CN106935772A - A kind of electrokinetic cell lithium battery diaphragm and preparation method thereof - Google Patents
A kind of electrokinetic cell lithium battery diaphragm and preparation method thereof Download PDFInfo
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- CN106935772A CN106935772A CN201710274280.9A CN201710274280A CN106935772A CN 106935772 A CN106935772 A CN 106935772A CN 201710274280 A CN201710274280 A CN 201710274280A CN 106935772 A CN106935772 A CN 106935772A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M50/431—Inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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
One aspect of the present invention provides a kind of power vehicle lithium battery diaphragm, it has four layers, basement membrane, nano flame retardant layer, Electrospun nano-fibers layer and hot closed layer are followed successively by from bottom to top, wherein, basement membrane is the PET nucleopore membranes of 5 μm~20 μm of thickness, nano flame retardant layer is 0.5 μm~10 μm of fire resistant ceramic slurry, and Electrospun nano-fibers thickness degree is 2 μm~5 μm, and hot closed layer is the high-temperature-resistant epoxy resin of 5 μm~10 μm of thickness；Present invention also offers the preparation method of the lithium battery diaphragm；Can be greatly improved according to the lithium battery diaphragm thermal shrinkage prepared by the inventive method, heat endurance and hot closed are significantly improved, and security is very good.
Description
Technical field
The invention belongs to battery diaphragm technical field, and in particular to a kind of electrokinetic cell lithium battery diaphragm and its preparation side
Method.
Background technology
Today of the New Energy Industries such as electric motor car, energy-storage battery is given priority in the whole world, lithium battery is used as generally acknowledged ideal
Energy-storage travelling wave tube, has obtained concern higher.But in recent years, a series of lithium battery motor-car firing accident tables of common occurrence
Bright, safety problem has turned into the primary bottleneck of restriction power lithium battery for electric vehicle development.In the structure of lithium battery, barrier film is to close
One of interior layer assembly of key.The performance of barrier film determines the interfacial structure of battery, internal resistance etc., directly affects the capacity of battery, follows
The characteristic such as ring and security performance, the barrier film of excellent performance has important effect to the combination property for improving battery.Barrier film
Main Function is that the positive and negative electrode for making battery is separated, and prevents the two poles of the earth from contacting and short-circuit, additionally with can make electrolyte ion
The function of passing through.During charging, lithium ion deintercalation and embedded positive pole from negative pole overcharge or when temperature is raised, and barrier film is also
Can be conducted come barrier ion by closed pore, prevent blast.So barrier film largely determines the security of lithium battery.
Barrier film material should have chemical stability, can be resistant to electrolytic corrosion, and do not reacted when being contacted with both positive and negative polarity；
Barrier film is also with certain aperture and porosity, it is ensured that low resistance and ionic conductivity high, preferably saturating to lithium ion
The property crossed；Heat endurance and mechanical property that barrier film should also have, such as tensile strength.Because electrolyte is organic solvent body
System, barrier film also needs to the diaphragm material of organic solvent-resistant.
The marketization diaphragm material be mainly with polyethylene (polyethylene, PE), polypropylene (polypropylene,
PP polyolefin (Polyolefin) the class barrier film based on), wherein PE products are mainly obtained by wet processing, and PP products are main by doing
Method technique is obtained.Diaphragm material product mainly have individual layer PP, individual layer PE, PP+ ceramic coated, PE+ ceramic coateds, bilayer PP/PE,
Double-deck PP/PP and three layer of PP/PE/PP etc., wherein preceding two classes product is mainly used in 3C baby batteries field, rear a few class products are mainly used
In dynamic lithium battery field.Lithium battery diaphragm belongs to the battery supplementary material that country encourages development, while long-term in belonging to country
Cutting edge technology listed in scientific and technological development planning outline (2006-2020) the 11st：In efficient energy material technology
High efficient secondary battery material and key technology special topic.
Existing industrialization lithium battery diaphragm property indices can not be taken into account, the fusing point phase of polyalkene diaphragm bulk material
To relatively low, about 130 DEG C~165 DEG C, when battery is heated to be reached near the melting temperature of diaphragm material, barrier film occurs substantially
Dimensional contraction, produce hole, cause both positive and negative polarity contact and it is short-circuit, and then trigger cells burst explode accident.Therefore, safety
Property be always restrict power-type lithium ion battery development one of the main reasons.
In sum, the research of the lithium battery diaphragm of high security has important market value.
The content of the invention
In order to obvious dimensional contraction occurs when being heated for lithium battery diaphragm in solving electrokinetic cell in the prior art, produce
Raw hole, causes both positive and negative polarity to contact and short-circuit, and then triggers the defect of the accidents such as cells burst, the present invention to design and be prepared for one kind
The preferable electrokinetic cell lithium battery diaphragm of security.
On the one hand, the present invention provides a kind of power vehicle lithium battery diaphragm, and it has four layers, base is followed successively by from bottom to top
Film, nano flame retardant layer, Electrospun nano-fibers layer and hot closed layer, wherein, basement membrane is the PET nucleopores of 5 μm~20 μm of thickness
Film, nano flame retardant layer is 0.5 μm~10 μm of fire resistant ceramic slurry, and Electrospun nano-fibers thickness degree is 2 μm~5 μm, heat
Closed layer is the high-temperature-resistant epoxy resin of 5 μm~10 μm of thickness.
Further, in power vehicle lithium battery diaphragm of the present invention, the etching aperture of the PET nucleopore membranes is
0.1 μm~1.0 μm, density is 1 × 105~5 × 106/cm2。
Further, in power vehicle lithium battery diaphragm of the present invention, the Electrospun nano-fibers layer
Polymeric material is polyacrylonitrile, polyimides or Kynoar.
On the other hand, present invention also offers the preparation method of the power vehicle lithium battery diaphragm, it includes following
Step：
Step (1)：The preparation of basement membrane
Irradiation processing is carried out to PET film using heavy ion avcceleration, chemical erosion then is carried out to the PET nucleopore membranes after irradiation
Carve, etching solution is sodium hydrate aqueous solution, etch temperature is 70 DEG C~90 DEG C, and etching period is 30 minutes, spent after etching from
It is basement membrane to obtain PET nucleopore membranes after sub- water cleaning；
Step (2)：Coating fire resistant ceramic slurry
Fire resistant ceramic powder is stirred in a solvent, binding agent, thickener are sequentially added after ball milling, be again stirring for
Fire resistant ceramic slurry uniformly is obtained, fire resistant ceramic slurry is coated uniformly on PET nucleopore membranes surface obtained in step (1), dried
After obtain two layers of composite membrane；
Step (3)：Precipitation adds Electrospun nano-fibers layer
Electrostatic spinning solution is prepared with polymeric material and electrostatic spinning solvent, electrospinning parameters are set, by Static Spinning
Silk solution forms jet aspersion on two layers of composite membrane obtained by step (2), and sandwich diaphragm is obtained after precipitation dried process；
Step (4)：Spray hot closed layer
The high-temperature-resistant epoxy resin of molten condition is sprayed on sandwich diaphragm obtained in step (3), must after cooling
To lithium battery diaphragm.
Further, in the preparation method of power vehicle lithium battery diaphragm of the present invention, step (1) PET
The preparation of nucleopore membranes, specially：
Energy is 10MeV/u~50MeV/u's before using heavy ion avcceleration to provide window86Kr 26+Ion pair PET film is carried out
Irradiation processing, sweep current is 120nA~200nA, then carries out chemical etching to the PET nucleopore membranes after irradiation, and etching solution is
The sodium hydrate aqueous solution of concentration 1M, etch temperature is set to 70 DEG C~90 DEG C, and etching period is 30 minutes, spent after etching from
PET nucleopore film layers are obtained after sub- water cleaning.
Further, in the preparation method of power vehicle lithium battery diaphragm of the present invention, step (2) coating
Fire resistant ceramic slurry, the composition of raw materials of the fire resistant ceramic slurry for being used, in parts by weight for：
0.05 part~3 parts of vinyltrimethoxy silane, 10 parts of inorganic ceramic particle~40 parts, melamine polyphosphate
5 parts~30 parts, 30 parts~50 parts of solvent, 2 parts~10 parts of binding agent, 0.5 part~2 parts of thickener；
Wherein, the inorganic ceramic particle is specially nano titanium oxide or nano silicon,
The binding agent be butadiene-styrene rubber or polyacrylic acid,
The thickener be polyurethane or cellulose derivative,
The solvent is dimethylacetylamide, acetone or N~methyl pyrrolidone.
Further, in the preparation method of power vehicle lithium battery diaphragm of the present invention, step (2) coating
Fire resistant ceramic slurry, specific preparation process is：
(2-1) obtains modifier solution with 90% ethanol water dilute ethylene base trimethoxy silane, and ethanol is water-soluble
The volume ratio of liquid and vinyltrimethoxy silane is 1：3；
(2-2) adds inorganic ceramic particle and melamine polyphosphate in agitator, after being warming up to 55 DEG C, thereto
Modifier solution is added, after stirring, is vacuum dried at mixture is placed in into 60 DEG C, obtain fire resistant ceramic powder；
(2-3) stirs fire resistant ceramic powder in a solvent, and binding agent, thickener are sequentially added after ball milling, then
It is secondary to be uniformly mixing to obtain fire resistant ceramic slurry, fire resistant ceramic slurry is coated uniformly on PET nucleopore membranes tables obtained in step (1)
Face, sandwich diaphragm is obtained after drying.
Further, in the preparation method of power vehicle lithium battery diaphragm of the present invention, step (3) precipitation
Electrospun nano-fibers layer is added, specially：
Electrostatic spinning solution is prepared with polymeric material and electrostatic spinning solvent, setting electrospinning parameters are spinning temperature
30 DEG C~40 DEG C, relative humidity 45%~60%, voltage 10KV~25KV receives 10 centimetres of distance~20 centimetres, solution flow rate
0.8mL/h~4mL/h, recipient rotating speed 300rpm~400rpm, jet aspersion is formed in step (2) institute by electrostatic spinning solution
On the two layers of composite membrane for obtaining, sandwich diaphragm is obtained after precipitation dried process；
The polymeric material is polyacrylonitrile, polyimides or Kynoar；
The electrostatic spinning solvent is dimethylacetylamide or 1-METHYLPYRROLIDONE；
The polymeric material is 10%~20% with the mass fraction ratio of electrostatic spinning solvent：80%~90%.
Compared with prior art, beneficial effects of the present invention are：
1st, lithium battery diaphragm of the invention, to improve barrier film thermal shrinkage, is prevented in coating on base films nano flame retardant layer
Diaphragm retracts cause large area short circuit；Some thermal runaway points expand and form overall thermal runaway in preventing battery, and battery diaphragm exists
Heat endurance during high temperature circulation, lifts security.
2nd, lithium battery diaphragm of the invention sets up Electrospun nano-fibers layer, and layers of nanofibers is firmly tied with adjacent film layers
Close, it is possible to prevent nano flame retardant layer in inorganic particle " dry linting ", Electrospun nano-fibers layer can improve battery diaphragm
Aperture structure, further improve heat endurance of the power battery diaphragm during high temperature circulation.
3rd, the basement membrane of lithium battery diaphragm of the invention employs PET film, and the heat resistance of PET film is better than PP materials, sets up heat
Closed layer so that after temperature reaches hot closed temperature, is also not in that basement membrane is destroyed completely even if temperature is further improved,
Large area short circuit is caused, or even triggers blast, hot closed layer uses high-temperature-resistant epoxy resin, further improves power battery diaphragm
Heat endurance and hot closed during high temperature circulation, improve security.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to institute in embodiment
The accompanying drawing for needing to use is briefly described, it should be apparent that, drawings in the following description are only some implementations of the invention
Example, for those of ordinary skill in the art, without having to pay creative labor, can also be according to these accompanying drawings
Obtain other accompanying drawings.
Fig. 1 is the structural representation of power vehicle lithium battery diaphragm of the present invention.
1- basement membranes, 2- nano flame retardants layer, 3- Electrospun nano-fibers layer, the hot closed layers of 4-.
Specific embodiment
Technological means and effect that predetermined purpose is taken are reached for the present invention is expanded on further, below in conjunction with accompanying drawing and reality
Example is applied to specific embodiment of the invention, architectural feature and its effect, is described in detail as follows.
Embodiment 1：
Power vehicle lithium battery diaphragm as shown in Figure 1, it has four layers, and the resistance of basement membrane 1, nanometer is followed successively by from bottom to top
Combustion layer 2, Electrospun nano-fibers layer 3 and hot closed layer 4, wherein, basement membrane 1 is the PET nucleopore membranes of 5 μm~20 μm of thickness, is received
Rice flame-retardant layer 2 is 0.5 μm~10 μm of fire resistant ceramic slurry, and Electrospun nano-fibers 3 thickness of layer are 2 μm~5 μm, heat closure
Layer 4 is the high-temperature-resistant epoxy resin of 5 μm~10 μm of thickness.Wherein, the etching aperture of PET nucleopore membranes is 0.1 μm~1.0 μm, close
Spend is 1 × 105~5 × 106/cm2.The polymeric material of Electrospun nano-fibers layer is polyacrylonitrile, polyimides or poly- inclined
PVF.
Prepare embodiment 1：Power vehicle is prepared with lithium battery diaphragm
The preparation of step (1) PET nucleopore membranes
Energy is 10MeV/u's before using heavy ion avcceleration to provide window86Kr 26+Ion pair PET film carries out irradiation processing,
Sweep current is 120nA, and then the PET nucleopore membranes after irradiation are carried out with chemical etching, and etching solution is the NaOH of concentration 1M
The aqueous solution, etch temperature is set to 70 DEG C, and etching period is 30 minutes, and PET cores are obtained after being cleaned with deionized water after etching
Pore membrane layer.
Step (2) coats fire resistant ceramic slurry
The composition of raw materials of fire resistant ceramic slurry, in parts by weight for：
0.05 part of vinyltrimethoxy silane, 10 parts of nano titanium oxide, 5 parts of parts of melamine polyphosphate, diformazan
30 parts of yl acetamide, 2 parts of butadiene-styrene rubber, 0.5 part of polyurethane；
Coat fire resistant ceramic slurry process be：
(2-1) obtains modifier solution with 90% ethanol water dilute ethylene base trimethoxy silane, and ethanol is water-soluble
The volume ratio of liquid and vinyltrimethoxy silane is 1：3；
(2-2) adds nano titanium oxide and melamine polyphosphate in agitator, after being warming up to 55 DEG C, thereto
Modifier solution is added, after stirring, is vacuum dried at mixture is placed in into 60 DEG C, obtain fire resistant ceramic powder；
(2-3) stirs fire resistant ceramic powder in dimethylacetylamide, sequentially added after ball milling butadiene-styrene rubber,
Polyurethane, is again stirring for uniformly obtaining fire resistant ceramic slurry, and fire resistant ceramic slurry is coated uniformly on into PET obtained in step (1)
Nucleopore membranes surface, sandwich diaphragm is obtained after drying.
Step (3) precipitation adds Electrospun nano-fibers layer
Electrostatic spinning solution is prepared according to 10% and 90% mass percent with polyacrylonitrile and dimethylacetylamide, if
Electrospinning parameters are put for 40 DEG C of spinning temperature, relative humidity 60%, voltage 25KV receives 20 centimetres of distance, solution flow rate
4mL/h, recipient rotating speed 400rpm, by electrostatic spinning solution formation jet aspersion on two layers of composite membrane obtained by step (2),
Sandwich diaphragm is obtained after precipitation dried process.
Step (4)：Spray hot closed layer
The high-temperature-resistant epoxy resin of molten condition is sprayed on sandwich diaphragm obtained in step (3), must after cooling
To lithium battery diaphragm product.
After testing, the electrolyte retention of the composite lithium battery membrane that embodiment 1 is obtained is prepared up to 315%, and heat closure is warm
Degree is warming up to 500 DEG C up to 280 DEG C, and barrier film will not break through, and tensile strength is 45MPa, and puncture strength is 378g/mil, 0.5C electricity
Up to 98%, percent thermal shrinkage is 0.08% under conditions of 140 DEG C/h to pond circulation volume conservation rate.
Prepare embodiment 2：Power vehicle is prepared with lithium battery diaphragm
The preparation of step (1) PET nucleopore membranes
Energy is 50MeV/u's before using heavy ion avcceleration to provide window86Kr 26+Ion pair PET film carries out irradiation processing,
Sweep current is 200nA, and then the PET nucleopore membranes after irradiation are carried out with chemical etching, and etching solution is the NaOH of concentration 1M
The aqueous solution, etch temperature is set to 90 DEG C, and etching period is 30 minutes, and PET cores are obtained after being cleaned with deionized water after etching
Pore membrane layer.
Step (2) coats fire resistant ceramic slurry
The composition of raw materials of fire resistant ceramic slurry, in parts by weight for：
3 parts of vinyltrimethoxy silane, 40 parts of nano silicon, 30 parts of melamine polyphosphate, 50 parts of solvent,
10 parts of polyacrylic acid, 2 parts of sodium carboxymethylcellulose；
Coat fire resistant ceramic slurry process be：
(2-1) obtains modifier solution with 90% ethanol water dilute ethylene base trimethoxy silane, and ethanol is water-soluble
The volume ratio of liquid and vinyltrimethoxy silane is 1：3；
(2-2) adds nano silicon and melamine polyphosphate in agitator, after being warming up to 55 DEG C, thereto
Modifier solution is added, after stirring, is vacuum dried at mixture is placed in into 60 DEG C, obtain fire resistant ceramic powder；
(2-3) stirs fire resistant ceramic powder in 1-METHYLPYRROLIDONE, and polypropylene is sequentially added after ball milling
Acid, sodium carboxymethylcellulose, are again stirring for uniformly obtaining fire resistant ceramic slurry, and fire resistant ceramic slurry is coated uniformly on into step
(1) PET nucleopore membranes surface obtained in, sandwich diaphragm is obtained after drying.
Step (3) precipitation adds Electrospun nano-fibers layer
Electrostatic spinning to be prepared according to 20% and 80% mass percent molten with Kynoar and 1-METHYLPYRROLIDONE
Liquid, setting electrospinning parameters are 30 DEG C of spinning temperature, and relative humidity 45%, voltage 10KV receives 10 centimetres of distance, solution stream
Fast 0.8mL/h, recipient rotating speed 300rpm, form electrostatic spinning solution jet aspersion and are combined in two layers obtained by step (2)
On film, sandwich diaphragm is obtained after precipitation dried process.
Step (4)：Spray hot closed layer
The high-temperature-resistant epoxy resin of molten condition is sprayed on sandwich diaphragm obtained in step (3), must after cooling
To lithium battery diaphragm product.
After testing, up to 345%, hot closed temperature is up to 320 for the electrolyte retention of the composite lithium battery membrane for preparing
DEG C, 500 DEG C are warming up to, barrier film will not break through, and tensile strength is 40MPa, and puncture strength is 396g/mil, and 0.5C circulating batteries hold
Up to 96%, percent thermal shrinkage is 0.05% under conditions of 140 DEG C/h to amount conservation rate.
Prepare embodiment 3：Power vehicle is prepared with lithium battery diaphragm
The preparation of step (1) PET nucleopore membranes
Energy is 30MeV/u's before using heavy ion avcceleration to provide window86Kr 26+Ion pair PET film carries out irradiation processing,
Sweep current is 180nA, and then the PET nucleopore membranes after irradiation are carried out with chemical etching, and etching solution is the NaOH of concentration 1M
The aqueous solution, etch temperature is set to 85 DEG C, and etching period is 30 minutes, and PET cores are obtained after being cleaned with deionized water after etching
Pore membrane layer.
Step (2) coats fire resistant ceramic slurry
The composition of raw materials of fire resistant ceramic slurry, in parts by weight for：
1.5 parts of vinyltrimethoxy silane, 25 parts of nano silicon, 20 parts of melamine polyphosphate, dimethyl
35 parts of acetamide, 8 parts of butadiene-styrene rubber, 1.5 parts of hydroxypropyl cellulose；
Coat fire resistant ceramic slurry process be：
(2-1) obtains modifier solution with 90% ethanol water dilute ethylene base trimethoxy silane, and ethanol is water-soluble
The volume ratio of liquid and vinyltrimethoxy silane is 1：3；
(2-2) adds nano silicon and melamine polyphosphate in agitator, after being warming up to 55 DEG C, thereto
Modifier solution is added, after stirring, is vacuum dried at mixture is placed in into 60 DEG C, obtain fire resistant ceramic powder；
(2-3) stirs fire resistant ceramic powder in dimethylacetylamide, sequentially added after ball milling butadiene-styrene rubber,
Hydroxypropyl cellulose, is again stirring for uniformly obtaining fire resistant ceramic slurry, and fire resistant ceramic slurry is coated uniformly on into step (1) is obtained
PET nucleopore membranes surface, dry after obtain sandwich diaphragm.
Step (3) precipitation adds Electrospun nano-fibers layer
Electrostatic spinning solution is prepared according to 16% and 84% mass percent with Kynoar and dimethylacetylamide,
Setting electrospinning parameters are 35 DEG C of spinning temperature, and relative humidity 55%, voltage 20KV receives 16 centimetres of distance, solution flow rate
2.8mL/h, recipient rotating speed 300rpm, jet aspersion is formed in two layers of composite membrane obtained by step (2) by electrostatic spinning solution
On, obtain sandwich diaphragm after precipitation dried process.
Step (4)：Spray hot closed layer
The high-temperature-resistant epoxy resin of molten condition is sprayed on sandwich diaphragm obtained in step (3), must after cooling
To lithium battery diaphragm.
After testing, up to 375%, hot closed temperature is up to 280 for the electrolyte retention of the composite lithium battery membrane for preparing
DEG C, 500 DEG C are warming up to, barrier film will not break through, and tensile strength is 65MPa, and puncture strength is 348g/mil, and 0.5C circulating batteries hold
Up to 97%, percent thermal shrinkage is 0.03% under conditions of 140 DEG C/h to amount conservation rate.
Prepare embodiment 4：Power vehicle is prepared with lithium battery diaphragm
The preparation of step (1) PET nucleopore membranes
Energy is 40MeV/u's before using heavy ion avcceleration to provide window86Kr 26+Ion pair PET film carries out irradiation processing,
Sweep current is 160nA, and then the PET nucleopore membranes after irradiation are carried out with chemical etching, and etching solution is the NaOH of concentration 1M
The aqueous solution, etch temperature is set to 80 DEG C, and etching period is 30 minutes, and PET cores are obtained after being cleaned with deionized water after etching
Pore membrane layer.
Step (2) coats fire resistant ceramic slurry
The composition of raw materials of fire resistant ceramic slurry, in parts by weight for：
2 parts of vinyltrimethoxy silane, 35 parts of nano titanium oxide, 15 parts of melamine polyphosphate, 40 parts of acetone,
6 parts of polyacrylic acid, 1 part of polyurethane；
Coat fire resistant ceramic slurry process be：
(2-1) obtains modifier solution with 90% ethanol water dilute ethylene base trimethoxy silane, and ethanol is water-soluble
The volume ratio of liquid and vinyltrimethoxy silane is 1：3；
(2-2) adds nano titanium oxide and melamine polyphosphate in agitator, after being warming up to 55 DEG C, thereto
Modifier solution is added, after stirring, is vacuum dried at mixture is placed in into 60 DEG C, obtain fire resistant ceramic powder；
(2-3) stirs fire resistant ceramic powder in acetone, and polyacrylic acid, polyurethane are sequentially added after ball milling,
It is again stirring for uniformly obtaining fire resistant ceramic slurry, fire resistant ceramic slurry is coated uniformly on PET nucleopore membranes tables obtained in step (1)
Face, sandwich diaphragm is obtained after drying.
Step (3) precipitation adds Electrospun nano-fibers layer
Electrostatic spinning solution is prepared according to 12% and 88% mass percent with polyimides and 1-METHYLPYRROLIDONE,
Setting electrospinning parameters are 30 DEG C of spinning temperature, and relative humidity 50%, voltage 20KV receives 18 centimetres of distance, solution flow rate
3.5mL/h, recipient rotating speed 400rpm, jet aspersion is formed in two layers of composite membrane obtained by step (2) by electrostatic spinning solution
On, obtain sandwich diaphragm after precipitation dried process.
The polymeric material is 10%~20% with the mass fraction ratio of electrostatic spinning solvent：80%~90%.
Step (4)：Spray hot closed layer
The high-temperature-resistant epoxy resin of molten condition is sprayed on sandwich diaphragm obtained in step (3), must after cooling
To lithium battery diaphragm.
After testing, up to 315%, hot closed temperature is up to 280 for the electrolyte retention of the composite lithium battery membrane for preparing
DEG C, 500 DEG C are warming up to, barrier film will not break through, and tensile strength is 45MPa, and puncture strength is 378g/mil, and 0.5C circulating batteries hold
Up to 98%, percent thermal shrinkage is 0.07% under conditions of 140 DEG C/h to amount conservation rate.
According to the experimental result for preparing embodiment 1-4, the lithium battery diaphragm prepared according to the inventive method has non-
The thermal contraction performance of Chang Youyi, thermal contraction very little when being heated will not also rupture when temperature is up to 500 DEG C, it is ensured that electricity
The security of pond barrier film, while circulating battery capability retention reaches more than 96%, overall performance is significantly better than current similar
Product.
Above content is to combine specific preferred embodiment further description made for the present invention, it is impossible to assert
Specific implementation of the invention is confined to these explanations.For general technical staff of the technical field of the invention,
On the premise of not departing from present inventive concept, some simple deduction or replace can also be made, should be all considered as belonging to of the invention
Protection domain.
Claims (8)
1. a kind of power vehicle lithium battery diaphragm, it is characterised in that with four layers, basement membrane (1), nanometer are followed successively by from bottom to top
Flame-retardant layer (2), Electrospun nano-fibers layer (3) and hot closed layer (4), wherein, basement membrane (1) is the PET of 5 μm~20 μm of thickness
Nucleopore membranes, nano flame retardant layer (2) is 0.5 μm~10 μm of fire resistant ceramic slurry, and Electrospun nano-fibers layer (3) thickness is 2 μ
M~5 μm, hot closed layer (4) is the high-temperature-resistant epoxy resin of 5 μm~10 μm of thickness.
2. power vehicle lithium battery diaphragm according to claim 1, it is characterised in that the etching of the PET nucleopore membranes
Aperture is 0.1 μm~1.0 μm, and density is 1 × 105~5 × 106/cm2。
3. power vehicle lithium battery diaphragm according to claim 1, it is characterised in that the Electrospun nano-fibers
The polymeric material of layer is polyacrylonitrile, polyimides or Kynoar.
4. the preparation method of the power vehicle lithium battery diaphragm described in any one of claims 1 to 3, it is characterised in that include
Following steps：
Step (1)：The preparation of basement membrane
Irradiation processing is carried out to PET film using heavy ion avcceleration, chemical etching then is carried out to the PET nucleopore membranes after irradiation,
Etching solution is sodium hydrate aqueous solution, and etch temperature is 70 DEG C~90 DEG C, and etching period is 30 minutes, and deionized water is used after etching
It is basement membrane that PET nucleopore membranes are obtained after cleaning；
Step (2)：Coating fire resistant ceramic slurry
Fire resistant ceramic powder is stirred in a solvent, binding agent, thickener are sequentially added after ball milling, be again stirring for uniform
Fire resistant ceramic slurry is obtained, fire resistant ceramic slurry is coated uniformly on PET nucleopore membranes surface obtained in step (1), after drying
To two layers of composite membrane；
Step (3)：Precipitation adds Electrospun nano-fibers layer
Electrostatic spinning solution is prepared with polymeric material and electrostatic spinning solvent, electrospinning parameters are set, electrostatic spinning is molten
Liquid forms jet aspersion on two layers of composite membrane obtained by step (2), and sandwich diaphragm is obtained after precipitation dried process；
Step (4)：Spray hot closed layer
The high-temperature-resistant epoxy resin of molten condition is sprayed on sandwich diaphragm obtained in step (3), lithium is just obtained after cooling
Battery diaphragm.
5. preparation method according to claim 4, it is characterised in that the preparation of step (1) the PET nucleopore membranes, specifically
For：
Energy is 10MeV/u~50MeV/u's before using heavy ion avcceleration to provide window86Kr 26+Ion pair PET film is irradiated
Processing, sweep current is 120nA~200nA, then carries out chemical etching to the PET nucleopore membranes after irradiation, and etching solution is concentration
The sodium hydrate aqueous solution of 1M, etch temperature is set to 70 DEG C~90 DEG C, and etching period is 30 minutes, and deionized water is used after etching
PET nucleopore film layers are obtained after cleaning.
6. preparation method according to claim 4, it is characterised in that the step (2) coats fire resistant ceramic slurry, is made
The composition of raw materials of fire resistant ceramic slurry, in parts by weight for：
0.05 part~3 parts of vinyltrimethoxy silane, 10 parts~40 parts of inorganic ceramic particle, 5 parts of melamine polyphosphate
~30 parts, 30 parts~50 parts of solvent, 2 parts~10 parts of binding agent, 0.5 part~2 parts of thickener；
Wherein, the inorganic ceramic particle is specially nano titanium oxide or nano silicon,
The binding agent be butadiene-styrene rubber or polyacrylic acid,
The thickener be polyurethane or cellulose derivative,
The solvent is dimethylacetylamide, acetone or N~methyl pyrrolidone.
7. preparation method according to claim 6, it is characterised in that the step (2) coats fire resistant ceramic slurry, specifically
Preparation process is：
(2-1) obtains modifier solution with 90% ethanol water dilute ethylene base trimethoxy silane, ethanol water and
The volume ratio of vinyltrimethoxy silane is 1：3；
(2-2) adds inorganic ceramic particle and melamine polyphosphate in agitator, after being warming up to 55 DEG C, is added thereto to
Modifier solution, after stirring, is vacuum dried at mixture is placed in into 60 DEG C, obtains fire resistant ceramic powder；
(2-3) stirs fire resistant ceramic powder in a solvent, and binding agent, thickener are sequentially added after ball milling, stirs again
Mix and uniformly obtain fire resistant ceramic slurry, fire resistant ceramic slurry is coated uniformly on PET nucleopore membranes surface obtained in step (1), do
Sandwich diaphragm is obtained after dry.
8. preparation method according to claim 4, it is characterised in that step (3) precipitation adds electrostatic spinning nano
Fibrage, specially：
Electrostatic spinning solution is prepared with polymeric material and electrostatic spinning solvent, setting electrospinning parameters are 30 DEG C of spinning temperature
~40 DEG C, relative humidity 45%~60%, voltage 10KV~25KV receives 10 centimetres~20 centimetres of distance, solution tasselled
0.8mL/h~4mL/h, recipient rotating speed 300rpm~400rpm, jet aspersion is formed in step (2) institute by electrostatic spinning solution
On the two layers of composite membrane for obtaining, sandwich diaphragm is obtained after precipitation dried process；
The polymeric material is polyacrylonitrile, polyimides or Kynoar；
The electrostatic spinning solvent is dimethylacetylamide or 1-METHYLPYRROLIDONE；
The polymeric material is 10%~20% with the mass fraction ratio of electrostatic spinning solvent：80%~90%.
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| CN113594634A (en) * | 2021-06-18 | 2021-11-02 | 苏州大学 | High-ionic-conductivity lithium battery diaphragm with self-closing function and preparation method thereof |
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| CN113675529A (en) * | 2021-08-19 | 2021-11-19 | 杭州君杭科技有限公司 | Lithium ion battery diaphragm material for new energy automobile and preparation method thereof |
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