agent by silane resin acceptor kh-550 and changes to toughened and reinforced material progress surface
Property, it being combined with the unsaturated bond of monomer surface, obtained toughening filler applies to the preparation of the lithium battery diaphragm of the present invention,
Effectively increase the toughness of lithium battery diaphragm of the present invention.
（3）By the data of comparative example 12-14 as it can be seen that polyester resin, microcrystalline cellulose, nanometer silicon carbide, ramee, again
The weight ratio that spar powder, toughness enhance modified additive, toughening filler and surface modifier does not exist（40-60）：（3-9）：（2-6）：
（1-5）：（4-8）：（22-26）：（16-32）：（1-3）When in range, the corresponding numerical value of toughness of lithium battery diaphragm obtained
It is very different with the numerical value of embodiment 1-3, the numerical value of embodiment 1-3 is much smaller than, with the prior art（Comparative example 10 and comparative example
11）Numerical value it is suitable.Polyester resin of the present invention, microcrystalline cellulose, nanometer silicon carbide, ramee, blanc fixe, toughness enhancing
Modified additive, toughening filler and surface modifier are as reinforcement system, when embodiment 1-3 controls prepare high tenacity lithium battery diaphragm
Enhance modified additive by adding polyester resin, microcrystalline cellulose, nanometer silicon carbide, ramee, blanc fixe, toughness, increase
The weight ratio of tough filler and surface modifier is（40-60）：（3-9）：（2-6）：（1-5）：（4-8）：（22-26）：（16-32）：
（1-3）, realize using the toughness that polyester resin is excellent in reinforcement system, and fine in microcrystalline cellulose, nanometer silicon carbide, ramie
Dimension, blanc fixe are as toughened and reinforced filler, using polyester resin as reinforcement system as major ingredient, realize less toughened and reinforced fill out
Material acts on polyester resin, improves the intensity of polyester resin, and under the grafting of surface modifier effect, toughness increasing is utilized
The toughness strengthening action of strong modified additive effectively increases the toughness of the lithium battery diaphragm, while coordinating with toughening filler, in table
It is applied in base-material under the action of the modifying agent of face, effectively increases the toughness of the lithium battery diaphragm, as a result, polyester resin, crystallite
Cellulose, nanometer silicon carbide, ramee, blanc fixe, toughness enhancing modified additive, toughening filler and surface modifier conduct
Reinforcement system applies in the preparation of the lithium battery diaphragm, effectively increases the toughness of the lithium battery diaphragm.
The above content is it cannot be assumed that present invention specific implementation is confined to these explanations, for the technical field of the invention
Those of ordinary skill for, under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all answers
When being considered as belonging to present invention scope of patent protection determined by the appended claims.
Claims (10)
1. a kind of high tenacity lithium battery diaphragm, which is characterized in that the lithium battery diaphragm is sandwich diaphragm, using nucleopore membranes as base
Material is compounded with high tenacity layer in nucleopore membranes, hot closed layer is compounded on the high tenacity layer, the high tenacity layer includes following original
Material：Polyester resin, Lauxite, epoxy resin, phenolic resin, microcrystalline cellulose, nanometer silicon carbide, ramee, barite
Powder, chlorinated paraffin, stearic acid, toughness enhancing modified additive, toughening filler, surface modifier；
The toughness enhances modified additive, as unit of parts by weight, including following raw material：15-25 parts of corn flour, distilled water 10-
20 parts, it is 4-8 parts of maleic anhydride, 2-5 parts of ammonium persulfate, 1-5 parts of styrene, 4-8 parts of wood fiber powder, 3-6 parts of tossa, empty
2-8 parts of heart glass microballoon, 4-6 parts of multi-walled carbon nanotube, 2-5 parts of dichloroethanes, 1-5 parts of silane coupling agent KH-560, peroxidating
2-6 parts of diisopropylbenzene (DIPB), 4-8 parts of hydroxy silicon oil；
The toughening filler, as unit of parts by weight, including following raw material：18-36 parts of neopelex, deionized water
5-15 parts, 4-8 parts of hydroxymethyl cellulose, 3-9 parts of butyl acrylate, 2-5 parts of potassium peroxydisulfate, mass fraction be 5-15% sulfuric acid
1-5 parts of aluminum water solution, 2-5 parts of 4-6 parts of hydrochloric acid solution, silane resin acceptor kh-550, the carbamic acid that mass percent is 4-6%
1-4 parts of ester, 3-6 parts of isopropyl acrylate, 4-8 parts of polyparaphenylene's benzo dioxazole fiber；
The polyester resin, nanometer silicon carbide, ramee, blanc fixe, toughness enhancing modified additive, increases microcrystalline cellulose
The weight ratio of tough filler and surface modifier is（40-60）：（3-9）：（2-6）：（1-5）：（4-8）：（22-26）：（16-32）：
（1-3）.
2. high tenacity lithium battery diaphragm according to claim 1, which is characterized in that the polyester resin, microcrystalline cellulose,
Nanometer silicon carbide, ramee, blanc fixe, toughness enhancing modified additive, toughening filler and surface modifier weight ratio be
50：6：4：3：6：24：24：2.
3. high tenacity lithium battery diaphragm according to claim 1, which is characterized in that as unit of parts by weight, including it is following
Raw material：40-60 parts of polyester resin, 25-45 parts of Lauxite, 18-36 parts of epoxy resin, 4-8 parts of phenolic resin, microcrystalline cellulose
3-9 parts, 2-6 parts of nanometer silicon carbide, 1-5 parts of ramee, 4-8 parts of blanc fixe, 3-6 parts of chlorinated paraffin, 2-5 parts of stearic acid,
Toughness enhances 22-26 parts of modified additive, 16-32 parts of toughening filler, 1-3 parts of surface modifier.
4. high tenacity lithium battery diaphragm according to claim 1, which is characterized in that the toughness enhancing modified additive is by such as
It is prepared by lower technique：Under nitrogen protection, corn flour, distilled water and maleic anhydride are uniformly mixed, then heat to 80-90
DEG C, 10-30min is kept the temperature, ammonium persulfate is then added and is uniformly mixed, addition styrene is uniformly mixed after stirring 5-15min, then
50-70min is stirred in 850-1250r/min rotating speeds, then heats to 85-95 DEG C, 40-50h is extracted, then in vacuum drying oven
In, 65-75 DEG C dries to constant weight, and is cooled to room temperature to obtain material a；By wood fiber powder, tossa, hollow glass micropearl, more
Wall carbon nano tube and dichloroethanes are uniformly mixed, and are ultrasonically treated 1-3h, are subsequently added into material a, silane coupling agent KH-560, peroxide
Change diisopropylbenzene (DIPB) and hydroxy silicon oil is uniformly mixed, stirs 20-40min in 650-850r/min rotating speeds, be then warming up to 80-90
DEG C, flow back 20-30h, is cooled to room temperature to obtain toughness enhancing modified additive.
5. high tenacity lithium battery diaphragm according to claim 1, which is characterized in that the toughening filler by following technique into
It is prepared by row：Neopelex and deionized water are uniformly mixed, 2-4min is stirred, it is mixed that hydroxymethyl cellulose is then added
It closes uniformly, stirs 20-30min in 1500-2500r/min rotating speeds, be then heated to 65-75 DEG C, keep the temperature 5-15min, then add
Enter butyl acrylate and potassium peroxydisulfate is uniformly mixed, react 1-3h, it is water-soluble that the aluminum sulfate that mass fraction is 5-15% is then added dropwise
Liquid is demulsified, filtering, after washing in 45-55 DEG C of vacuum drying oven dry 5-7h, be cooled to room temperature, then in calcining furnace
2-5h is calcined at 820-920 DEG C, it is cooling, it is put into the hydrochloric acid solution that mass percent is 4-6% and impregnates 1-3h, filtering is taken out, and is used
Clear water cleans drying, and silane resin acceptor kh-550, carbamate, isopropyl acrylate and polyparaphenylene's benzo are added after crushing
Dioxazole fiber is uniformly mixed, and is warming up to 110-130 DEG C, keeps the temperature 10-30min, and 20- is stirred in 650-850r/min rotating speeds
30min is cooled to room temperature up to toughening filler.
6. high tenacity lithium battery diaphragm according to claim 1, which is characterized in that the surface modifier is 1,3- fourths two
One or more of alcohol, Silane coupling reagent KH-570 and anilinomethyl triethoxysilane mixture.
7. a kind of preparation method according to claim 1-6 any one of them high tenacity lithium battery diaphragms, which is characterized in that packet
Include following steps：
S1：Liquid sizing material will be obtained after the heating melting of Lauxite, epoxy resin and phenolic resin, then by chlorinated paraffin and firmly
Resin acid is added in liquid sizing material, is continued heating stirring, is cooled to room temperature to obtain base-material；
S2：Microcrystalline cellulose, nanometer silicon carbide, ramee and blanc fixe are uniformly mixed, stirred after continuing heating, is added
Surface modifier is uniformly mixed, and is stirred after heating, is cooled to room temperature to obtain surface modifying stuffing；
S3：It will be stirred after base-material and polyester resin heating, toughness enhancing modified additive be then added and toughening filler is uniformly mixed,
It is stirred after heating, then in double screw extruder, shear at high temperature is plasticized, and is stirred, and is plasticized, and is blended, is obtained blend melt, so
It afterwards by melt conveying to die head, is cooled and solidified in rapidly chilling roller, obtains sheet material, then carry out biaxial tension, extracted, heat is fixed
Lithium battery diaphragm is obtained after type.
8. the preparation method of high tenacity lithium battery diaphragm according to claim 7, which is characterized in that in S1, by ureaformaldehyde tree
Fat, epoxy resin and phenolic resin obtain liquid sizing material after being melted after being warming up to 120-140 DEG C, then by chlorinated paraffin and tristearin
Acid is added in liquid sizing material, is continuously heating to 160-180 DEG C, is stirred 1-2h in 1100-1300r/min rotating speeds, is cooled to room
Temperature obtains base-material.
9. the preparation method of high tenacity lithium battery diaphragm according to claim 7, which is characterized in that in S2, by crystallite fibre
It ties up element, nanometer silicon carbide, ramee and blanc fixe to be uniformly mixed, be stirred after heating, surface modifier is added and is uniformly mixed,
20-30min is stirred in 650-850r/min rotating speeds after being warming up to 90-110 DEG C, is cooled to room temperature to obtain surface modifying stuffing.
10. the preparation method of high tenacity lithium battery diaphragm according to claim 7, which is characterized in that in S3, by base-material and
Polyester resin be warming up to 90-110 DEG C after in 550-650r/min rotating speeds stir 1-2h, then be added toughness enhancing modified additive and
Toughening filler is uniformly mixed, and 20-40min is stirred in 850-1050r/min rotating speeds after being warming up to 130-150 DEG C, then in double spiral shells
In bar extruder, shear at high temperature is plasticized 5-15mi in 125-145 DEG C, stirs, is blended, obtains blend melt, then that melt is defeated
It send into die head, is cooled and solidified in rapidly chilling roller, obtain sheet material, then carry out biaxial tension, extract, lithium is obtained after thermal finalization
Battery diaphragm.
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| CN109411674A (en) * | 2018-09-29 | 2019-03-01 | 湖北江升新材料有限公司 | A kind of compound lithium ion battery separator and preparation method thereof |
| CN112409617A (en) * | 2020-11-09 | 2021-02-26 | 毛泽龙 | Polymer film and preparation method thereof |
| CN113782797A (en) * | 2021-08-19 | 2021-12-10 | 深圳氢时代新能源科技有限公司 | MOF material and preparation method thereof, proton exchange membrane and preparation method thereof, and fuel cell |
| CN113832776A (en) * | 2021-08-13 | 2021-12-24 | 江苏劲源新能源科技有限公司 | Highland barley paper for lithium battery packaging and preparation method thereof |
| CN114069156A (en) * | 2021-10-27 | 2022-02-18 | 江西永德立新能源有限公司 | Anti-puncture diaphragm and application thereof in lithium battery |
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| CN114069156A (en) * | 2021-10-27 | 2022-02-18 | 江西永德立新能源有限公司 | Anti-puncture diaphragm and application thereof in lithium battery |
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