CN107919452A - A kind of diaphragm for lithium ion battery and preparation method thereof and lithium ion battery - Google Patents
A kind of diaphragm for lithium ion battery and preparation method thereof and lithium ion battery Download PDFInfo
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- CN107919452A CN107919452A CN201711137173.8A CN201711137173A CN107919452A CN 107919452 A CN107919452 A CN 107919452A CN 201711137173 A CN201711137173 A CN 201711137173A CN 107919452 A CN107919452 A CN 107919452A
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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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention belongs to field of lithium ion battery material, more particularly to a kind of diaphragm for lithium ion battery and preparation method thereof and lithium ion battery.The present invention provides a kind of diaphragm for lithium ion battery, including：Polymeric matrix and sb oxide particle containing halogens；The sb oxide particle is coated with the polymeric matrix containing halogens.Diaphragm for lithium ion battery of the present invention has used the polymeric matrix containing halogens, and is coated with sb oxide particle on the surface of the polymeric matrix containing halogens.Performance test shows that the diaphragm for lithium ion battery heat endurance is strong, imbibition rate is high, ionic conductivity is high, the self-gravitation time is short, can solve the problems, such as existing diaphragm for lithium ion battery is poor with the wellability of electrolyte, security is low etc..
Description
Technical field
The invention belongs to field of lithium ion battery material, more particularly to a kind of diaphragm for lithium ion battery and preparation method thereof
And lithium ion battery.
Background technology
In recent years, with digital product to volume and continuation of the journey require continuous improvement and electric automobile fast development,
Traditional chemical power supply such as lead accumulator, Ni-MH battery and nickel-cadmium cell can not meet demands.Lithium ion battery is due to its work
Make voltage height, have extended cycle life, energy density is big and is widely used and gradually instead of traditional chemical power supply.Lithium ion battery
It is made of cathode, anode, membrane and four big key component of electrolyte, wherein, the property of membrane in itself can largely shadow
Ring performance such as cycle life, high rate performance and the security to lithium ion battery.
The material of now widely used membrane is polyolefin, such as polyethylene, polypropylene.Asked existing for polyalkene diaphragm
Topic includes：The wellability of membrane and electrolyte is poor, membrane cannot well with electrolyte infiltrate, influence battery circulation and times
Rate performance.In addition, the heat endurance of polyalkene diaphragm is also poor, the fusing point of polyethylene diagrams is only 130 DEG C or so, and polypropylene
For 160 DEG C or so, electrolyte is inflammable organic solvent again, when battery is in the extreme case such as high temperature or partial short-circuit heat release
Under, membrane heat shrinkable causes positive and negative anodes to come into contact in a large area short circuit and releases heat, so as to trigger the burning and explosion of battery.
The content of the invention
In view of this, the present invention provides a kind of diaphragm for lithium ion battery, for solve existing lithium ion battery with every
The problem of film is poor with the wellability of electrolyte, security is low.
The concrete technical scheme of the present invention is as follows：
A kind of diaphragm for lithium ion battery, including：Polymeric matrix and sb oxide particle containing halogens；
The sb oxide particle is coated with the polymeric matrix containing halogens.
Preferably, the mass percent of the sb oxide particle is 1%~50%.
Preferably, the polymeric matrix containing halogens includes Kynoar matrix, poly tetrafluoro ethylene matrix, gathers
Vinyl chloride matrix, Kynoar-hexafluoropropylene copolymer matrix, Kynoar-chlorotrifluoroethylene matrix, chlorination
One or more in base polyethylene and chlorinated polypropylene matrix.
Preferably, the sb oxide particle include antimony oxide, antimony pentoxide and algaroth in one kind or
It is a variety of.
Present invention also offers a kind of preparation method of diaphragm for lithium ion battery described in above-mentioned technical proposal, including：
A) sb oxide particle is added after binding agent is mixed with solvent and forms slurry；
B) slurry is coated on the polymeric matrix containing halogens, obtains diaphragm for lithium ion battery.
Preferably, the mass ratio of the sb oxide particle and the binding agent is 1~49：1.
Preferably, the binding agent includes Kynoar, Kynoar-hexafluoropropene, Kynoar-trifluoro chlorine
Ethene, polyvinyl alcohol, the one or more of butadiene-styrene rubber and carboxymethyl cellulose；
The solvent includes dimethylformamide, dimethylacetylamide, 1-methyl-2-pyrrolidinone, tetrahydrofuran, acetone, second
The one or more of alcohol and water.
Preferably, it is described to be coated applied to spraying process or prolong the coating of stream method.
Present invention also offers a kind of lithium ion battery, including membrane and electrolyte, the membrane is above-mentioned technical proposal
Diaphragm for lithium ion battery prepared by the preparation method of the diaphragm for lithium ion battery or above-mentioned technical proposal.
Further, further include：Flame-retardant additive；
The flame retardant additives are made an addition in the electrolyte.
In conclusion the present invention provides a kind of diaphragm for lithium ion battery, including：Polymeric matrix containing halogens
With sb oxide particle；The sb oxide particle is coated with the polymeric matrix containing halogens.Lithium of the present invention from
Sub- battery separator has used the polymeric matrix containing halogens, and is coated on the surface of the polymeric matrix containing halogens
Sb oxide particle.Performance test shows, the diaphragm for lithium ion battery heat endurance is strong, imbibition rate is high, ionic conductivity is high,
The self-gravitation time is short, can solve the problems, such as existing diaphragm for lithium ion battery is poor with the wellability of electrolyte, security is low etc..
Embodiment
The present invention provides a kind of diaphragm for lithium ion battery, for solving existing diaphragm for lithium ion battery and electrolyte
Wellability is poor, the problem of security is low.
The technical solution in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation
Example is only part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this area is common
Technical staff's all other embodiments obtained without making creative work, belong to the model that the present invention protects
Enclose.
A kind of diaphragm for lithium ion battery, including：Polymeric matrix and sb oxide particle containing halogens；
Sb oxide particle is coated with polymeric matrix containing halogens.
In the present invention, the mass percent of sb oxide particle is 1%~50%, the mass percent of sb oxide particle
More preferably 10%~30%.
In the present invention, the polymeric matrix containing halogens includes Kynoar matrix, poly tetrafluoro ethylene matrix, polychlorostyrene
Ethene matrix, Kynoar-hexafluoropropylene copolymer matrix, Kynoar-chlorotrifluoroethylene matrix, chlorination gather
One or more in ethene matrix and chlorinated polypropylene matrix.
In the present invention, the polymeric matrix containing halogens is electrospinning or non-woven polymers, the polymerization containing halogens
The thickness of thing matrix is 5~200 μm, and porosity is 30%~90%.Polymeric matrix containing halogens is self-control or commercially available.
In the present invention, sb oxide particle includes one kind or more in antimony oxide, antimony pentoxide and algaroth
Kind, the particle diameter of sb oxide particle is 0.02~2 μm.
In the present invention, the presence of membrane surface sb oxide particle can not only improve the heat endurance of membrane, membrane with
Other chemical properties of the wellability of electrolyte, ionic conductivity and membrane, and positioned at the sb oxide grain of membrane surface
Son gives full play to the fire resistance of sb oxide particle, has membrane and play excellent resistance under the action of halogens
Fire performance.
Present invention also offers the preparation method of diaphragm for lithium ion battery, including：
A) sb oxide particle is added after binding agent is mixed with solvent and forms slurry；
B) slurry is coated on the polymeric matrix containing halogens, obtains diaphragm for lithium ion battery.
In the present invention, the mass ratio of sb oxide particle and binding agent is 1~49：1, sb oxide particle and binding agent
Mass ratio is more preferably 5.67~19：1.
Binding agent includes Kynoar, Kynoar-hexafluoropropene, Kynoar-chlorotrifluoroethylene, polyethylene
The one or more of alcohol, butadiene-styrene rubber and carboxymethyl cellulose；
Solvent include dimethylformamide, dimethylacetylamide, 1-methyl-2-pyrrolidinone, tetrahydrofuran, acetone, ethanol and
The one or more of water.
In the present invention, after the slurry is coated on the polymeric matrix containing halogens, lithium ion is obtained
Before battery separator, further include：It is dry to remove solvent.
It should be noted that slurry is coated on a surface or two surfaces for the polymeric matrix containing halogens.
In the present invention, coated applied to spraying process or prolong the coating of stream method.
In the present invention, the preparation method of diaphragm for lithium ion battery is easy to operate, is adapted to promote and apply.
Present invention also offers a kind of lithium ion battery, including：Diaphragm for lithium ion battery and electrolyte.
In the present invention, further include：Flame-retardant additive；
Flame-retardant additive is made an addition in electrolyte.
In the present invention, flame-retardant additive for trimethyl phosphate, triethyl phosphate, triphenyl phosphate, di(2-ethylhexyl)phosphate benzene toluene ester,
In tributyl phosphate, dimethyl methyl phosphonate, a fluoromethyl ethylene carbonate, difluoromethyl ethylene carbonate and butyrolactone
One or more, the mass fraction of flame-retardant additive is 0.1%~10%.
In the prior art, it is the security of raising lithium ion battery, the usually heat by improving diaphragm for lithium ion battery
Start with terms of stability and in the electrolytic solution addition flame retardant constituent two.Inorganic particulate is introduced in membrane can not only carry
The heat endurance of high membrane can also improve the wellability of membrane and electrolyte, and the ionic conductivity for increasing membrane finally improves electricity
The chemical property in pond.But the safety issue of electrolyte burning can not be solved by only improving the heat endurance of membrane.And
Fire retardant is added in electrolyte can slow down the burning of electrolyte, but actual flame retardant effect has with the flame retardant agent content in electrolyte
Close, do not reach flame retardant effect when flame retardant agent content is relatively low in electrolyte, understand strong influence battery when flame retardant agent content is higher again
Chemical property.
In the present invention, including the lithium ion battery of diaphragm for lithium ion battery has excellent chemical property, gathers around at the same time
There is very high security.Fire-retardant membrane in the present invention uses electrospinning containing halogens or non-woven polymers as base
Body, sb oxide particle is coated on the matrix by spraying or the tape casting, prepares the lithium-ion electric with high efficiency flame retardance
Pond membrane.In membrane the presence of sb oxide particle can not only improve membrane heat endurance, with the wellability of electrolyte,
Other of ionic conductivity and membrane chemical property, while sb oxide particle can fully be sent out under the action of halogens
Fire resistance is waved, realizes the security for improving battery from many aspects while diaphragm electrochemical performance is improved.
In the present invention, sb oxide particle is incorporated into membrane as a kind of inorganic matter, can improve the thermostabilization of membrane
Property, the chemical property with the wellability of electrolyte, ionic conductivity and membrane, so as to improve the security and electrochemistry of battery
Performance.
Sb oxide particle is attached to the surface of membrane by coating, can be melted rapidly on the surface of object initial stage in burning
Change, which forms protective film and reduces ignition temperature by the internal endothermic reaction, plays flame retardant effect, and sb oxide particle is coated in base
The anti-flammability of sb oxide particle will be improved in the surface of body.Although sb oxide particle flame retardant effect when being used alone is general,
But then there is good cooperative effect with halide and used time, can greatly improve overall flame retardant effect.Antimony is aoxidized
Thing particle is coated to the heat endurance and wetability that membrane can be not only improved in the electrospinning or non-woven fabrics of halogen matrix, may be used also
To hinder the burning of electrolyte and membrane as fire retardant, so as to achieve the purpose that to improve battery security from many aspects.Secondly
Sb oxide particle quickly resolves into various antimonials and halogen radical under the action of halogen, and consumption flame energy is simultaneously
The chemical process of change burning, makes membrane have efficient fire resistance.
The present invention provides a kind of diaphragm for lithium ion battery, including：Polymeric matrix and antimony oxidation containing halogens
Thing particle；Sb oxide particle is coated with polymeric matrix containing halogens.Diaphragm for lithium ion battery of the present invention uses
Polymeric matrix containing halogens, and coat sb oxide particle on the surface of the polymeric matrix containing halogens.Property
It can test and show, the diaphragm for lithium ion battery heat endurance is strong, imbibition rate is high, ionic conductivity is high, the self-gravitation time is short, energy
Enough solve the problems, such as existing diaphragm for lithium ion battery is poor with the wellability of electrolyte, security is low etc..
Embodiment 1
Kynoar-chlorotrifluoroethylene of molecular weight 27~290,000 is dissolved in dimethylformamide, configuration quality
Percentage is 20% spinning solution.Take out 3mL spinning solutions to be placed in syringe, syringe needle internal diameter is 0.8mm, and positive high voltage is
12kV, negative high voltage 1.3kV, it is 0.030mm/min that spinning solution, which injects speed, and temperature is 35 DEG C, is made by electrostatic spinning
Polymeric matrix.It is dissolved in as Kynoar-chlorotrifluoroethylene of binding agent in solvent dimethylformamide, configures matter
Measure percentage be 2% coating solution, by antimony oxide add coating solution in and be uniformly dispersed, wherein antimony oxide with
The mass ratio of Kynoar-chlorotrifluoroethylene is 9：1.Coating solution containing antimony oxide is coated to and passes through electrostatic spinning
Two surfaces of the matrix of preparation, the wherein mass fraction of antimony oxide are 16%, up to lithium ion after dry removing solvent
Battery separator.
Embodiment 2
Kynoar-hexafluoropropene of molecular weight 57~600,000 is dissolved in dimethylformamide, configuration quality hundred
Fraction is 20% spinning solution.Take out 3mL spinning solutions to be placed in syringe, syringe needle internal diameter is 0.8mm, and positive high voltage is
12kV, negative high voltage 1.3kV, it is 0.028mm/min that spinning solution, which injects speed, and temperature is 35 DEG C, is made by electrostatic spinning
Polymeric matrix.It is dissolved in as Kynoar-hexafluoropropene of binding agent in solvent dimethylformamide, configuration quality
Percentage is 2% coating solution, and antimony oxide is added in coating solution and is uniformly dispersed, wherein antimony oxide is with gathering
The mass ratio of vinylidene chlorotrifluoroethylene is 92：8.Coating solution containing antimony oxide is coated to by electrostatic spinning system
Two surfaces of standby matrix, the wherein mass fraction of antimony oxide are 18%, up to lithium-ion electric after dry removing solvent
Pond membrane.
Embodiment 3
The Kynoar of Kynoar-chlorotrifluoroethylene of molecular weight 27~290,000 and molecular weight 57~600,000 is molten
For solution in dimethylformamide, configuration quality percentage is 18% spinning solution.Take out 3mL spinning solutions and be placed in syringe
In, syringe needle internal diameter is 0.8mm, positive high voltage 12.2kV, negative high voltage 1.3kV, and it is 0.028mm/ that spinning solution, which injects speed,
Min, temperature are 35 DEG C, and polymeric matrix is made by electrostatic spinning.Using as Kynoar-chlorotrifluoroethylene of binding agent
It is dissolved in solvent dimethylformamide, configuration quality percentage is 2% coating solution, and it is molten that antimony pentoxide is added coating
In liquid and it is uniformly dispersed, coating solution containing antimony pentoxide is coated to two surfaces of the matrix prepared by electrostatic spinning, its
The mass fraction of middle antimony pentoxide is 16%, up to diaphragm for lithium ion battery after dry removing solvent.
Embodiment 4
The Kynoar of molecular weight 100~1,200,000 is dissolved in dimethylformamide, configuration quality percentage is
18% spinning solution.Take out 3mL spinning solutions to be placed in syringe, syringe needle internal diameter is 0.8mm, positive high voltage 12kV, bears height
Press as 1.3kV, it is 0.028mm/min that spinning solution, which injects speed, and temperature is 35 DEG C, and polymer matrix is made by electrostatic spinning
Body.It is dissolved in as Kynoar-chlorotrifluoroethylene of binding agent in solvent dimethylformamide, configuration quality percentage
For 2% spray solution, antimony oxide is added in spray solution and is uniformly dispersed, wherein antimony oxide and polyvinylidene fluoride
The mass ratio of alkene chlorotrifluoroethylene is 9：1.The coating solution containing antimony oxide is sprayed to electrostatic spinning using spray gun to prepare
Matrix two surfaces, the wherein mass fraction of antimony oxide is 22%, through it is dry remove solvent after up to lithium ion battery
Use membrane.
Embodiment 5
Kynoar-chlorotrifluoroethylene of molecular weight 27~290,000 is dissolved in dimethylformamide, configuration quality
Percentage is 20% spinning solution.Take out 3mL spinning solutions to be placed in syringe, syringe needle internal diameter is 0.8mm, and positive high voltage is
12kV, negative high voltage 1.3kV, it is 0.028mm/min that spinning solution, which injects speed, and temperature is 35 DEG C, is made by electrostatic spinning
Polymeric matrix.It is dissolved in as Kynoar-chlorotrifluoroethylene of binding agent in solvent dimethylformamide, configures matter
Measure percentage be 2% spray solution, by antimony pentoxide add spray solution in and be uniformly dispersed, wherein antimony pentoxide with
The mass ratio of Kynoar chlorotrifluoroethylene is 92：8.The coating solution containing antimony pentoxide is sprayed into electrostatic using spray gun
Two surfaces of matrix prepared by spinning, the wherein mass fraction of antimony oxide are 20%, up to lithium after dry removing solvent
Ion battery membrane.
Comparative example 1
The Kynoar of molecular weight 100~1,200,000 is dissolved in dimethylformamide, configuration quality percentage is
18% spinning solution.Take out 3mL spinning solutions to be placed in syringe, syringe needle internal diameter is 0.8mm, positive high voltage 12kV, bears height
Press as 1.3kV, it is 0.028mm/min that spinning solution, which injects speed, and temperature is 35 DEG C, obtained after spinning Kynoar without
Woven fabric membrane.
Comparative example 2
Kynoar-chlorotrifluoroethylene of molecular weight 27~290,000 is dissolved in dimethylformamide, configuration quality
Percentage is 20% spinning solution.By antimony oxide add spinning solution in and be uniformly dispersed, wherein antimony oxide with
The mass ratio of Kynoar-chlorotrifluoroethylene is 1：60.Take out 3mL spinning solutions to be placed in syringe, syringe needle internal diameter is
0.8mm, positive high voltage 12kV, negative high voltage 1.3kV, it is 0.028mm/min that spinning solution, which injects speed, and temperature is 35 DEG C, is spun
Membrane is obtained after silk.
Comparative example 3
The Kynoar of molecular weight 100~1,200,000 is dissolved in dimethylformamide, configuration quality percentage is
20% spinning solution.Antimony pentoxide is added in spinning solution and is uniformly dispersed, wherein antimony pentoxide and polyvinylidene fluoride
The mass ratio of alkene is 1：50.Take out 3mL spinning solutions to be placed in syringe, syringe needle internal diameter is 0.8mm, positive high voltage 12kV, is born
High pressure is 1.3kV, and it is 0.028mm/min that spinning solution, which injects speed, and temperature is 35 DEG C, and membrane is obtained after spinning.
Comparative example 4
The polyacrylonitrile of molecular weight 150,000 is dissolved in dimethylformamide, configuration quality percentage is 10% spinning
Solution.5mL spinning solutions are taken out to be placed in syringe, syringe needle internal diameter is 0.7mm, positive high voltage 15kV, negative high voltage 2.2kV,
It is 0.075mm/min that spinning solution, which injects speed, and temperature is 35 DEG C, and polymeric matrix is made by electrostatic spinning.It will be used as viscous
Kynoar-chlorotrifluoroethylene of knot agent is dissolved in solvent dimethylformamide, and configuration quality percentage is 2% coating
Solution, antimony oxide is added in coating solution and is uniformly dispersed, wherein antimony oxide and Kynoar-trifluoro chloroethene
The mass ratio of alkene is 9：1.Coating solution containing antimony oxide is coated to two surfaces of the matrix prepared by electrostatic spinning,
Wherein the mass fraction of antimony oxide is 16%, up to ion battery membrane after dry removing solvent.
Comparative example 5
The Kynoar of molecular weight 100~1,200,000 is dissolved in dimethylformamide, configuration quality percentage is
18% spinning solution.Take out 3mL spinning solutions to be placed in syringe, syringe needle internal diameter is 0.8mm, positive high voltage 12kV, bears height
Press as 1.3kV, it is 0.028mm/min that spinning solution, which injects speed, and temperature is 35 DEG C, and polymer matrix is made by electrostatic spinning
Body.It is dissolved in as Kynoar-hexafluoropropene of binding agent in solvent dimethylformamide, configuration quality percentage is
2% coating solution, alundum (Al2O3) is added in coating solution and is uniformly dispersed, wherein alundum (Al2O3) and Kynoar
The mass ratio of chlorotrifluoroethylene is 9：1.Coating solution containing alundum (Al2O3) is coated to the matrix prepared by electrostatic spinning
Two surfaces, the wherein mass fraction of alundum (Al2O3) is 18%, through it is dry remove solvent after up to diaphragm for lithium ion battery.
Embodiment 6
Membrane in above-described embodiment 1~5 and comparative example 1~5 is tested for the property, performance test includes：Thermostabilization
Property test, imbibition rate test, ionic conductivity test and self-gravitation time test.
Heat stability testing：Membrane is cut into the square of 2cm × 2cm, at 130 DEG C place 30min after measurement every
The area of film and compared with initial area, calculates the percentage of the area of membrane after heat treatment and initial area.
Imbibition rate is tested：Weigh the quality m of membrane1, membrane is all then infiltrated into 4h in the electrolytic solution, takes out membrane,
The unnecessary electrolyte of membrane surface is removed with filter paper and weighs quality m2.Imbibition rate is calculated as follows：
Imbibition rate
Ionic conductivity is tested：Sheet of two stainless steel substrates as working electrode test membrane is used using Electrode with Electrochemical Impedance Spectroscopy
Impedance R is levied, uses micrometer (precision degree：5 points on sample 0.01mm) are arbitrarily taken to test the thickness of membrane simultaneously on membrane
It is averaged and is calculated as thickness d.The calculation formula of the ionic conductivity of membrane is as follows：
Ionic conductivity
Wherein S is the effective area of contact area, that is, membrane of stainless steel substrates and membrane.
Self-gravitation time test：The membrane of 5cm × 5cm is taken, the electrolyte of 1g is added dropwise on membrane, is lighted and remembered with lighter
It is recorded from the time lighted to extinguishing.
In above performance test, the electrolyte used in imbibition rate test and self-gravitation time test is 1mo/L LiPF6/
Ethylene carbonate+diethyl carbonate (volume ratio 1：1) electrolyte.
Above-mentioned the performance test results such as table 1, the heat endurance of 1~5 membrane of the results show embodiment is apparently higher than comparative example 1
The heat endurance of membrane is suitable with the heat endurance of 2~5 membrane of comparative example；The imbibition rate of 1~5 membrane of embodiment apparently higher than
The imbibition rate of 1 membrane of comparative example, higher than the imbibition rate of 2~5 membrane of comparative example；The ionic conductivity of 1~5 membrane of embodiment is obvious
Higher than the ionic conductivity of 1 membrane of comparative example, higher than the ionic conductivity of 2~5 membrane of comparative example；1~5 membrane of embodiment from
Fall time is significantly shorter than the self-gravitation time of 1~5 membrane of comparative example.The result shows that membrane of the present invention, which uses, contains halogens
Polymeric matrix, and the polymeric matrix containing halogens surface coating sb oxide particle can significantly improve lithium from
The performance of sub- battery separator, solves the problems, such as that existing diaphragm for lithium ion battery is poor with the wellability of electrolyte, security is low.
1 membrane properties test result of table
| Heat endurance (%) | Imbibition rate (%) | Ionic conductivity (mS/cm) | The self-gravitation time (s) | |
| Embodiment 1 | 98 | 643 | 1.07 | 11 |
| Embodiment 2 | 97 | 701 | 1.13 | 9 |
| Embodiment 3 | 95 | 683 | 1.10 | 10 |
| Embodiment 4 | 94 | 653 | 1.08 | 11 |
| Embodiment 5 | 95 | 689 | 1.10 | 10 |
| Comparative example 1 | 86 | 572 | 0.89 | 22 |
| Comparative example 2 | 94 | 589 | 0.98 | 19 |
| Comparative example 3 | 95 | 613 | 1.02 | 21 |
| Comparative example 4 | 94 | 592 | 1.05 | 22 |
| Comparative example 5 | 93 | 603 | 0.99 | 20 |
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
- A kind of 1. diaphragm for lithium ion battery, it is characterised in that including：Polymeric matrix and sb oxide grain containing halogens Son；The sb oxide particle is coated with the polymeric matrix containing halogens.
- 2. diaphragm for lithium ion battery according to claim 1, it is characterised in that the quality hundred of the sb oxide particle Divide than being 1%~50%.
- 3. diaphragm for lithium ion battery according to claim 1, it is characterised in that the polymer matrix containing halogens Body includes Kynoar matrix, poly tetrafluoro ethylene matrix, PVC base system, Kynoar-hexafluoropropylene copolymer base Body, Kynoar-chlorotrifluoroethylene matrix, haloflex matrix and one kind or more in chlorinated polypropylene matrix Kind.
- 4. diaphragm for lithium ion battery according to claim 1, it is characterised in that the sb oxide particle includes three oxygen Change the one or more in two antimony, antimony pentoxide and algaroth.
- A kind of 5. preparation method of diaphragm for lithium ion battery described in claim 1, it is characterised in that including：A) sb oxide particle is added after binding agent is mixed with solvent and forms slurry；B) slurry is coated on the polymeric matrix containing halogens, obtains diaphragm for lithium ion battery.
- 6. the preparation method of diaphragm for lithium ion battery according to claim 5, it is characterised in that the sb oxide particle Mass ratio with the binding agent is 1~49：1.
- 7. the preparation method of diaphragm for lithium ion battery according to claim 5, it is characterised in that the binding agent includes poly- Vinylidene, Kynoar-hexafluoropropene, Kynoar-chlorotrifluoroethylene, polyvinyl alcohol, butadiene-styrene rubber and carboxymethyl The one or more of cellulose；The solvent include dimethylformamide, dimethylacetylamide, 1-methyl-2-pyrrolidinone, tetrahydrofuran, acetone, ethanol and The one or more of water.
- 8. the preparation method of diaphragm for lithium ion battery according to claim 5, it is characterised in that described to be applied to spraying process Coat or prolong the coating of stream method.
- 9. a kind of lithium ion battery, including membrane and electrolyte, it is characterised in that the membrane is any one for Claims 1-4 Lithium ion battery prepared by the preparation method described in the item diaphragm for lithium ion battery or claim 5 to 8 any one is used Membrane.
- 10. lithium ion battery according to claim 9, it is characterised in that further include：Flame-retardant additive；The flame-retardant additive is made an addition in the electrolyte.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112048209A (en) * | 2020-09-21 | 2020-12-08 | 广东电网有限责任公司电力科学研究院 | Filler, grounding grid anticorrosive paint and preparation method thereof |
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| CN103633273A (en) * | 2013-12-10 | 2014-03-12 | 深圳市星源材质科技有限公司 | High-puncture-strength lithium ion battery diaphragm and preparation method thereof |
| CN104349897A (en) * | 2012-05-31 | 2015-02-11 | Lg化学株式会社 | Gas barrier film and method for manufacturing same |
| CN107195837A (en) * | 2017-04-28 | 2017-09-22 | 深圳市沃特玛电池有限公司 | Ceramic diaphragm and lithium ion battery |
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| CN87100195A (en) * | 1986-01-08 | 1987-10-07 | 氢系统公司 | The remodeling iontophoretic injection barrier film of electrolyzer |
| CN101501895A (en) * | 2006-02-16 | 2009-08-05 | 株式会社Lg化学 | Lithium secondary battery with enhanced heat-resistance |
| CN104349897A (en) * | 2012-05-31 | 2015-02-11 | Lg化学株式会社 | Gas barrier film and method for manufacturing same |
| CN103633273A (en) * | 2013-12-10 | 2014-03-12 | 深圳市星源材质科技有限公司 | High-puncture-strength lithium ion battery diaphragm and preparation method thereof |
| CN107195837A (en) * | 2017-04-28 | 2017-09-22 | 深圳市沃特玛电池有限公司 | Ceramic diaphragm and lithium ion battery |
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| CN112048209A (en) * | 2020-09-21 | 2020-12-08 | 广东电网有限责任公司电力科学研究院 | Filler, grounding grid anticorrosive paint and preparation method thereof |
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| CN107919452B (en) | 2021-03-12 |
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