CN107742689A - A kind of lithium battery organo-mineral complexing barrier film, preparation method and the lithium battery for including the barrier film - Google Patents
A kind of lithium battery organo-mineral complexing barrier film, preparation method and the lithium battery for including the barrier film Download PDFInfo
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- CN107742689A CN107742689A CN201711012596.7A CN201711012596A CN107742689A CN 107742689 A CN107742689 A CN 107742689A CN 201711012596 A CN201711012596 A CN 201711012596A CN 107742689 A CN107742689 A CN 107742689A
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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
- 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
- H01M50/409—Separators, membranes or diaphragms characterised by the 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 present invention relates to a kind of lithium battery organo-mineral complexing barrier film, preparation method and the lithium battery for including the barrier film, belong to technical field of lithium batteries.Composite diaphragm, include the inorganic, ceramic layer of centre and the organic layer of its both sides, following component by weight is included in the raw material of the organic layer：45~50 parts of polyolefin, 12~18 parts of graphene modacrylic fibers, 2~4 parts of surfactant, 0.5~3 part of antioxidant, 0.5~3 part of lubricant, 2.5~6 parts of filler, 18~35 parts of the first solvent；Include following component by weight in the raw material of described inorganic, ceramic layer：25~40 parts of particle, 15~18 parts of nano alumina particles, 12~15 parts of adhesive, 2~4 parts of non-ionic surface active, 15~24 parts of the second solvent of ionic liquid positive electricity modification.Lithium battery provided by the invention employs organo-mineral complexing membrane configuration, has the advantages of resistance to elevated temperatures is good, intensity is high.
Description
Technical field
The present invention relates to a kind of lithium battery organo-mineral complexing barrier film, preparation method and comprising the barrier film lithium electricity
Pond, belong to technical field of lithium batteries.
Background technology
Inside lithium ion cell is into spiral-shaped structure, by one layer of film with many tiny holes between positive pole and negative pole
Paper separates.Lithium-ion electric core is a kind of new battery power, and it is free of lithium metal, in charge and discharge process, only lithium ion
In positive and negative interpolar accommodating movement, electrode and electrolyte are not involved in reacting.The energy capacity density of lithium-ion electric core can reach
300Wh/L, gravimetric density can reach 125Wh/L.The reaction mechanism of lithium-ion electric core is the progress with discharge and recharge,
Lithium ion embedded abjection between both positive and negative polarity, without the presence of lithium metal inside the battery core that shuttles back and forth, therefore lithium-ion electric core
More safety and stability.The positive pole of lithium ion battery uses cobalt acid lithium, and plus plate current-collecting body is aluminium foil；Negative pole uses carbon, negative pole currect collecting
Body is copper foil, and the electrolyte of lithium ion battery is the organism for having dissolved LiPF6.The positive electrode of lithium ion battery is cobalt oxide
Lithium, negative pole are carbon.When being charged to battery, there is lithium ion generation on the positive pole of battery, lithium ion passes through electrolyte movement
To negative pole.And layer structure is presented in the carbon as negative pole, it has many micropores, and the lithium ion for reaching negative pole is just embedded into carbon-coating
In micropore, embedded lithium ion is more, and charging capacity is higher.As a same reason, when discharging battery, embedded in negative pole carbon-coating
In lithium ion abjection, move back into positive pole.Return to that the lithium ion of positive pole is more, and discharge capacity is higher.We are usually said
Battery capacity refers to is exactly discharge capacity.There is explosionproof hole on lithium ion battery cover, in the case that internally pressure is excessive,
Explosionproof hole can automatically open up pressure release, to prevent the phenomenon of blast.
Lithium ion battery is made up of positive pole, negative pole, electrolyte and barrier film etc..Positive electrode is by the transiting metal oxidation containing lithium
Thing forms, and conventional material has cobalt acid lithium, LiMn2O4, ternary material and LiFePO4.Negative material can be graphite, graphitization
Carbon material, modified graphite, graphitized intermediate-phase carbon particulate.Electrolyte is largely by lithium hexafluoro phosphate（LiFL6）Plus organic
Solvent is made into.Battery diaphragm is a kind of special composite membrane, and its function is isolation both positive and negative polarity, prevents electronics from passing through, while energy
Enough allow lithium ion by so as to complete quick transmission of the lithium ion between both positive and negative polarity during charge discharge.Mesh
Preceding mainly polyethylene（PE）Or polypropylene（PP）Microporous barrier.
The security of battery diaphragm is to lithium ion battery, and whether the security of high-capacity battery or high-power battery is all
It is most important.It is understood that the lithium battery diaphragm of current commercial applications is PP and PE bilayers or three layers of composite diaphragm, it is such a
The most outstanding problem that barrier film is applied now is exactly that melting point polymer is typically relatively low, and PE fusing points are 130 degrees Celsius, and PP fusing points are
180 degrees Celsius.Under abuse conditions, inside battery heat increased dramatically so that great problems occur for battery security.
CN103746087A discloses a kind of lithium ion battery separator manufacture method and lithium battery, belongs to lithium ion battery neck
Domain, its processing step include：A kind of lithium ion battery separator manufacture method, its processing step include：A, organic polymer material
Material is dissolved in solvent by agitating mode, forms organic macromolecule material solution, the weight hundred of high polymer material in the solution
It is 1%-20% to divide ratio.B, ceramic material is added in high-molecular organic material solution to be stirred as uniform slurry, ceramic material
The weight ratio of material and high-molecular organic material solution is 0.05-1.C, by slurry by intaglio printing mode be coated in be used for lithium from
On the barrier film of sub- battery, coated area is the 1-95% of the barrier film gross area.CN104993088A discloses a kind of low temperature closed pore high temperature
Stable non-woven fabric type lithium battery diaphragm and preparation method.The preparation method is：With silane coupler modified silica, make
Obtain and carry double bond on silica, then trigger MMA and TMPTA polymerizations, it is good, good to electrolyte wetability to obtain heat endurance
Core-shell particles；Core-shell particles are configured to lotion and are immersed in non-woven fabrics wherein, drying is taken out and obtains core-shell particles modification
Film；Then Modified Membrane is immersed in PVDF-HFP and PEGDMA mixed solution, be dried in vacuo after taking-up, obtain low temperature closed pore
The non-woven fabric type lithium battery diaphragm of high-temperature stable.
But above-mentioned barrier film there is low intensity, resistance to elevated temperatures is not high the problem of.
The content of the invention
The purpose of the present invention is：Solve the problems, such as that the barrier film of lithium battery interior is not high there is low intensity, resistance to elevated temperatures,
Propose a kind of organo-mineral complexing barrier film excellent with high intensity, resistance to elevated temperatures.
Technical scheme：
A kind of lithium battery organo-mineral complexing barrier film, include the inorganic, ceramic layer of centre and the organic layer of its both sides, institute
State the following component included in the raw material of organic layer by weight：45~50 parts of polyolefin, graphene modified polyacrylic acid
12~18 parts of fiber, 2~4 parts of surfactant, 0.5~3 part of antioxidant, 0.5~3 part of lubricant, 2.5~6 parts of filler,
One 18~35 parts of solvent；Include following component by weight in the raw material of described inorganic, ceramic layer：Ionic liquid is just
25~40 parts modified of particle of electricity, 15~18 parts of nano alumina particles, 12~15 parts of adhesive, non-ionic surface active 2~4
Part, 15~24 parts of the second solvent.
The material shape of described organic layer is non-woven fabrics.
Described polyolefin is selected from polypropylene or polyethylene.
One or several kinds of mixing of the first described solvent in ethyl acetate, butyl acetate, ethanol, propyl alcohol.
A kind of or both mixing of the second described solvent in water or ethanol.
The preparation method of graphene modacrylic fibers, comprises the following steps：
1st step, by weight, by 35~40 parts of hydroxy silicon oils, 12~18 parts of Silane coupling reagent KH-570s, 4~6 parts of KOH, second
8~12 parts of acetoacetic ester is well mixed, keeps 2~3h of reaction in a nitrogen atmosphere, after being warming up to 85 DEG C, obtains modified polyorganosiloxane
Performed polymer；
2nd step, by weight, take 18~22 parts of butyl acrylate, 8~12 parts of methyl acrylate, 0.5~3 part of emulsifying agent and
25~35 parts, 0.5~1h of high-speed stirred of deionized water, adds 1~2.5 part of initiator, and 1~3h is reacted at 75~85 DEG C,
1.5~3 parts of 3~5 parts of modified polyorganosiloxane performed polymers and initiator are added dropwise again, 1~4h are reacted at 75~85 DEG C, then use ammoniacal liquor
PH to 7 is adjusted, obtains acrylic emulsion；
3rd step, 1~3 part of 8~12 parts of titanium oxide and anion surfactant will be added in acrylic emulsion, will be uniformly dispersed
Afterwards, modified acrylic acid emulsion is obtained；
4th step, by weight, by 22~30 parts of graphene, 1~3 part of cationic surfactant, silane resin acceptor kh-550
1~5 part, 4~8 parts of organic solvent it is well mixed, obtain cation-modified graphene；
6th step, by cation-modified graphene and modified acrylic acid emulsion according to weight than 1：3~6 is well mixed, then by feed liquid
Fiber is sprayed into by spinning nozzle, then after drying, obtains graphene modacrylic fibers.
A diameter of 0.2~0.4mm of spinning head.
The azo-initiator is selected from azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, the formyl of azo two
Amine, azo dicyclohexyl formonitrile HCN hydrochloride, azo isobutyl cyano group formamide, azo diisopropyl imidazoline hydrochloride, azo dicyano penta
One or more in acid, azo dicyclohexyl formonitrile HCN, azodiisobutyronitrile, AMBN and ABVN.
The preparation method for the particle that ionic liquid positive electricity is modified, comprises the following steps：
1st step, the preparation of the ionic liquid of silane coupler grafting：Prepare the silane coupler KH560 and 3 containing 1~5wt%
The alcohol solution of~6% glyoxaline ion liquid, at 85~90 DEG C react 3~8h after, obtain silane coupler grafting from
The solution of sub- liquid；
2nd step, porous oxidation aluminum is immersed in the solution for the ionic liquid that silane coupler is grafted and handled, then will
Powder filters out, and after being cleaned successively with ethanol, water, drying, obtains the particle of ionic liquid positive electricity modification.
In the 1st described step, glyoxaline ion liquid is selected from chlorination -1- pi-allyl -3- methylimidazoles or chlorination 1- fourths
One or more of mixing in base -3- methylimidazoles or imidazole radicals tetrafluoroborate ion liquid；Described alcohols solvent
One or more of mixing in methanol, ethanol, propane diols, butanol or isoamyl alcohol.
In the 2nd described step, processing step refers to handle 5~10h under the conditions of 70~85 DEG C.
The preparation method of described composite diaphragm, comprises the following steps：
S1, by polyolefin, graphene modacrylic fibers, surfactant, antioxidant, lubricant, filler, first molten
Agent mixes, and the melting extrusion at 220~240 DEG C, is sprayed onto by a diameter of 0.2~0.4mm spinning head on lace curtaining, 140~150
DEG C roll-in sizing, obtain the nonwoven layer that thickness is 10~20 μm；
S2, the particle that ionic liquid positive electricity is modified, nano alumina particles, adhesive, non-ionic surface active, the second solvent
It is well mixed, obtain inorganic particle slurry；
S3, the coating inorganic particle slurry in nonwoven layer, after drying, then another layer is placed on the drying pulp layer of formation
Nonwoven layer；Again after 140~150 DEG C of roll-ins are shaped, composite diaphragm is obtained.
The painting method may be selected from spraying, scratch or roller coat in one kind.
Include the lithium battery of above-mentioned composite diaphragm.
Beneficial effect
Lithium battery provided by the invention employs organo-mineral complexing membrane configuration, and it is excellent to have that resistance to elevated temperatures is good, intensity is high
Point.
Embodiment
The present invention is described in further detail below by embodiment.But those skilled in the art will manage
Solution, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Unreceipted specific skill in embodiment
Art or condition person, carried out according to the technology described by document in the art or condition or according to product description.Examination used
Agent or the unreceipted production firm person of instrument, being can be by the conventional products of acquisition purchased in market.
Word " comprising " used herein, "comprising", " having " or its any other variant are intended to cover non-exclusionism
Including.Technique, method, article or the equipment for e.g., including listing key element are not necessarily limited by those key elements, but can include
Other are not expressly set out or belonged to this technique, method, article or the intrinsic key element of equipment.
Scope is used as using what the value of range format expression should be interpreted as not only including clearly including in a flexible way
The numerical value of limit value, but also including covering all single numbers or subinterval within the range, just as each numerical value and sub-district
Between be expressly recited out.For example, " about 0.1% to about 5% " concentration range should be understood to not only include what is clearly included
The concentration of about 0.1% to about 5%, in addition to the single concentration in the range of alluding to（Such as, 1%, 2%, 3% and 4%）And subinterval（Example
Such as, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%）.Percentage in the present invention refers to weight in the case of without specified otherwise
Percentage.
The structure of composite diaphragm provided by the present invention, include centre inorganic, ceramic layer and its both sides it is organic
Layer, following component by weight is included in the raw material of the organic layer：45~50 parts of polyolefin, graphene are modified poly- third
12~18 parts of olefin(e) acid fiber, 2~4 parts of surfactant, 0.5~3 part of antioxidant, 0.5~3 part of lubricant, filler 2.5~6
Part, 18~35 parts of the first solvent；Include following component by weight in the raw material of described inorganic, ceramic layer：Ionic liquid
25~40 parts of particle, 15~18 parts of nano alumina particles, 12~15 parts of adhesive, the non-ionic surface active of body positive electricity modification
2~4 parts, 15~24 parts of the second solvent.
The polyolefin used in the present invention can for example include polyethylene, polypropylene and by ethene or propylene with it is other
The polymer that the resins such as the copolymer of alpha-olefin are formed.
Polypropylene can be the polymer synthesized using common Ziegler-Natta catalyst, or can also be profit
The polymer synthesized to metallocene for the single site catalysts of representative.It is carbon number 3~10 as other alpha-olefins
Alkene, specifically, propylene, 1- butylene, 1- amylenes, 1- hexenes, 4-methyl-1-pentene and 1- octenes etc. can be included.These
It can be used alone, two or more can also be combined.
Graphene modacrylic fibers, it is enhancing ingredients, can after its surface have passed through graphene modification
Preferable hydrophily is provided, can make organic layer that there is more preferable amalgamation with middle inorganic ceramic membrane, using the teaching of the invention it is possible to provide be good
Compatibility simultaneously provides the stronger effect of adhesion between improved adjacent layer.
The preparation method of graphene modacrylic fibers, comprises the following steps：
1st step, by weight, by 35~40 parts of hydroxy silicon oils, 12~18 parts of Silane coupling reagent KH-570s, 4~6 parts of KOH, second
8~12 parts of acetoacetic ester is well mixed, keeps 2~3h of reaction in a nitrogen atmosphere, after being warming up to 85 DEG C, obtains modified polyorganosiloxane
Performed polymer；
2nd step, by weight, take 18~22 parts of butyl acrylate, 8~12 parts of methyl acrylate, 0.5~3 part of emulsifying agent and
25~35 parts, 0.5~1h of high-speed stirred of deionized water, adds 1~2.5 part of initiator, and 1~3h is reacted at 75~85 DEG C,
1.5~3 parts of 3~5 parts of modified polyorganosiloxane performed polymers and initiator are added dropwise again, 1~4h are reacted at 75~85 DEG C, then use ammoniacal liquor
PH to 7 is adjusted, obtains acrylic emulsion；
3rd step, 1~3 part of 8~12 parts of titanium oxide and anion surfactant will be added in acrylic emulsion, will be uniformly dispersed
Afterwards, modified acrylic acid emulsion is obtained；
4th step, by weight, by 22~30 parts of graphene, 1~3 part of cationic surfactant, silane resin acceptor kh-550
1~5 part, 4~8 parts of organic solvent it is well mixed, obtain cation-modified graphene；
6th step, by cation-modified graphene and modified acrylic acid emulsion according to weight than 1：3~6 is well mixed, then by feed liquid
Fiber is sprayed into by spinning nozzle, then after drying, obtains graphene modacrylic fibers.
A diameter of 0.2~0.4mm of spinning head.
The azo-initiator is selected from azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, the formyl of azo two
Amine, azo dicyclohexyl formonitrile HCN hydrochloride, azo isobutyl cyano group formamide, azo diisopropyl imidazoline hydrochloride, azo dicyano penta
One or more in acid, azo dicyclohexyl formonitrile HCN, azodiisobutyronitrile, AMBN and ABVN.
As antioxidant, such as triphenyl phosphite, three can be used（4- aminomethyl phenyls）Phosphite ester, three（4-
Tert-butyl-phenyl）Phosphite ester, three（Single nonyl phenyl）Phosphite ester, three（2- methyl -4- ethylphenyls）Phosphite ester, three
（2- methyl -4- tert-butyl-phenyls）Phosphite ester, three（2,4- di-t-butyl phenyl）Phosphite ester, three（2,6- di-t-butyls
Phenyl）Phosphite ester, three（2,4- di-t-butyl -5- aminomethyl phenyls）Phosphite ester, three（It is single, dinonylphenyl）Phosphite ester,
It is double（Single nonyl phenyl）It is pentaerythrite-two-phosphite ester, double（2,4- di-t-butyl phenyl）Pentaerythrite-two-phosphite ester,
It is double（2,6- di-t-butyl -4- aminomethyl phenyls）It is pentaerythrite-two-phosphite ester, double（Tri--tert-butyl-phenyls of 2,4,6-）Season penta
It is tetrol-two-phosphite ester, double（2,4- di-t-butyl -5- aminomethyl phenyls）Pentaerythrite-two-phosphite ester, 2,2- methylene
It is double（4,6- 3,5-dimethylphenyls）Octyl group phosphite ester, 2,2- di-2-ethylhexylphosphine oxides（The 4- tert-butyl group -6- aminomethyl phenyls）Octyl group phosphite ester,
2,2- di-2-ethylhexylphosphine oxides（4,6- di-t-butyl phenyl）Octyl group phosphite ester, 2,2- di-2-ethylhexylphosphine oxides（4,6- 3,5-dimethylphenyls）Hexyl
Phosphite ester, 2,2- di-2-ethylhexylphosphine oxides（4,6- 3,5-dimethylphenyls）Hexyl phosphite ester, 2,2- di-2-ethylhexylphosphine oxides（4,6- di-t-butyls
Phenyl）The bi-ester of phosphite such as stearyl phosphite ester；[the 3- of pentaerythrite base-four（3,5- di-t-butyl 4- hydroxy phenyls）
Propionic ester], 1,6-HD-bis- [3-（3,5- di-t-butyl 4- hydroxy phenyls）Propionic ester], octadecyl -3-（3,5- bis--
Tert-butyl-hydroxy phenyl）Propionic ester, 1,3,5- trimethyls -2,4,6- three（3,5- di-t-butyl -4- hydroxyphenylmethyls）Benzene,
Triethylene glycol-bis- [3-（The 3- tert-butyl group -5- methyl -4- hydroxy phenyls）Propionic ester], the double { 2- [3- of 3,9-（The 3- tert-butyl group -4- hydroxyls
Base -5- aminomethyl phenyls）Propionyloxy] -1,1- dimethyl ethyls 2,4,8,10- tetra- oxaspiro [5,5] hendecane, 1,1,3- tri-
[2- methyl -4-（3,5- di-t-butyl -4- hydroxy phenylpropionyl epoxides）- 5- tert-butyl-phenyls] the fortified phenol class such as butane
Compound；5,7- di-t-butyl -s 3-（3,4- 3,5-dimethylphenyls）- 3H- benzofuran-2-ones etc..These can be used alone or
Two or more is used in combination.
The lubricant used in the present invention is not particularly limited, as long as it is improving the mobility side of thermoplastic polymer
Face plays a role, and their example includes hydrocarbon lubricants, such as atoleine, solid paraffin, microcrystalline wax and poly- second
Alkene wax；Fatty acid lubricant, such as stearic acid, behenic acid and 1,2-hydroxystearic acid；And ester lubricant, such as it is stearic
Acid butyl ester, glyceryl monostearate, pentaerythritol tetrastearate, hardened castor oil and stearyl stearate.
Filler employed in the present invention generally refers to refer to inert solid particle shape material, such as silicic acid in small, broken bits, is such as pyrolyzed
Silicic acid or silica gel, titanium dioxide, hydroxide such as aluminium hydroxide, potassium carbonate, magnesium carbonate and calcium carbonate, silicate such as sodium metasilicate,
Magnesium silicate, talcum, calcium silicates, zinc silicate, aluminosilicate such as sodium aluminosilicate, potassium aluminotrisilicate orthoclase, calcium aluminosilicate, bentonite, kaolin.
These can be used alone can also two or more be used in combination.
The first solvent is used in this reaction.The concrete example for the organic solvent that can be used, can enumerate hexane, hexamethylene,
The alcohol such as the arene compounds such as the alkanes such as heptane, toluene, dimethylbenzene, methanol, ethanol, isopropanol, butanol, hexanol, cyclohexanol
Class.In addition, it can also according to circumstances use ketone, ether, the tetrahydrochysene furans such as MEK, methyl iso-butyl ketone (MIBK), cycloheptanone, cyclohexanone
Mutter, the nitrile compound such as ester compounds, the acetonitrile such as ethers, ethyl acetate, butyl acetate, the methyl formate such as dioxane etc..
As particularly preferred solvent, there is the arene compound such as the alkanes such as hexane, hexamethylene, heptane, toluene, dimethylbenzene.It is more excellent
Select one or several kinds of mixing in ethyl acetate, butyl acetate, ethanol, propyl alcohol.
Raw material in inorganic, ceramic layer includes：25~40 parts of particle, the nano aluminium oxide of ionic liquid positive electricity modification
15~18 parts of particle, 12~15 parts of adhesive, 2~4 parts of non-ionic surface active, 15~24 parts of the second solvent.
For particulate matter by after ion liquid modified, its surface has the positive charge group of ionic liquid, can be with organic layer
Between realize and preferably merge, improve every film strength and conductance.
The preparation method for the particle that ionic liquid positive electricity is modified, comprises the following steps：1st step, silane coupler grafting
The preparation of ionic liquid：The alcohols for preparing the glyoxaline ion liquid of the silane coupler KH560 and 3~6% containing~5wt% is molten
Liquid, after reacting 3~8h at 85~90 DEG C, obtain the solution of the ionic liquid of silane coupler grafting；2nd step, by porous oxygen
Change and handled in the solution for the ionic liquid that aluminum is immersed in silane coupler grafting, then powder is filtered out, use second successively
After alcohol, water cleaning, drying, the particle of ionic liquid positive electricity modification is obtained.In the 1st described step, glyoxaline ion liquid is selected from
Chlorination -1- pi-allyl -3- methylimidazoles or chlorination 1- butyl -3- methylimidazoles or imidazole radicals tetrafluoroborate ion liquid
In one or more of mixing；The one kind of described alcohols solvent in methanol, ethanol, propane diols, butanol or isoamyl alcohol
Or several mixing.In the 2nd described step, processing step refers to handle 5~10h under the conditions of 70~85 DEG C.
Adhesive includes glycerine, hydroxypropyl methylcellulose, dextrin, polyethylene glycol, syrup, Arabic gum, sorbierite, gelatin
Or polyvinylpyrrolidone etc..
A kind of or both mixing of the second described solvent in water or ethanol.
The surfactant used in organic layer and inorganic, ceramic layer, can using nonionic surfactant,
For example, line style polyoxyalkylene alkyl class, such as polyethylene glycol oxide hexyl ether, polyoxyethylene octyl ether, polyethylene glycol oxide decyl
Ether, polyoxyethylene lauryl ether and polyethylene glycol oxide cetyl ether；Branched polyoxyalkylenes primary alkyl ethers, such as polyoxygenated
Ethene 2- ethylhexyl ethers, polyethylene glycol oxide isocetyl ether and polyethylene glycol oxide iso stearyl ether；Branched polyoxyalkylene is secondary
Alkyl ether, such as polyethylene glycol oxide 1- hexyl hexyl ethers, polyethylene glycol oxide 1- octyl group hexyl ethers, polyethylene glycol oxide 1- hexyl octyl groups
Ether, polyethylene glycol oxide 1- amyl group heptyl ethers and polyethylene glycol oxide 1- heptyl amyl ethers；Polyoxyalkylene alkenyl ethers class, such as polyoxygenated
Ethene oleyl ether；Polyoxyalkylene alkyl phenyl ethers, such as polyoxyethylene octylphenyl ether, polyoxyethylene nonyl phenyl
Ether, and polyethylene glycol oxide dodecylphenyl ether；Polyoxyalkylene alkyl aryl phenyl ethers, such as polyethylene glycol oxide triphenylethylene base
Phenyl ether, polyethylene glycol oxide diphenylethyllene phenyl ether, polyethylene glycol oxide styrylphenyl ether, polyethylene glycol oxide tribenzyl-benzene
Base, polyethylene glycol oxide dibenzylphenyl ether, and polyethylene glycol oxide benzyl phenyl ether；Polyoxyalkylene fatty acid ester class, such as polyoxy
Change ethene monolaurate, polyethylene glycol oxide monoleate, polyoxyethylene monostearate ester, polyethylene glycol oxide list myristic acid
Ester, polyethylene glycol oxide dilaurate, polyethylene glycol oxide dioleate, the myristinate of polyethylene glycol oxide two, and polyoxygenated
Ethene distearate；Sorbitan ester class, such as span 40 and sorbitan list oleic acid
Ester；Polyoxyalkylene sorbitan polyol fatty acid esters, such as TWEEN 60 and polyoxygenated
Ethene dehydrated sorbitol mono-fatty acid ester；Glycerine fatty acid esters, such as glyceryl monostearate, glyceryl monolaurate and glycerine
Monopalmitate；Polyoxyalkylene sorbitan polyol fatty acid esters；Sucrose-fatty esters；Polyoxyalkylene castor oil ethers, it is such as poly-
Ethylene oxide castor oil ether；Polyoxyalkylene hydrogenated castor oil ethers, such as polyoxyethylene hydrogenated castor oil ether；Polyoxyalkylene alkyl
Amino ethers, such as polyoxyethylene lauryl base amino ethers and polyethylene glycol oxide stearyl ether；Ethylene oxide-propylene oxide is embedding
Section or random copolymer；Oxyethylene group-oxypropylene group the block or random copolymer of end alkyl etherificate；With end sugarcane
The ethylene oxide-propylene oxide block or random copolymer of sugar-etherificate.
Anion surfactant includes, for example, fatty acid and their salt, such as oleic acid, palmitic acid, enuatrol, palm fibre
Palmitic acid acid potassium, and triethanolamine oleate；Hydroxyl institute's acids and their salt, such as hydroxyacetic acid, hydroxyacetic acid potassium, lactic acid and lactic acid
Potassium；Polyoxyalkylene alkyl acetic acid class and their salt, such as the decyl ether acetic acid of polyoxyalkylene three and its sodium salt；Carboxyl-polysubstituted
Aromatic compounds salt, such as trimellitic acid potassium and pyromellitic acid potassium；Benzene sulfonamide acids and their salt, such as detergent alkylate
Sulfonic acid and its sodium salt；Polyoxyalkylene alkyl ethers sulfonic acid and their salt, such as polyethylene glycol oxide 2- ethylhexyls ether sulfonic acid and its
Sylvite；Higher fatty acid amides sulfonic acid and their salt, such as stearic acyl methyl taurine and its sodium salt, lauroyl methyl taurine
And its sodium salt, myristoyl methyl taurine and its sodium salt and PMT and its sodium salt；N- acyl group sarcosinates
With their salt, such as Hamposyl L and its sodium salt；Alkyl phosphonic acid and their salt, such as octylphosphonate and its sylvite；Virtue
Race's phosphonic acids and their salt, such as phenyl phosphonic acid esters and its sylvite；Alkyl phosphonic acid phosphonate ester and their salt, such as 2- ethyl hexyls
Base phosphonic acids list -2- ethylhexyls and its sylvite；Nitrogenous alkyl phosphonic acid and their salt, such as aminoethyl phosphonic acid and its diethanol amine
Salt；Alkyl sulfate and their salt, such as 2- ethyl hexyls sulfuric ester and its sodium salt；Polyoxyalkylene sulfuric acid ester and their salt,
Such as polyethylene glycol oxide 2- ethylhexyls ether sulfuric ester and its sodium salt；Alkyl phosphoric acid esters and their salt, such as base succinic acid salt,
Such as two -2- ethylhexyls sodium sulfo-succinates and dioctyl sodium sulfosuccinate；And long-chain N- acyl glutamates, such as the N- months
Osmanthus acyl monosodium glutamate and N- stearoyls-Pidolidone disodium.
Cationic surfactant includes, for example, quaternary ammonium salt, such as hexadecyltrimethylammonium chloride, chlorination lauryl three
Ammonium methyl and ethyl sulfuric acid oleyl Methylethyl ammonium；And (polyoxyalkylenes) alkyl amino ether salt, such as (polyethylene glycol oxide
Base) lauryl amino ether lactate, stearyl ether lactate, and (polyethylene oxide base) lauryl amino ether trimethyl phosphorus
Hydrochlorate.
Embodiment 1
Lithium battery organo-mineral complexing barrier film, include the inorganic, ceramic layer of centre and the organic layer of its both sides, it is described to have
Include following component by weight in the raw material of machine layer：45 parts of polypropylene, 12 parts of graphene modacrylic fibers,
2 parts of non-ionic surface active sorbitan monooleate, 0.5 part of antioxidant triphenyl phosphite, lubricant microcrystalline wax
0.5 part, 2.5 parts of filler titanium dioxide, 18 parts of ethyl acetate；Include by weight in the raw material of described inorganic, ceramic layer
Following component：Ionic liquid positive electricity be modified 25 parts of particle, 15 parts of nano alumina particles, 12 parts of adhesive polyethylene glycol,
2 parts of non-ionic surface active sorbitan monooleate, 15 parts of ethanol.
The preparation method of graphene modacrylic fibers, comprises the following steps：
1st step, it is by weight, 35 parts of hydroxy silicon oils, 12 parts of Silane coupling reagent KH-570s, 4 parts of KOH, 8 parts of ethyl acetate is mixed
Close uniformly, keep reaction 2h in a nitrogen atmosphere, after being warming up to 85 DEG C, obtain modified polyorganosiloxane performed polymer；
2nd step, by weight, take 18 parts of butyl acrylate, 8 parts of methyl acrylate, emulsifying agent anhydrous sorbitol monostearate
25 parts, high-speed stirred 0.5h of 0.5 part of ester and deionized water, add 1 part of initiator azodicarbonamide, are reacted at 75 DEG C
1h, then 1.5 parts of 3 parts of modified polyorganosiloxane performed polymers and initiator azodicarbonamide are added dropwise, 1~4h is reacted at 75 DEG C, then
PH to 7 is adjusted with ammoniacal liquor, obtains acrylic emulsion；
3rd step, 1 part of 8 parts of titanium oxide and anion surfactant cetyl benzenesulfonic acid sodium will be added in acrylic emulsion,
After being uniformly dispersed, modified acrylic acid emulsion is obtained；
4th step, by weight, by 22 parts of graphene, 1 part of cationic surfactant hexadecyltrimethylammonium chloride, silicon
1 part of alkane coupling agent KH-550,4 parts of ethyl acetate are well mixed, obtain cation-modified graphene；
6th step, by cation-modified graphene and modified acrylic acid emulsion according to weight than 1：3 is well mixed, then feed liquid is led to
Cross spinning nozzle and be sprayed into fiber, a diameter of 0.2mm of spinning head, then after drying, obtain graphene modified polyacrylic acid
Fiber.
The preparation method for the particle that ionic liquid positive electricity is modified, comprises the following steps：
1st step, the preparation of the ionic liquid of silane coupler grafting：Prepare the silane coupler KH560's and 3% containing 1wt%
The ethanol solution of chlorination -1- pi-allyl -3- methylimidazole ionic liquids, after reacting 3h at 85 DEG C, obtain silane coupler and connect
The solution of the ionic liquid of branch；
2nd step, porous oxidation aluminum is immersed in the solution for the ionic liquid that silane coupler is grafted and handled, handled
Step refers to handle 5h under the conditions of 70 DEG C, then powder is filtered out, and after being cleaned successively with ethanol, water, drying, obtains ionic liquid
The particle that positive electricity is modified.
The preparation method of described composite diaphragm, comprises the following steps：
S1, by polyolefin, graphene modacrylic fibers, surfactant, antioxidant, lubricant, filler, first molten
Agent mixes, and the melting extrusion at 240 DEG C, is sprayed onto by a diameter of 0.4mm spinning head on lace curtaining, 150 DEG C of roll-in sizings, obtains
Thickness is 10~20 μm of nonwoven layer；
S2, the particle that ionic liquid positive electricity is modified, nano alumina particles, adhesive, non-ionic surface active, the second solvent
It is well mixed, obtain inorganic particle slurry；
S3, the roller coat inorganic particle slurry in nonwoven layer, after drying, then another layer is placed on the drying pulp layer of formation
Nonwoven layer；Again after 150 DEG C of roll-ins are shaped, composite diaphragm is obtained.
Embodiment 2
Lithium battery organo-mineral complexing barrier film, include the inorganic, ceramic layer of centre and the organic layer of its both sides, it is described to have
Include following component by weight in the raw material of machine layer：50 parts of polypropylene, 18 parts of graphene modacrylic fibers,
4 parts of non-ionic surface active sorbitan monooleate, 3 parts of antioxidant triphenyl phosphite, lubricant microcrystalline wax 3
Part, 6 parts of filler titanium dioxide, 35 parts of ethyl acetate；Include in the raw material of described inorganic, ceramic layer by weight as
Lower component：Ionic liquid positive electricity be modified 40 parts of particle, 18 parts of nano alumina particles, 15 parts of adhesive polyethylene glycol, it is non-from
Sub- 4 parts of surface-active sorbitan monooleate, 24 parts of ethanol.
The preparation method of graphene modacrylic fibers, comprises the following steps：
1st step, by weight, by 40 parts of hydroxy silicon oils, 18 parts of Silane coupling reagent KH-570s, 6 parts of KOH, 12 parts of ethyl acetate
It is well mixed, reaction 3h is kept in a nitrogen atmosphere, after being warming up to 85 DEG C, obtains modified polyorganosiloxane performed polymer；
2nd step, by weight, take 22 parts of butyl acrylate, 12 parts of methyl acrylate, emulsifying agent anhydrous sorbitol monostearate
35 parts, high-speed stirred 1h of 3 parts of ester and deionized water, add 2.5 parts of initiator azodicarbonamide, react 3h at 85 DEG C,
3 parts of 5 parts of modified polyorganosiloxane performed polymers and initiator azodicarbonamide are added dropwise again, 4h are reacted at 85 DEG C, then adjusted with ammoniacal liquor
PH to 7 is saved, obtains acrylic emulsion；
3rd step, 12 parts of titanium oxide and anion surfactant cetyl benzenesulfonic acid sodium 3 will be added in acrylic emulsion
Part, after being uniformly dispersed, obtain modified acrylic acid emulsion；
4th step, by weight, by 30 parts of graphene, 3 parts of cationic surfactant hexadecyltrimethylammonium chloride, silicon
5 parts of alkane coupling agent KH-550,8 parts of ethyl acetate are well mixed, obtain cation-modified graphene；
6th step, by cation-modified graphene and modified acrylic acid emulsion according to weight than 1：6 is well mixed, then feed liquid is led to
Cross spinning nozzle and be sprayed into fiber, a diameter of 0.4mm of spinning head, then after drying, obtain graphene modified polyacrylic acid
Fiber.
The preparation method for the particle that ionic liquid positive electricity is modified, comprises the following steps：
1st step, the preparation of the ionic liquid of silane coupler grafting：Prepare the silane coupler KH560's and 6% containing 5wt%
The ethanol solution of chlorination -1- pi-allyl -3- methylimidazole ionic liquids, after reacting 8h at 90 DEG C, obtain silane coupler and connect
The solution of the ionic liquid of branch；
2nd step, porous oxidation aluminum is immersed in the solution for the ionic liquid that silane coupler is grafted and handled, handled
Step refers to handle 10h under the conditions of 85 DEG C, then powder is filtered out, and after being cleaned successively with ethanol, water, drying, obtains ionic liquid
The particle that body positive electricity is modified.
The preparation method of described composite diaphragm, comprises the following steps：
S1, by polyolefin, graphene modacrylic fibers, surfactant, antioxidant, lubricant, filler, first molten
Agent mixes, and the melting extrusion at 240 DEG C, is sprayed onto by a diameter of 0.4mm spinning head on lace curtaining, 150 DEG C of roll-in sizings, obtains
Thickness is 10~20 μm of nonwoven layer；
S2, the particle that ionic liquid positive electricity is modified, nano alumina particles, adhesive, non-ionic surface active, the second solvent
It is well mixed, obtain inorganic particle slurry；
S3, the roller coat inorganic particle slurry in nonwoven layer, after drying, then another layer is placed on the drying pulp layer of formation
Nonwoven layer；Again after 150 DEG C of roll-ins are shaped, composite diaphragm is obtained.
Embodiment 3
Lithium battery organo-mineral complexing barrier film, include the inorganic, ceramic layer of centre and the organic layer of its both sides, it is described to have
Include following component by weight in the raw material of machine layer：46 parts of polypropylene, 16 parts of graphene modacrylic fibers,
3 parts of non-ionic surface active sorbitan monooleate, 1.5 parts of antioxidant triphenyl phosphite, lubricant microcrystalline wax 2
Part, 5 parts of filler titanium dioxide, 22 parts of ethyl acetate；Include in the raw material of described inorganic, ceramic layer by weight as
Lower component：Ionic liquid positive electricity be modified 35 parts of particle, 16 parts of nano alumina particles, 13 parts of adhesive polyethylene glycol, it is non-from
Sub- 3 parts of surface-active sorbitan monooleate, 18 parts of ethanol.
The preparation method of graphene modacrylic fibers, comprises the following steps：
1st step, by weight, by 36 parts of hydroxy silicon oils, 16 parts of Silane coupling reagent KH-570s, 5 parts of KOH, 10 parts of ethyl acetate
It is well mixed, reaction 3h is kept in a nitrogen atmosphere, after being warming up to 85 DEG C, obtains modified polyorganosiloxane performed polymer；
2nd step, by weight, take 20 parts of butyl acrylate, 10 parts of methyl acrylate, emulsifying agent anhydrous sorbitol monostearate
30 parts, high-speed stirred 0.7h of 1 part of ester and deionized water, add 1.5 parts of initiator azodicarbonamide, are reacted at 80 DEG C
2h, then 2 parts of 4 parts of modified polyorganosiloxane performed polymers and initiator azodicarbonamide are added dropwise, 2h is reacted at 80 DEG C, then use ammoniacal liquor
PH to 7 is adjusted, obtains acrylic emulsion；
3rd step, 10 parts of titanium oxide and anion surfactant cetyl benzenesulfonic acid sodium 2 will be added in acrylic emulsion
Part, after being uniformly dispersed, obtain modified acrylic acid emulsion；
4th step, by weight, by 25 parts of graphene, 2 parts of cationic surfactant hexadecyltrimethylammonium chloride, silicon
3 parts of alkane coupling agent KH-550,5 parts of ethyl acetate are well mixed, obtain cation-modified graphene；
6th step, by cation-modified graphene and modified acrylic acid emulsion according to weight than 1：5 is well mixed, then feed liquid is led to
Cross spinning nozzle and be sprayed into fiber, a diameter of 0.3mm of spinning head, then after drying, obtain graphene modified polyacrylic acid
Fiber.
The preparation method for the particle that ionic liquid positive electricity is modified, comprises the following steps：
1st step, the preparation of the ionic liquid of silane coupler grafting：Prepare the silane coupler KH560's and 5% containing 2wt%
The ethanol solution of chlorination -1- pi-allyl -3- methylimidazole ionic liquids, after reacting 5h at 86 DEG C, obtain silane coupler and connect
The solution of the ionic liquid of branch；
2nd step, porous oxidation aluminum is immersed in the solution for the ionic liquid that silane coupler is grafted and handled, handled
Step refers to handle 8h under the conditions of 75 DEG C, then powder is filtered out, and after being cleaned successively with ethanol, water, drying, obtains ionic liquid
The particle that positive electricity is modified.
The preparation method of described composite diaphragm, comprises the following steps：
S1, by polyolefin, graphene modacrylic fibers, surfactant, antioxidant, lubricant, filler, first molten
Agent mixes, and the melting extrusion at 230 DEG C, is sprayed onto by a diameter of 0.3mm spinning head on lace curtaining, 145 DEG C of roll-in sizings, obtains
Thickness is 10~20 μm of nonwoven layer；
S2, the particle that ionic liquid positive electricity is modified, nano alumina particles, adhesive, non-ionic surface active, the second solvent
It is well mixed, obtain inorganic particle slurry；
S3, the roller coat inorganic particle slurry in nonwoven layer, after drying, then another layer is placed on the drying pulp layer of formation
Nonwoven layer；Again after 145 DEG C of roll-ins are shaped, composite diaphragm is obtained.
Reference examples 1
Difference with embodiment 3 is：Polyacrylic fibre is without graphene modification.
Lithium battery organo-mineral complexing barrier film, include the inorganic, ceramic layer of centre and the organic layer of its both sides, institute
State the following component included in the raw material of organic layer by weight：46 parts of polypropylene, 16 parts of polyacrylic fibre, nonionic
3 parts of surface-active sorbitan monooleate, 1.5 parts of antioxidant triphenyl phosphite, 2 parts of lubricant microcrystalline wax, fill out
Expect 5 parts of titanium dioxide, 22 parts of ethyl acetate；Include in the raw material of described inorganic, ceramic layer by weight such as the following group
Point：35 parts of particle, 16 parts of nano alumina particles, 13 parts of adhesive polyethylene glycol, the nonionic table of ionic liquid positive electricity modification
3 parts of face activity sorbitan monooleate, 18 parts of ethanol.
The preparation method of polyacrylic fibre, comprises the following steps：
1st step, by weight, by 36 parts of hydroxy silicon oils, 16 parts of Silane coupling reagent KH-570s, 5 parts of KOH, 10 parts of ethyl acetate
It is well mixed, reaction 3h is kept in a nitrogen atmosphere, after being warming up to 85 DEG C, obtains modified polyorganosiloxane performed polymer；
2nd step, by weight, take 20 parts of butyl acrylate, 10 parts of methyl acrylate, emulsifying agent anhydrous sorbitol monostearate
30 parts, high-speed stirred 0.7h of 1 part of ester and deionized water, add 1.5 parts of initiator azodicarbonamide, are reacted at 80 DEG C
2h, then 2 parts of 4 parts of modified polyorganosiloxane performed polymers and initiator azodicarbonamide are added dropwise, 2h is reacted at 80 DEG C, then use ammoniacal liquor
PH to 7 is adjusted, obtains acrylic emulsion；
3rd step, 10 parts of titanium oxide and anion surfactant cetyl benzenesulfonic acid sodium 2 will be added in acrylic emulsion
Part, after being uniformly dispersed, obtain modified acrylic acid emulsion；
4th step, by weight, by 2 parts of cationic surfactant hexadecyltrimethylammonium chloride, silane coupler KH-
550 3 parts, 5 parts of ethyl acetate it is well mixed, obtain cation-modified agent composition；
6th step, by cation-modified agent composition and modified acrylic acid emulsion according to weight than 1：5 is well mixed, then by feed liquid
Fiber, a diameter of 0.3mm of spinning head are sprayed into by spinning nozzle, then after drying, obtain polyacrylic fibre.
The preparation method for the particle that ionic liquid positive electricity is modified, comprises the following steps：
1st step, the preparation of the ionic liquid of silane coupler grafting：Prepare the silane coupler KH560's and 5% containing 2wt%
The ethanol solution of chlorination -1- pi-allyl -3- methylimidazole ionic liquids, after reacting 5h at 86 DEG C, obtain silane coupler and connect
The solution of the ionic liquid of branch；
2nd step, porous oxidation aluminum is immersed in the solution for the ionic liquid that silane coupler is grafted and handled, handled
Step refers to handle 8h under the conditions of 75 DEG C, then powder is filtered out, and after being cleaned successively with ethanol, water, drying, obtains ionic liquid
The particle that positive electricity is modified.
The preparation method of described composite diaphragm, comprises the following steps：
S1, by polyolefin, graphene modacrylic fibers, surfactant, antioxidant, lubricant, filler, first molten
Agent mixes, and the melting extrusion at 230 DEG C, is sprayed onto by a diameter of 0.3mm spinning head on lace curtaining, 145 DEG C of roll-in sizings, obtains
Thickness is 10~20 μm of nonwoven layer；
S2, the particle that ionic liquid positive electricity is modified, nano alumina particles, adhesive, non-ionic surface active, the second solvent
It is well mixed, obtain inorganic particle slurry；
S3, the roller coat inorganic particle slurry in nonwoven layer, after drying, then another layer is placed on the drying pulp layer of formation
Nonwoven layer；Again after 145 DEG C of roll-ins are shaped, composite diaphragm is obtained.
Reference examples 2
Difference with embodiment 3 is：Porous oxidation alumina particles in inorganic, ceramic layer are without ion liquid modified.
Lithium battery organo-mineral complexing barrier film, include the inorganic, ceramic layer of centre and the organic layer of its both sides, institute
State the following component included in the raw material of organic layer by weight：46 parts of polypropylene, graphene modacrylic fibers
16 parts, 3 parts of non-ionic surface active sorbitan monooleate, 1.5 parts of antioxidant triphenyl phosphite, lubricant crystallite
2 parts of paraffin, 5 parts of filler titanium dioxide, 22 parts of ethyl acetate；Include by weight in the raw material of described inorganic, ceramic layer
Following component：35 parts of porous oxidation alumina particles, 16 parts of nano alumina particles, 13 parts of adhesive polyethylene glycol, nonionic table
3 parts of face activity sorbitan monooleate, 18 parts of ethanol.
The preparation method of graphene modacrylic fibers, comprises the following steps：
1st step, by weight, by 36 parts of hydroxy silicon oils, 16 parts of Silane coupling reagent KH-570s, 5 parts of KOH, 10 parts of ethyl acetate
It is well mixed, reaction 3h is kept in a nitrogen atmosphere, after being warming up to 85 DEG C, obtains modified polyorganosiloxane performed polymer；
2nd step, by weight, take 20 parts of butyl acrylate, 10 parts of methyl acrylate, emulsifying agent anhydrous sorbitol monostearate
30 parts, high-speed stirred 0.7h of 1 part of ester and deionized water, add 1.5 parts of initiator azodicarbonamide, are reacted at 80 DEG C
2h, then 2 parts of 4 parts of modified polyorganosiloxane performed polymers and initiator azodicarbonamide are added dropwise, 2h is reacted at 80 DEG C, then use ammoniacal liquor
PH to 7 is adjusted, obtains acrylic emulsion；
3rd step, 10 parts of titanium oxide and anion surfactant cetyl benzenesulfonic acid sodium 2 will be added in acrylic emulsion
Part, after being uniformly dispersed, obtain modified acrylic acid emulsion；
4th step, by weight, by 25 parts of graphene, 2 parts of cationic surfactant hexadecyltrimethylammonium chloride, silicon
3 parts of alkane coupling agent KH-550,5 parts of ethyl acetate are well mixed, obtain cation-modified graphene；
6th step, by cation-modified graphene and modified acrylic acid emulsion according to weight than 1：5 is well mixed, then feed liquid is led to
Cross spinning nozzle and be sprayed into fiber, a diameter of 0.3mm of spinning head, then after drying, obtain graphene modified polyacrylic acid
Fiber.
The preparation method for the particle that ionic liquid positive electricity is modified, comprises the following steps：
1st step, the preparation of the ionic liquid of silane coupler grafting：Prepare the silane coupler KH560's and 5% containing 2wt%
The ethanol solution of chlorination -1- pi-allyl -3- methylimidazole ionic liquids, after reacting 5h at 86 DEG C, obtain silane coupler and connect
The solution of the ionic liquid of branch；
2nd step, porous oxidation aluminum is immersed in the solution for the ionic liquid that silane coupler is grafted and handled, handled
Step refers to handle 8h under the conditions of 75 DEG C, then powder is filtered out, and after being cleaned successively with ethanol, water, drying, obtains ionic liquid
The particle that positive electricity is modified.
Performance test
Test battery performance
（1）The preparation of positive pole
By 100 grams of positive active material LiCoO2, 2 grams of adhesive vinylidene fluorides（PVDF）, 3 grams of conductive agent acetylene black mixing
Thing is added to 40 grams of METHYLPYRROLIDONEs（NMP）In, then stirring forms uniform positive pole slurry in de-airing mixer
Material.
The slurry is uniformly coated on aluminium foil, then drying, roll-in at 150 DEG C, cut obtained size as 390 millimeters
× 40 millimeters × 18 microns（It is thick）Positive pole, wherein containing 5.8 grams of active component LiCoO2。
（2）The preparation of negative pole
By 100 grams of negative electrode active material native graphites, 1.5 grams of adhesive polytetrafluoroethylene (PTFE)（PTFE）With 1.5 grams of carboxymethyl celluloses
Element（CMC）Mixture be added in 100 grams of water, then in de-airing mixer stirring form uniform cathode size.
The cathode size is uniformly coated on the both sides of copper foil, then dried at 90 DEG C, roll-in, cuts obtained chi
Very little is 395 millimeters × 41 millimeters × 12 microns（It is thick）Negative pole, wherein containing 2.6 grams of active component native graphites.
（3）Battery is made with the composite diaphragm of the present invention
4.0 millimeters × 34 millimeters × 46 millimeters will be included after positive pole obtained above, negative pole and barrier film successively lamination and winding
Square aluminum hull in.The barrier film is respectively by obtained composite diaphragm in embodiment and reference examples.
Will be in solvent（Ethylene carbonate：Methyl ethyl carbonate：Diethyl carbonate（EC/EMC/DEC）Volume ratio is 1:1:
1）In contain 1 mole of lithium hexafluoro phosphate（LiPF6）The above-mentioned batteries of about 2.4 grams of electrolyte injection in, and in a conventional manner
Ageing, sealed cell aluminum hull obtain lithium rechargeable battery.The design capacity of the battery is 750 MAHs.
（4）Battery resistance to elevated temperatures is tested
Method of testing is as follows：Battery progress 1C is charged to 100% Charging state, placed in an oven, oven temperature is with 5 DEG C/min
150 DEG C and 180 DEG C are increased to from room temperature, wherein cell voltage falls is considered as short circuit more than 0.2 volt.
（5）Battery life is tested
Method of testing is as follows：At 25 DEG C ± 5 DEG C, battery is subjected to cycle charge-discharge 500 times, records dump energy.Remaining electricity
Amount is higher, and battery life is longer.
The battery that will be made of the composite diaphragm made by embodiment and reference examples, battery is carried out according to above-mentioned method of testing
Resistance to elevated temperatures and life test, resulting the results are shown in Table 1.
Table 1
As can be seen from the above table, battery diaphragm provided by the invention has preferable intensity and resistance to elevated temperatures, is repeatedly following
Still more than 80% dump energy can be kept after ring electric discharge；And there is the advantages of conductance is low.Embodiment 3 is relative to right
As usual for 1, by carrying out graphene modification to the surface of polyacrylic fibre, the surface hydrophilicity of organic layer can be improved,
It can preferably be integrated with intermediate layer, improve the intensity of diaphragm material；Additional embodiment 3 is for reference examples 2, by right
The oxidation aluminium surface of inorganic particles can make surface particles carry positive charge group using ion liquid modified, and organic
More preferable electrostatic fusion is formed between layer, improves ionic conductivity.
Claims (9)
- A kind of 1. lithium battery organo-mineral complexing barrier film, it is characterised in that include centre inorganic, ceramic layer and its two The organic layer of side, following component by weight is included in the raw material of the organic layer：45~50 parts of polyolefin, graphene 12~18 parts of modacrylic fibers, 2~4 parts of surfactant, 0.5~3 part of antioxidant, 0.5~3 part of lubricant, fill out Expect 2.5~6 parts, 18~35 parts of the first solvent；Include in the raw material of described inorganic, ceramic layer by weight such as the following group Point：Ionic liquid positive electricity be modified 25~40 parts of particle, 15~18 parts of nano alumina particles, 12~15 parts of adhesive, it is non-from Sub- 2~4 parts of surface-active, 15~24 parts of the second solvent.
- 2. lithium battery according to claim 1 organo-mineral complexing barrier film, it is characterised in that the material of described organic layer Expect that form is non-woven fabrics；Described polyolefin is selected from polypropylene or polyethylene；The first described solvent is selected from ethyl acetate, second One or several kinds of mixing in acid butyl ester, ethanol, propyl alcohol.
- 3. lithium battery according to claim 1 organo-mineral complexing barrier film, it is characterised in that described the second solvent choosing From a kind of or both mixing in water or ethanol.
- 4. lithium battery according to claim 1 organo-mineral complexing barrier film, it is characterised in that graphene modified polypropene The preparation method of sour fiber, comprises the following steps：1st step, by weight, by 35~40 parts of hydroxy silicon oils, 12~18 parts of silicon Alkane coupling agent kh-570,4~6 parts of KOH, 8~12 parts of ethyl acetate are well mixed, in a nitrogen atmosphere, are protected after being warming up to 85 DEG C 2~3h of reaction is held, obtains modified polyorganosiloxane performed polymer；2nd step, by weight, take 18~22 parts of butyl acrylate, propylene 25~35 parts of sour 8~12 parts of methyl esters, 0.5~3 part of emulsifying agent and deionized water, 0.5~1h of high-speed stirred, add initiator 1 ~2.5 parts, 1~3h is reacted at 75~85 DEG C, then 1.5~3 parts of 3~5 parts of modified polyorganosiloxane performed polymers and initiator are added dropwise, 1~4h is reacted at 75~85 DEG C, then pH to 7 is adjusted with ammoniacal liquor, obtains acrylic emulsion；3rd step, will be in acrylic emulsion 1~3 part of 8~12 parts of titanium oxide and anion surfactant are added, after being uniformly dispersed, obtains modified acrylic acid emulsion；4th Step, by weight, by 22~30 parts of graphene, 1~3 part of cationic surfactant, silane resin acceptor kh-550 1~5 Part, 4~8 parts of organic solvent are well mixed, obtain cation-modified graphene；6th step, by cation-modified graphene and modification Acrylic emulsion is according to weight than 1：3~6 is well mixed, then feed liquid is sprayed into fiber by spinning nozzle, then by drying Afterwards, graphene modacrylic fibers are obtained.
- 5. lithium battery according to claim 4 organo-mineral complexing barrier film, it is characterised in that spinning head it is a diameter of 0.2~0.4mm；The azo-initiator is selected from azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, azo diformazan Acid amides, azo dicyclohexyl formonitrile HCN hydrochloride, azo isobutyl cyano group formamide, azo diisopropyl imidazoline hydrochloride, azo dicyano One kind or more in valeric acid, azo dicyclohexyl formonitrile HCN, azodiisobutyronitrile, AMBN and ABVN Kind.
- 6. lithium battery according to claim 1 organo-mineral complexing barrier film, it is characterised in that ionic liquid positive electricity is modified Particle preparation method, comprise the following steps：1st step, the preparation of the ionic liquid of silane coupler grafting：Preparation contains 1 The alcohol solution of~5wt% silane coupler KH560 and 3~6% glyoxaline ion liquid, at 85~90 DEG C react 3~ After 8h, the solution of the ionic liquid of silane coupler grafting is obtained；2nd step, porous oxidation aluminum is immersed in silane coupled Handled, then powder filtered out in the solution of the ionic liquid of agent grafting, after clean successively with ethanol, water, dried, obtain from The particle that sub- liquid positive electricity is modified.
- 7. lithium battery according to claim 6 organo-mineral complexing barrier film, it is characterised in that in the 1st described step, miaow Azole ionic liquid is selected from chlorination -1- pi-allyl -3- methylimidazoles or chlorination 1- butyl -3- methylimidazoles or imidazole radicals four One or more of mixing in borofluoride ion liquid；Described alcohols solvent is selected from methanol, ethanol, propane diols, butanol Or one or more of mixing in isoamyl alcohol；In the 2nd described step, processing step refers to handle 5 under the conditions of 70~85 DEG C ~10h.
- 8. the preparation method of the composite diaphragm described in any one of claim 1~7, it is characterised in that comprise the following steps：S1, Polyolefin, graphene modacrylic fibers, surfactant, antioxidant, lubricant, filler, the first solvent are mixed, The melting extrusion at 220~240 DEG C, it is sprayed onto by a diameter of 0.2~0.4mm spinning head on lace curtaining, 140~150 DEG C of roll-ins Sizing, obtain the nonwoven layer that thickness is 10~20 μm；S2, the particle that ionic liquid positive electricity is modified, nano alumina particles, Adhesive, non-ionic surface active, the second solvent are well mixed, and obtain inorganic particle slurry；S3, nothing is coated in nonwoven layer Machine particle slurry, after drying, then place on the drying pulp layer of formation another layer of nonwoven layer；Pass through 140~150 DEG C again After roll-in sizing, composite diaphragm is obtained.
- 9. include the lithium battery of the lithium battery organo-mineral complexing barrier film described in any one of claim 1~7.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111029514A (en) * | 2019-11-14 | 2020-04-17 | 珠海冠宇电池有限公司 | Diaphragm and high-voltage battery comprising same |
| CN112531292A (en) * | 2020-12-11 | 2021-03-19 | 宁波启新精合新能源研究院有限公司 | Lithium ion battery diaphragm prepared from inorganic-organic composite material |
| CN114267922A (en) * | 2021-12-02 | 2022-04-01 | 中材锂膜有限公司 | Organic/inorganic composite isolating membrane and preparation method thereof, electrochemical cell and electricity utilization device |
| CN114976489A (en) * | 2022-07-01 | 2022-08-30 | 珠海冠宇电池股份有限公司 | Coating and diaphragm and battery comprising same |
| CN115799676A (en) * | 2022-12-13 | 2023-03-14 | 上海恩捷新材料科技有限公司 | Electrolyte additive and preparation method and application thereof |
| CN116259923A (en) * | 2023-01-31 | 2023-06-13 | 刘勇 | Preparation method and device of lithium battery diaphragm |
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| CN102828267A (en) * | 2012-09-10 | 2012-12-19 | 浙江大学 | Preparation method of conductive high-strength graphene-reinforced polymer fiber |
| CN106244092A (en) * | 2016-07-28 | 2016-12-21 | 王烽 | A kind of nanometer alumina modified high thermally conductive LED organic silicon packaging glue and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111029514A (en) * | 2019-11-14 | 2020-04-17 | 珠海冠宇电池有限公司 | Diaphragm and high-voltage battery comprising same |
| CN111029514B (en) * | 2019-11-14 | 2021-09-28 | 珠海冠宇电池股份有限公司 | Diaphragm and high-voltage battery comprising same |
| CN112531292A (en) * | 2020-12-11 | 2021-03-19 | 宁波启新精合新能源研究院有限公司 | Lithium ion battery diaphragm prepared from inorganic-organic composite material |
| CN112531292B (en) * | 2020-12-11 | 2023-03-31 | 宁波启新精合新能源研究院有限公司 | Lithium ion battery diaphragm prepared from inorganic-organic composite material |
| CN114267922A (en) * | 2021-12-02 | 2022-04-01 | 中材锂膜有限公司 | Organic/inorganic composite isolating membrane and preparation method thereof, electrochemical cell and electricity utilization device |
| CN114976489A (en) * | 2022-07-01 | 2022-08-30 | 珠海冠宇电池股份有限公司 | Coating and diaphragm and battery comprising same |
| CN114976489B (en) * | 2022-07-01 | 2024-04-05 | 珠海冠宇电池股份有限公司 | Coating, separator comprising same and battery |
| CN115799676A (en) * | 2022-12-13 | 2023-03-14 | 上海恩捷新材料科技有限公司 | Electrolyte additive and preparation method and application thereof |
| CN115799676B (en) * | 2022-12-13 | 2023-09-22 | 江西省通瑞新能源科技发展有限公司 | Electrolyte additive and preparation method and application thereof |
| CN116259923A (en) * | 2023-01-31 | 2023-06-13 | 刘勇 | Preparation method and device of lithium battery diaphragm |
| CN116259923B (en) * | 2023-01-31 | 2024-01-05 | 南京贝迪新材料科技股份有限公司 | Preparation method of lithium battery diaphragm |
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Application publication date: 20180227 |