CN108807818A - A kind of aromatic polyamide composite diaphragm and preparation method thereof - Google Patents
A kind of aromatic polyamide composite diaphragm and preparation method thereof Download PDFInfo
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- CN108807818A CN108807818A CN201810603632.5A CN201810603632A CN108807818A CN 108807818 A CN108807818 A CN 108807818A CN 201810603632 A CN201810603632 A CN 201810603632A CN 108807818 A CN108807818 A CN 108807818A
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- aromatic polyamide
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M50/44—Fibrous material
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- 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
Abstract
The invention discloses a kind of aromatic polyamide composite diaphragms and preparation method thereof, and the composite diaphragm is made of basement membrane and coating, and coating is provided on the basement membrane one or both sides；The coating is coated by aromatic polyamide casting solution, washes, is formed after drying；The aromatic polyamide casting solution is formed using the material combination of following weight proportion：Aromatic polyamide fibre：1-6 parts, the first solvent：70-95 parts, pore creating material：3-20 parts, cosolvent：2-8 parts；First solvent is one or more of NMP, DMF, DMAC or DMSO；The pore creating material is organic alcohols compound；The cosolvent is KOH, CaCl2, one or more of LiCl or pyridine.Gained composite diaphragm has higher thermal stability, while permeability is good, can large-scale application in production.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of aromatic polyamide composite diaphragm and its preparation
Method.
Background technology
Recently as flourishing for new-energy automobile, lithium battery demand increases in blowout, as lithium battery core
The lithium battery diaphragm of one of center portion part also obtains high speed development.Current commercialized lithium battery diaphragm is mainly polyolefin material,
It is with higher porosity, higher tensile strength, preferable antiacid alkali ability, but its temperature tolerance is poor, polyolefins
The fusing point of diaphragm is 160 DEG C or lower, and when temperature reaches the fusing point of polyolefins diaphragm, the heat of diaphragm meeting occurrence of large-area is received
Contracting causes battery thermal runaway to cause safety accident so as to cause positive and negative anodes contact short circuit；Meanwhile polyolefin material is born
Hydrophobicity and low-surface-energy make it be unfavorable for being soaked by electrolyte, limit its application in lithium battery.
Numerous battery enterprises initially enter the modified field of diaphragm coating, and current commercialized composite diaphragm is mainly that ceramics apply
Layer diaphragm, but the main component aluminium oxide of generally existing thermal stability difference and ceramic slurry is due to being that inorganic particle easily occurs to sink
It forms sediment, needs to stir before film, be unfavorable for large-scale production.And aromatic polyamide Type of Collective object (PPTA, PMIA, PBA, PSA
Deng) have many advantages, such as that high temperature resistant, superhigh intensity, acid and alkali-resistance, light-weight, insulation, anti-aging, life cycle is long, therefore be used to
As coating material, gained aromatic polyamide, which coats diaphragm, has good thermal stability, good permeability, porosity height, wellability
Excellent, the advantages that service life is long.
At present when preparing the lithium ion battery separator of aromatic polyamide coating, it is mostly used DMF, DMAc, NMP, DMSO etc.
Organic solvent coordinates cosolvent to dissolve aromatic polyamide, and inorganic particle pore-foaming agent is then added and obtains aromatic polyamide casting film
Liquid obtains the lithium ion battery separator of aromatic polyamide coating by coating, washing and drying.But inorganic particle pore-foaming agent is having
Difficulties in dispersion in solvent influences coating and pore-forming uniformity, is not used to mass produce.
Invention content
It is existing to solve the purpose of the present invention is to provide a kind of aromatic polyamide composite diaphragm and preparation method thereof
Inorganic particle pore-foaming agent difficulties in dispersion in organic solvent in the lithium ion battery separator of aromatic polyamide coating, influences to apply
Layer and pore-forming uniformity, the problem of being not used to mass produce.
To achieve the above object, the technical scheme is that：
A kind of aromatic polyamide composite diaphragm, the composite diaphragm are made of basement membrane and coating, basement membrane one side or
Coating is provided on two sides；The coating is coated by aromatic polyamide casting solution, washes, is formed after drying；
The aromatic polyamide casting solution is formed using the material combination of following weight proportion：Aromatic polyamide is fine
Dimension：1-6 parts, the first solvent：70-95 parts, pore creating material：3-20 parts, cosolvent：2-8 parts；The pore creating material is organic alcohols chemical combination
Object.
In one embodiment, first solvent is one or more of NMP, DMF, DMAC or DMSO；It is described
Cosolvent is KOH, CaCl2, one or more of LiCl or pyridine；The organic alcohols compound is methanol, ethyl alcohol, second two
One or several kinds in alcohol, propylene glycol, hexylene glycol, glycerine, tripropylene glycol, 3 third glycol, polypropylene glycol.
In one embodiment, the aromatic polyamide fibre be Fanglun 1414, it is poly- between
One or more of phenyl-diformyl m-phenylene diamine (MPD) fiber, poly fiber or polyphenylsulfone terephthalamide fiber；
The aromatic polyamide fibre molecular weight is 5000~100000.
In one embodiment, the basement membrane is polyethylene film, polypropylene screen, polypropylene, polyethylene composite membrane, gathers partially
One kind in fluoride film, polyimide film, polyethylene nonwoven film, polypropylene non-woven fabric film, polyimide nonwoven fabric film；Institute
The thickness for stating basement membrane is 5~30 μm, and porosity is 30~80%, and air penetrability is 50~300s/100cc.
The preparation method of above-mentioned composite diaphragm is prepared, the preparation method includes the following steps：
A, cosolvent is added into the first solvent, heating stirring is to being completely dissolved, then under conditions of heating stirring
Aromatic polyamide fibre is added, continues heating stirring and waits for that aromatic polyamide fibre is completely dissolved to get Fibrinolysis liquid；
B, under conditions of heating stirring, it is slowly added to pore creating material into the Fibrinolysis liquid, continues heating stirring extremely
It is uniformly mixed to get aromatic polyamide casting solution；
C, the painting of the one or both sides of basement membrane is covered with the aromatic polyamide casting solution, being then placed into coagulation bath makes
Aromatic polyamide casting film liquid-phase conversion forms a film, and the film is again successively by washing and high temperature drying to get aromatic polyamide
Composite diaphragm；The coagulation bath is one kind in deionized water or mixed liquor including deionized water and the second solvent, described the
Two solvents are mixed by the first solvent and pore creating material.
In one embodiment, in step b, the preparation temperature of the aromatic polyamide casting solution is 50~80 DEG C.
In one embodiment, in step b, mixing speed when preparing the aromatic polyamide casting solution is 300
~2000rpm.
In one embodiment, the coagulation bath is deionization when including the mixed liquor of deionized water and the second solvent
The quality parts ratio of water and the second solvent is (0.5:1)~(5:1), in the second solvent the first solvent and pore creating material mass fraction
It is more consistent with the quality parts ratio of pore creating material than with the first solvent in aromatic polyamide casting solution.
In one embodiment, the thickness of the composite diaphragm is 11~30 μm, and air penetrability is 50~500s/100cc.
In one embodiment, the thickness of the composite diaphragm is 11~25 μm, and air penetrability is 100~160s/
100cc。
The invention has the advantages that：
A kind of lithium ion battery separator of aromatic polyamide coating of the present invention is by lithium ion battery basement membrane and in basement membrane
The coating of one or both sides forms.The lithium ion battery basement membrane is the composite diaphragm of polyethylene, polypropylene, polyethylene polypropylene
Equal microporous polyolefins hydro carbons diaphragm, coating are obtained by aromatic polyamide casting solution after coating, washing, drying, the fragrance
Polyamide casting solution is made of aromatic polyamide fibre, the good solvent of aromatic polyamide fibre, cosolvent and pore creating material.
The aromatic polyamide casting solution stability of composite diaphragm of the present invention is good；The casting solution raw material is simple, introduces hydrophilic
Property organic alcohols pore creating material substitute inorganic particle pore creating material, improve the uniformity and pore-forming uniformity of coating；Gained is compound
Diaphragm has higher thermal stability, while permeability is good, can large-scale application in production.
Description of the drawings
Fig. 1 is the SEM figures of composite lithium ion cell diaphragm in the embodiment of the present invention 1.
Specific implementation mode
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment 1
A kind of aromatic polyamide composite diaphragm is made of basement membrane and coating, and painting is provided on the basement membrane one or both sides
Layer；The coating is coated by aromatic polyamide casting solution, washes, is formed after drying；
The aromatic polyamide casting solution is formed using the material combination of following weight proportion：Aromatic polyamide is fine
Dimension：1 part, the first solvent：91.2 parts, pore creating material：4.8 parts, cosolvent：4 parts；First solvent is NMP；The pore creating material is
Tripropylene glycol；The cosolvent is LiCl.
A kind of preparation method of aromatic polyamide composite diaphragm is as follows：
A, 4 parts of cosolvent LiCl is added to in 91.2 parts of the first solvent NMP heating stirring is to after being completely dissolved, side
1 part of Fanglun 1414 is added in high-speed stirred side, and poly(p-phenylene terephthalamide) is fine after heating stirring 1h
Dimension is completely dissolved to obtain Fibrinolysis liquid, then is slowly added to 4 parts of tripropylene glycol while stirring, and fragrance is obtained after heating stirring 1h
Polyamide casting solution.
B, coagulation bath solution is configured：80 parts of deionized waters, NMP and 4 of 76 parts part of tripropylene glycol are taken to be mixed and heated to
40~50 DEG C obtain coagulation bath solution for standby.
C, the polyethylene diagrams of 12 μ m-thicks are chosen as basement membrane, are coated on aramid fiber casting solution using wound rod coating method
The unilateral side of basement membrane, application rate 15m/min take out and use during immersion precipitation is bathed after evaporation 20s in air after inversion of phases 1min
After deionized water soaking and water washing 2min, in baking oven 60 DEG C drying can be obtained aromatic polyamide coating lithium ion battery every
Film.The thickness of the composite diaphragm is 14 μm, air penetrability 160s/100cc, is swept to gained composite lithium ion cell diaphragm
Electron microscope analysis is retouched, as shown in Figure 1, find that the diaphragm pore-forming is uniform in figure, and porosity is high, does not have large area aporate area, has
Conducive to the transmission of lithium ion.
Embodiment 2
A kind of aromatic polyamide composite diaphragm is made of basement membrane and coating, and painting is provided on the basement membrane one or both sides
Layer；The coating is coated by aromatic polyamide casting solution, washes, is formed after drying；
The aromatic polyamide casting solution is formed using the material combination of following weight proportion：Aromatic polyamide is fine
Dimension：1.2 parts, the first solvent：73 parts, pore creating material：3.8 parts, cosolvent：3.2 part；First solvent is NMP；The pore creating material
For tripropylene glycol；The cosolvent is LiCl.
A kind of preparation method of aromatic polyamide composite diaphragm is as follows：
A, it weighs 3.2 parts of cosolvent LiCl and is added in 73 parts of the first solvent NMP heating stirring to after being completely dissolved,
1.2 parts of Fanglun 1414 is added in high-speed stirred, poly- paraphenylene terephthalamide is to benzene two after heating stirring 1h
Amine fiber is completely dissolved to obtain Fibrinolysis liquid, then is slowly added to 3.8 parts of tripropylene glycol while stirring, after heating stirring 1h
To aromatic polyamide casting solution.
B, coagulation bath solution is configured：80 parts of deionized waters, NMP and 4 of 76 parts part of tripropylene glycol are taken to be mixed and heated to
40~50 DEG C obtain coagulation bath solution for standby.
C, the polyethylene diagrams of 12 μ m-thicks are chosen as basement membrane, are coated on aramid fiber casting solution using wound rod coating method
The unilateral side of basement membrane, application rate 15m/min take out and use during immersion precipitation is bathed after evaporation 20s in air after inversion of phases 1min
After deionized water washes 2min, the lithium ion battery separator that can be obtained aromatic polyamide coating is dried for 60 DEG C in baking oven.
The thickness of the composite diaphragm is 14 μm, air penetrability 147s/100cc.
Embodiment 3
A kind of aromatic polyamide composite diaphragm is made of basement membrane and coating, and painting is provided on the basement membrane one or both sides
Layer；The coating is coated by aromatic polyamide casting solution, washes, is formed after drying；
The aromatic polyamide casting solution is formed using the material combination of following weight proportion：Aromatic polyamide is fine
Dimension：2.09 parts, the first solvent：95 parts, pore creating material：4.75 parts, cosolvent：4.18 part；First solvent is NMP；It is described to make
Hole agent is tripropylene glycol；The cosolvent is LiCl.
A kind of preparation method of aromatic polyamide composite diaphragm is as follows：
A, it weighs 4.18 parts of cosolvent LiCl and is added in 95 parts of the first solvent NMP heating stirring to being completely dissolved
Afterwards, it is added 2.09 parts of Fanglun 1414 in high-speed stirred, poly- paraphenylene terephthalamide couple after heating stirring 1h
Fibers are completely dissolved to obtain Fibrinolysis liquid, then are slowly added to 4.75 parts of tripropylene glycol, heating stirring while stirring
Aromatic polyamide casting solution is obtained after 1h.
B, coagulation bath solution is configured：76 parts of deionized waters, NMP and 3.8 of 72.2 parts part of tripropylene glycol are taken to mix and add
Heat obtains coagulation bath solution to 40~50 DEG C.
C, the polyethylene diagrams of 12 μ m-thicks are chosen as basement membrane, are coated on aramid fiber casting solution using wound rod coating method
The unilateral side of basement membrane, application rate 15m/min take out and use during immersion precipitation is bathed after evaporation 20s in air after inversion of phases 1min
After deionized water washes 2min, the lithium ion battery separator that can be obtained aromatic polyamide coating is dried for 60 DEG C in baking oven.
The thickness of the composite diaphragm is 14 μm, air penetrability 165s/100cc.
Embodiment 4
A kind of aromatic polyamide composite diaphragm is made of basement membrane and coating, and painting is provided on the basement membrane one or both sides
Layer；The coating is coated by aromatic polyamide casting solution, washes, is formed after drying；
The aromatic polyamide casting solution is formed using the material combination of following weight proportion：Aromatic polyamide is fine
Dimension：1 part, the first solvent：86 parts, pore creating material：9.6 parts, cosolvent：4 parts；First solvent is DMAC；The pore creating material is
Tripropylene glycol；The cosolvent is CaCl2。
A kind of preparation method of aromatic polyamide composite diaphragm is as follows：
A, 4 parts of cosolvent CaCl is weighed2Heating stirring is added in 86 parts of the first solvent DMAC to after being completely dissolved,
It is added 1 part of Fanglun 1414 in high-speed stirred, poly(p-phenylene terephthalamide) after heating stirring 1h
Fiber is completely dissolved to obtain Fibrinolysis liquid, then is slowly added to 9.6 parts of tripropylene glycol while stirring, is obtained after heating stirring 1h
Aromatic polyamide casting solution.
B, coagulation bath solution is configured：128 parts of deionized waters, DMAC and 3.2 of 28.8 parts part of tripropylene glycol are taken to mix
To coagulation bath solution.
C, the polyethylene diagrams of 12 μ m-thicks are chosen as basement membrane, are coated on aramid fiber casting solution using wound rod coating method
The unilateral side of basement membrane, application rate 15m/min take out and use during immersion precipitation is bathed after evaporation 20s in air after inversion of phases 1min
After deionized water washes 2min, the lithium ion battery separator that can be obtained aromatic polyamide coating is dried for 60 DEG C in baking oven.
The thickness of the composite diaphragm is 16 μm, air penetrability 182s/100cc.
Embodiment 5
A kind of aromatic polyamide composite diaphragm is made of basement membrane and coating, and painting is provided on the basement membrane one or both sides
Layer；The coating is coated by aromatic polyamide casting solution, washes, is formed after drying；
The aromatic polyamide casting solution is formed using the material combination of following weight proportion：Aromatic polyamide is fine
Dimension：1 part, the first solvent：91.2 parts, pore creating material：4.8 parts, cosolvent：4 parts；First solvent is DMAC；The pore creating material
For tripropylene glycol；The cosolvent is CaCl2。
A kind of preparation method of aromatic polyamide composite diaphragm is as follows：
A, 4 parts of cosolvent CaCl is weighed2Heating stirring is added in 91.2 parts of the first solvent DMAC to being completely dissolved
Afterwards, 1 part of Fanglun 1414 is added in high-speed stirred, poly- paraphenylene terephthalamide is to benzene two after heating stirring 1h
Amine fiber is completely dissolved to obtain Fibrinolysis liquid, then is slowly added to 4.8 parts of tripropylene glycol while stirring, after heating stirring 1h
To aromatic polyamide casting solution.
B, coagulation bath solution is configured：128 parts of deionized waters, DMAc and 1.6 of 30 parts part of tripropylene glycol are taken to be mixed to get
Coagulation bath solution.
C, the polyethylene diagrams of 12 μ m-thicks are chosen as basement membrane, are coated on aramid fiber casting solution using wound rod coating method
The unilateral side of basement membrane, application rate 15m/min take out and use during immersion precipitation is bathed after evaporation 20s in air after inversion of phases 1min
After deionized water washes 2min, the lithium ion battery separator that can be obtained aromatic polyamide coating is dried for 60 DEG C in baking oven.
The thickness of the composite diaphragm is 16 μm, air penetrability 187s/100cc.
Embodiment 6
A kind of aromatic polyamide composite diaphragm is made of basement membrane and coating, and painting is provided on the basement membrane one or both sides
Layer；The coating is coated by aromatic polyamide casting solution, washes, is formed after drying；
The aromatic polyamide casting solution is formed using the material combination of following weight proportion：Aromatic polyamide is fine
Dimension：1.5 parts, the first solvent：76.8 parts, pore creating material：19.2 parts, cosolvent：4 parts；First solvent is NMP；The pore-creating
Agent is tripropylene glycol；The cosolvent is LiCl.
A kind of preparation method of aromatic polyamide composite diaphragm is as follows：
A, it weighs 4 parts of cosolvent LiCl and is added in 76.8 parts of the first solvent NMP heating stirring to after being completely dissolved,
1.5 parts of Fanglun 1414 is added in high-speed stirred, poly- paraphenylene terephthalamide is to benzene two after heating stirring 1h
Amine fiber is completely dissolved to obtain Fibrinolysis liquid, then is slowly added to 19.2 parts of tripropylene glycol while stirring, after heating stirring 1h
Obtain aromatic polyamide casting solution.
B, coagulation bath solution is configured：80 parts of deionized waters, NMP and 16 of 64 parts part of tripropylene glycol are taken to be mixed and heated to
40~50 DEG C obtain coagulation bath solution for standby.
C, the polyethylene diagrams of 12 μ m-thicks are chosen as basement membrane, are coated on aramid fiber casting solution using wound rod coating method
The unilateral side of basement membrane, application rate 15m/min take out and use during immersion precipitation is bathed after evaporation 20s in air after inversion of phases 1min
After deionized water washes 2min, the lithium ion battery separator that can be obtained aromatic polyamide coating is dried for 60 DEG C in baking oven.
The thickness of the composite diaphragm is 14 μm, air penetrability 196s/100cc.
Embodiment 7
A kind of aromatic polyamide composite diaphragm is made of basement membrane and coating, and painting is provided on the basement membrane one or both sides
Layer；The coating is coated by aromatic polyamide casting solution, washes, is formed after drying；
The aromatic polyamide casting solution is formed using the material combination of following weight proportion：Aromatic polyamide is fine
Dimension：6 parts, the first solvent：86 parts, pore creating material：9.6 parts, cosolvent：4 parts；First solvent is NMP；The pore creating material is three
Propylene glycol；The cosolvent is LiCl.
A kind of preparation method of aromatic polyamide composite diaphragm is as follows：
A, it weighs 4 parts of cosolvent LiCl and is added in 86 parts of the first solvent NMP that heating stirring is to after being completely dissolved, side
6 parts of Fanglun 1414 is added in high-speed stirred side, and poly(p-phenylene terephthalamide) is fine after heating stirring 1h
Dimension is completely dissolved to obtain Fibrinolysis liquid, then is slowly added to 9.6 parts of tripropylene glycol while stirring, and virtue is obtained after heating stirring 1h
Fragrant polyamide casting solution.
B, coagulation bath solution is configured：80 parts of deionized waters, NMP and 8 of 72 parts part of tripropylene glycol are taken to be mixed and heated to
40~50 DEG C obtain coagulation bath solution for standby.
C, the polyethylene diagrams of 12 μ m-thicks are chosen as basement membrane, are coated on aramid fiber casting solution using wound rod coating method
The unilateral side of basement membrane, application rate 15m/min take out and use during immersion precipitation is bathed after evaporation 20s in air after inversion of phases 1min
After deionized water washes 2min, the lithium ion battery separator that can be obtained aromatic polyamide coating is dried for 60 DEG C in baking oven.
The thickness of the composite diaphragm is 14 μm, air penetrability 283s/100cc.
Embodiment 8
A kind of aromatic polyamide composite diaphragm is made of basement membrane and coating, and painting is provided on the basement membrane one or both sides
Layer；The coating is coated by aromatic polyamide casting solution, washes, is formed after drying；
The aromatic polyamide casting solution is formed using the material combination of following weight proportion：Aromatic polyamide is fine
Dimension：2 parts, the first solvent：88 parts, pore creating material：9.8 parts, cosolvent：2 parts；First solvent is NMP；The pore creating material is three
Propylene glycol；The cosolvent is LiCl.
A kind of preparation method of aromatic polyamide composite diaphragm is as follows：
A, it weighs 2 parts of cosolvent LiCl and is added in 88 parts of the first solvent NMP that heating stirring is to after being completely dissolved, side
2 parts of Fanglun 1414 is added in high-speed stirred side, and poly(p-phenylene terephthalamide) is fine after heating stirring 1h
Dimension is completely dissolved to obtain Fibrinolysis liquid, then is slowly added to 9.8 parts of tripropylene glycol while stirring, and virtue is obtained after heating stirring 1h
Fragrant polyamide casting solution.
B, coagulation bath solution is configured：80 parts of deionized waters, NMP and 8 of 72 parts part of tripropylene glycol are taken to be mixed and heated to
40~50 DEG C obtain coagulation bath solution for standby.
C, the polyethylene diagrams of 12 μ m-thicks are chosen as basement membrane, are coated on aramid fiber casting solution using wound rod coating method
The unilateral side of basement membrane, application rate 15m/min take out and use during immersion precipitation is bathed after evaporation 20s in air after inversion of phases 1min
After deionized water washes 2min, the lithium ion battery separator that can be obtained aromatic polyamide coating is dried for 60 DEG C in baking oven.
The thickness of the composite diaphragm is 14 μm, air penetrability 356s/100cc.
Embodiment 9
A kind of aromatic polyamide composite diaphragm is made of basement membrane and coating, and painting is provided on the basement membrane one or both sides
Layer；The coating is coated by aromatic polyamide casting solution, washes, is formed after drying；
The aromatic polyamide casting solution is formed using the material combination of following weight proportion：Aromatic polyamide is fine
Dimension：2 parts, the first solvent：87 parts, pore creating material：4.6 parts, cosolvent：8 parts；First solvent is NMP；The pore creating material is three
Propylene glycol；The cosolvent is LiCl.
A kind of preparation method of aromatic polyamide composite diaphragm is as follows：
A, it weighs 8 parts of cosolvent LiCl and is added in 87 parts of the first solvent NMP that heating stirring is to after being completely dissolved, side
2 parts of Fanglun 1414 is added in high-speed stirred side, and poly(p-phenylene terephthalamide) is fine after heating stirring 1h
Dimension is completely dissolved to obtain Fibrinolysis liquid, then is slowly added to 4.6 parts of tripropylene glycol while stirring, and virtue is obtained after heating stirring 1h
Fragrant polyamide casting solution.
B, coagulation bath solution is configured：80 parts of deionized waters, NMP and 4 of 76 parts part of tripropylene glycol are taken to be mixed and heated to
40~50 DEG C obtain coagulation bath solution for standby.
C, the polyethylene diagrams of 12 μ m-thicks are chosen as basement membrane, are coated on aramid fiber casting solution using wound rod coating method
The unilateral side of basement membrane, application rate 15m/min take out and use during immersion precipitation is bathed after evaporation 20s in air after inversion of phases 1min
After deionized water washes 2min, the lithium ion battery separator that can be obtained aromatic polyamide coating is dried for 60 DEG C in baking oven.
The thickness of the composite diaphragm is 14 μm, air penetrability 325s/100cc.
Embodiment 10
The performance of basement membrane used in the lithium ion battery separator of aramid fiber coating obtained by embodiment 1-9 and embodiment is surveyed
Examination, correction data are shown in Table 1：
By upper table data it is found that the present invention coats composite diaphragm obtained by aromatic polyamide coating on polyolefins diaphragm
Air permeability compared with basement membrane, 20~60s/100cc is increased only, while thermal contraction performance is much better than basement membrane, in embodiment 7
Thermal contraction at 140 DEG C is only 2%, substantially increases the thermal stability of diaphragm, ensures the security performance of battery.
Although above having used general explanation and specific embodiment, the present invention is described in detail, at this
On the basis of invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Therefore,
These modifications or improvements without departing from theon the basis of the spirit of the present invention belong to the scope of protection of present invention.
Claims (10)
1. a kind of aromatic polyamide composite diaphragm, which is characterized in that the composite diaphragm is made of basement membrane and coating, the base
It is provided with coating on film one or both sides；The coating is coated by aromatic polyamide casting solution, washes, is formed after drying；
The aromatic polyamide casting solution is formed using the material combination of following weight proportion：Aromatic polyamide fibre：1-6
Part, the first solvent：70-95 parts, pore creating material：3-20 parts, cosolvent：2-8 parts；The pore creating material is organic alcohols compound.
2. a kind of aromatic polyamide composite diaphragm as described in claim 1, which is characterized in that first solvent be NMP,
One or more of DMF, DMAC or DMSO；The cosolvent is KOH, CaCl2, one or more of LiCl or pyridine；
The organic alcohols compound be methanol, ethyl alcohol, ethylene glycol, propylene glycol, hexylene glycol, glycerine, tripropylene glycol, 3 third glycol,
One or several kinds in polypropylene glycol.
3. a kind of aromatic polyamide composite diaphragm as described in claim 1, which is characterized in that the aromatic polyamide is fine
Dimension is Fanglun 1414, Fanglun 1313, poly fiber or polyphenyl
One or more of sulfone terephthalamide fiber；The aromatic polyamide fibre molecular weight is 5000~100000.
4. a kind of aromatic polyamide composite diaphragm as described in claim 1, which is characterized in that the basement membrane is polyethylene
Film, polypropylene screen, polypropylene, polyethylene composite membrane, polyvinylidene fluoride film, polyimide film, polyethylene nonwoven film, polypropylene
One kind in non-woven membrane, polyimide nonwoven fabric film；The thickness of the basement membrane is 5~30 μm, and porosity is 30~80%, thoroughly
Gas rate is 50~300s/100cc.
5. the preparation method of composite diaphragm as described in claim any one of 1-4, which is characterized in that the preparation method includes such as
Lower step：
A, cosolvent is added into the first solvent, then heating stirring adds again to being completely dissolved under conditions of heating stirring
Enter aromatic polyamide fibre, continues heating stirring and wait for that aromatic polyamide fibre is completely dissolved to get Fibrinolysis liquid；
B, under conditions of heating stirring, it is slowly added to pore creating material into the Fibrinolysis liquid, continues heating stirring to mixing
Uniformly to get aromatic polyamide casting solution；
C, the painting of the one or both sides of basement membrane is covered with the aromatic polyamide casting solution, being then placed into coagulation bath makes fragrance
Polyamide casting film liquid-phase conversion forms a film, and the film is compound to get aromatic polyamide by washing and high temperature drying successively again
Diaphragm；One kind in mixed liquor of the coagulation bath for deionized water or including deionized water and the second solvent, described second is molten
Agent is mixed by the first solvent and pore creating material.
6. preparation method as claimed in claim 5, which is characterized in that in step b, the aromatic polyamide casting solution is matched
Temperature processed is 50~80 DEG C.
7. preparation method as claimed in claim 5, which is characterized in that in step b, prepare the aromatic polyamide casting solution
When mixing speed be 300~2000rpm.
8. preparation method as claimed in claim 5, which is characterized in that the coagulation bath be include deionized water and the second solvent
Mixed liquor when, the quality parts ratio of deionized water and the second solvent is (0.5:1)~(5:1), the first solvent in the second solvent
It is consistent with the quality parts ratio of pore creating material with the quality parts ratio of pore creating material and the first solvent in aromatic polyamide casting solution.
9. preparation method as claimed in claim 5, which is characterized in that the thickness of the composite diaphragm is 11~30 μm, is breathed freely
Rate is 50~500s/100cc.
10. preparation method as claimed in claim 9, which is characterized in that the thickness of the composite diaphragm is 11~25 μm, is breathed freely
Rate is 100~160s/100cc.
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| CN111370625A (en) * | 2020-03-22 | 2020-07-03 | 华南理工大学 | Aramid fiber phase-transition coating lithium ion battery diaphragm and preparation method thereof |
| CN111603948A (en) * | 2020-05-21 | 2020-09-01 | 杭州科百特科技有限公司 | Nylon membrane and preparation method and application thereof |
| CN111603946A (en) * | 2020-05-21 | 2020-09-01 | 杭州科百特科技有限公司 | Nylon membrane and preparation method and application thereof |
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| CN103242556A (en) * | 2013-04-17 | 2013-08-14 | 广东精进能源有限公司 | Method for preparing aramid composite diaphragm |
| CN103531736A (en) * | 2013-10-27 | 2014-01-22 | 中国乐凯集团有限公司 | High-heat-resistance lithium-ion battery diaphragm and preparation method thereof |
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| CN103242556A (en) * | 2013-04-17 | 2013-08-14 | 广东精进能源有限公司 | Method for preparing aramid composite diaphragm |
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Cited By (5)
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| CN110550818A (en) * | 2019-08-20 | 2019-12-10 | 生态环境部华南环境科学研究所 | Efficient biogas slurry desalting treatment process after fermentation of dairy cow breeding wastewater |
| CN110550818B (en) * | 2019-08-20 | 2021-12-07 | 生态环境部华南环境科学研究所 | Efficient biogas slurry desalting treatment process after fermentation of dairy cow breeding wastewater |
| CN111370625A (en) * | 2020-03-22 | 2020-07-03 | 华南理工大学 | Aramid fiber phase-transition coating lithium ion battery diaphragm and preparation method thereof |
| CN111603948A (en) * | 2020-05-21 | 2020-09-01 | 杭州科百特科技有限公司 | Nylon membrane and preparation method and application thereof |
| CN111603946A (en) * | 2020-05-21 | 2020-09-01 | 杭州科百特科技有限公司 | Nylon membrane and preparation method and application thereof |
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