CN107742690A - A kind of preparation method of poly-lithium battery barrier film - Google Patents
A kind of preparation method of poly-lithium battery barrier film Download PDFInfo
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- CN107742690A CN107742690A CN201711017019.7A CN201711017019A CN107742690A CN 107742690 A CN107742690 A CN 107742690A CN 201711017019 A CN201711017019 A CN 201711017019A CN 107742690 A CN107742690 A CN 107742690A
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- barrier film
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- poly
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- 230000004888 barrier function Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
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- PRBXPAHXMGDVNQ-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]acetic acid Chemical compound OCCOCCOCC(O)=O PRBXPAHXMGDVNQ-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- JRXXEXVXTFEBIY-UHFFFAOYSA-N 3-ethoxypropanoic acid Chemical compound CCOCCC(O)=O JRXXEXVXTFEBIY-UHFFFAOYSA-N 0.000 description 1
- YSIKHBWUBSFBRZ-UHFFFAOYSA-N 3-methoxypropanoic acid Chemical class COCCC(O)=O YSIKHBWUBSFBRZ-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 241000721047 Danaus plexippus Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- WVRPFQGZHKZCEB-UHFFFAOYSA-N Isopropyl 2-methylpropanoate Chemical compound CC(C)OC(=O)C(C)C WVRPFQGZHKZCEB-UHFFFAOYSA-N 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- LCTONWCANYUPML-UHFFFAOYSA-N PYRUVIC-ACID Natural products CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- IDSMHEZTLOUMLM-UHFFFAOYSA-N [Li].[O].[Co] Chemical group [Li].[O].[Co] IDSMHEZTLOUMLM-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- BTMVHUNTONAYDX-UHFFFAOYSA-N butyl propionate Chemical compound CCCCOC(=O)CC BTMVHUNTONAYDX-UHFFFAOYSA-N 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229940117360 ethyl pyruvate Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- QXLBKTGZGPVJOO-UHFFFAOYSA-N hexyl dihydrogen phosphite Chemical compound CCCCCCOP(O)O QXLBKTGZGPVJOO-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- 229940024423 isopropyl isobutyrate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- CSWFWSPPZMEYAY-UHFFFAOYSA-N octadecyl dihydrogen phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(O)O CSWFWSPPZMEYAY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of preparation method of poly-lithium battery barrier film, belong to technical field of lithium batteries.Lower step：The epoxy resin that 25~35 parts of polymer and glyoxaline ion liquid are modified is dissolved in solvent, obtains the first mixture；Surfactant, antioxidant, lubricant, filler are added in the first mixture, after being well mixed, aromatic amine curing agent is added, stirs, obtain the second mixture；Then the second mixture is obtained into spinning film by electrostatic spinning；4th step, by the elevated cure of spinning film, obtain polymer film.The present invention carries out method of electrostatic spinning with polymer by using the epoxy resin that glyoxaline ion liquid is modified and battery separator is prepared, and by the charge interaction during ionic liquid and electrostatic spinning, the barrier film for making to be prepared has higher porosity.
Description
Technical field
The present invention relates to a kind of preparation method of poly-lithium battery barrier film, 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 whether high to lithium ion battery
The security of capacity batteries or high-power battery is all most important.It is understood that the lithium battery diaphragm of commercial applications is at present
PP and PE bilayers or three layers of composite diaphragm, the most outstanding problem that such a barrier film is applied now is exactly that melting point polymer is general
Relatively low, PE fusing points are 130 degrees Celsius, and PP fusing points are 180 degrees Celsius.Under abuse conditions, inside battery heat increased dramatically from
And make battery security that great problems occur.
CN104157818A discloses the compound lithium battery diaphragm of a kind of water-based polymer and inorganic nano-particle, including
Polyolefin supporting layer, the polyolefin supporting layer side are polymer coating, and opposite side is ceramic coating；The polymer coating
Compound all using coating process with ceramic coating, the coating sizing-agent used in the polymer coating and ceramic coating is all water-based slurry
Expect, Aqueous Adhesives and polymer particle are comprised at least in the polymer coating, is comprised at least in the ceramic coating water-based
Adhesive and inorganic nano-particle.CN104183867A one kind nanometers single ion conductor coats lithium battery diaphragm and its preparation side
Method, lithium battery diaphragm are using polymer porous film or non-woven fabrics as base material, using single ion conductor nano particle and polymer pair
Base material carries out what surface modification obtained.CN104022245A is related to a kind of high safety composite diaphragm for lithium battery, by by coaxially melting
Melt the composite fibre composition of method of electrostatic spinning preparation, composite fibre is in concentric shaft-like, and jackshaft is by PET
（PET）Composition, a diameter of 0.8 ~ 4 μm, outer layer is by polyethylene（PE）Or polypropylene（PP）Composition, thickness are 2 ~ 3 μm.On but
The barrier film that the method for stating is prepared there is porosity it is not high the problem of.
The content of the invention
The purpose of the present invention is：Porosity existing for the polymer film that solution blend method is prepared is not high and polymerize
The problem of thing film-strength is low.The present invention carries out Static Spinning by using the epoxy resin that glyoxaline ion liquid is modified and polymer
Battery separator is prepared in silk method, by the charge interaction during ionic liquid and electrostatic spinning, makes to be prepared
Barrier film there is higher porosity.
Technical scheme is：
The preparation method of poly-lithium battery barrier film, comprises the following steps：
1st step, by weight, 25~30 parts of the epoxy resin that 25~35 parts of polymer and glyoxaline ion liquid are modified are molten
Solution obtains the first mixture in 15~20 parts of solvent；
2nd step, 0.5~1 part of surfactant, 1~4 part of antioxidant are added in the first mixture, 2~4 parts of lubricant, is filled out
3~5 parts of material, after being well mixed, 15~18 parts of aromatic amine curing agent is added, is stirred, obtains the second mixture；
3rd step, the second mixture is then obtained into spinning film by electrostatic spinning；
4th step, by the elevated cure of spinning film, obtain polymer film.
Described surfactant be lecithin, fatty glyceride, fatty acid sorbitan, APES,
High-carbon fatty alcohol polyoxyethylene ether, polyoxyethylene carboxylate, fatty acid methyl ester ethoxylate, polyoxyethylene blocks copolymerization
It is one or more of in thing, glycerine pentaerythrite, anhydrous sorbitol, sucrose fatty ester, alkylolamides, polyacrylamide
Mixture.
Described antioxidant is the compound of Hinered phenols, such as can enumerate 2,6- di-t-butyls-paracresol, season penta
Tetrol-four (3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic ester), triethylene glycol-bis- [3- (the 3- tert-butyl group -5- methyl -4- hydroxyls
Phenyl) propionic ester) etc..
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.
The preparation method for the epoxy resin that glyoxaline ion liquid is modified comprises the following steps：
S1, by weight, by 15~20 parts of tung oil, 25~30 parts of fatty alcohol, acid or 0.06~0.1 part of hair of base catalyst
Raw alcoholysis reaction, obtains the first reactant；
S2,35~45 parts of organic acid anhydride, 6~12 parts of glyoxaline ion liquid, 0.2~0.6 part of polymerization inhibitor are then added, carried out anti-
Should, obtain the second reactant；
S3, the second reactant, 5~10 parts of α-methacrylic acid, 3~5 parts of cyclohexyl acrylate are added to Bisphenol F epoxy tree
In 100~150 parts of fat, reacted, obtain the epoxy resin of glyoxaline ion liquid modification.
Fatty alcohol is a kind of or several in isomerous tridecanol, the alcohol of isomery ten, the alcohol of isomery seven, polyethylene glycol or polypropylene glycol
The mixture of kind；One or several kinds of mixtures of the organic acid anhydride in maleic anhydride, acetic anhydride, phthalic anhydride.
Base catalyst be sodium hydroxide, potassium hydroxide, calcium hydroxide, caustic alcohol, potassium ethoxide, sodium methoxide, potassium methoxide or
Calcium oxalate；Acidic catalyst is sulfuric acid, hydrochloric acid, nitric acid or sulfonic acid.
In described S1, reaction temperature is 180~220 DEG C, 1~10h of reaction time.
In described S2, reaction temperature is 50~120 DEG C, 1~10h of reaction time.
In described S3, reaction temperature is 110~120 DEG C, 1~3 hour reaction time.
Include the lithium battery of above-mentioned polymer film.
Beneficial effect
The present invention carries out method of electrostatic spinning with polymer by using the epoxy resin that glyoxaline ion liquid is modified and is prepared
Battery separator, by the charge interaction during ionic liquid and electrostatic spinning, the barrier film for making to be prepared has more
High porosity.
Embodiment
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.
In addition, can also be added in above-mentioned polyolefin and the mixture of epoxy resin other nucleators, antioxidant,
Lubricant, filler, plasticizer etc., as long as the functional aid added does not interfere with the main character of polymer.
Wherein, as antioxidant, such as triphenyl phosphite, three can be used（4- aminomethyl phenyls）Phosphite ester,
Three（4- tert-butyl-phenyls）Phosphite ester, three（Single nonyl phenyl）Phosphite ester, three（2- methyl -4- ethylphenyls）Phosphorous acid
Ester, three（2- methyl -4- tert-butyl-phenyls）Phosphite ester, three（2,4- di-t-butyl phenyl）Phosphite ester, three（Bis--uncles of 2,6-
Butyl phenyl）Phosphite ester, three（2,4- di-t-butyl -5- aminomethyl phenyls）Phosphite ester, three（It is single, dinonylphenyl）Phosphorous
It is acid esters, double（Single nonyl phenyl）It is pentaerythrite-two-phosphite ester, double（2,4- di-t-butyl phenyl）Pentaerythrite-two-phosphorous
It is acid esters, double（2,6- di-t-butyl -4- aminomethyl phenyls）It is pentaerythrite-two-phosphite ester, double（Tri--tert-butyl-phenyls of 2,4,6-）
It is pentaerythrite-two-phosphite ester, double（2,4- di-t-butyl -5- aminomethyl phenyls）Pentaerythrite-two-phosphite ester, 2,2- are sub-
Methyl 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 phosphorous
Acid esters, 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（Bis--uncles of 4,6-
Butyl phenyl）The bi-ester of phosphite such as stearyl phosphite ester；[the 3- of pentaerythrite base-four（3,5- di-t-butyl 4- hydroxyls
Phenyl）Propionic ester], 1,6-HD-bis- [3-（3,5- di-t-butyl 4- hydroxy phenyls）Propionic ester], octadecyl -3-（3,
5- di-t-butyl -4- hydroxy phenyls）Propionic ester, 1,3,5- trimethyls -2,4,6- three（3,5- di-t-butyl -4- hydroxy benzenes first
Base）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 tertiary fourths of 3-
Base -4- hydroxy-5-methyl base phenyl）Propionyloxy] -1,1- dimethyl ethyls 2,4,8,10- tetra- oxaspiro [5,5] hendecane, 1,
[2- methyl-the 4- of 1,3- tri-（3,5- di-t-butyl -4- hydroxy phenylpropionyl epoxides）- 5- tert-butyl-phenyls] benzene that is obstructed such as butane
Phenolic compound；5,7- di-t-butyl -s 3-（3,4- 3,5-dimethylphenyls）- 3H- benzofuran-2-ones etc..These can individually make
With or two or more be 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.
As the preparation method of above-mentioned polymer film, can carry out as follows：
1st step, by weight, 25~30 parts of the epoxy resin that 25~35 parts of polymer and glyoxaline ion liquid are modified are molten
Solution obtains the first mixture in 15~20 parts of solvent；
2nd step, 0.5~1 part of surfactant, 1~4 part of antioxidant are added in the first mixture, 2~4 parts of lubricant, is filled out
3~5 parts of material, after being well mixed, 15~18 parts of aromatic amine curing agent is added, is stirred, obtains the second mixture；
3rd step, the second mixture is then obtained into spinning film by electrostatic spinning；
4th step, by the elevated cure of spinning film, obtain polymer film.
Wherein, the preparation method for the epoxy resin that glyoxaline ion liquid is modified comprises the following steps：
S1, by weight, by 15~20 parts of tung oil, 25~30 parts of fatty alcohol, acid or 0.06~0.1 part of hair of base catalyst
Raw alcoholysis reaction, obtains the first reactant；
S2,35~45 parts of organic acid anhydride, 6~12 parts of glyoxaline ion liquid, 0.2~0.6 part of polymerization inhibitor are then added, carried out anti-
Should, obtain the second reactant；
S3, the second reactant, 5~10 parts of α-methacrylic acid, 3~5 parts of cyclohexyl acrylate are added to Bisphenol F epoxy tree
In 100~150 parts of fat, reacted, obtain the epoxy resin of glyoxaline ion liquid modification.
Fatty alcohol is a kind of or several in isomerous tridecanol, the alcohol of isomery ten, the alcohol of isomery seven, polyethylene glycol or polypropylene glycol
The mixture of kind；One or several kinds of mixtures of the organic acid anhydride in maleic anhydride, acetic anhydride, phthalic anhydride.
Base catalyst be sodium hydroxide, potassium hydroxide, calcium hydroxide, caustic alcohol, potassium ethoxide, sodium methoxide, potassium methoxide or
Calcium oxalate.
Acidic catalyst is sulfuric acid, hydrochloric acid, nitric acid or sulfonic acid.
The used solvent of the present invention, general more common person be ethylene glycol monomethyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether,
Diethylene glycol ether, diethylene glycol (DEG) positive propyl ether, diethylene glycol n-butyl ether, triethylene glycol methyl ether, triethylene glycol ether, propylene glycol monomethyl ether, propane diols
Ether, dipropylene glycol methyl ether, dipropylene glycol ether, dipropylene glycol positive propyl ether, dipropylene glycol n-butyl ether,
Its (poly-) alkylene glycol mono alkane ethers such as tripropylene glycol methyl ether, tripropylene glycol ether；Glycol methyl ether acetate,
Ethylene glycol ether acetate, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetate etc. (poly-) alkylene glycol mono alkane ether acetic acid
Esters；Other ethers such as diethylene glycol dimethyl ether, diethylene glycol (DEG) ethyl methyl ether, diethyl carbitol, tetrahydrofuran；MEK, cyclohexanone,
The ketones such as 2-HEPTANONE, 3- heptanone；The lactic acid alkyl ester class such as 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester；2- hydroxy-2-methyls third
Sour methyl esters, 2- hydroxy-2-methyls ethyl propionate, 3- methoxy methyl propionates, 3- methoxypropionates, 3- ethoxy-propionic acid first
Ester, 3- ethoxyl ethyl propionates, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2- hydroxy-3-methyls methyl butyrate, 3- methyl-
3- methoxybutyls acetic acid esters, 3- methyl -3- methoxybutyls propionic ester, ethyl acetate, n-butyl acetate, n-propyl acetate,
Isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, fourth
Sour n-propyl, isopropyl isobutyrate, butyric acid N-butyl, methyl pyruvate, ethyl pyruvate, pyruvic acid n-propyl, acetoacetate first
Other esters such as ester, ethyl acetoacetate, 2- epoxide ethyl butyrates；The aromatic hydrocarbons class such as toluene, dimethylbenzene；N- first
Carboxylic acyloxy amine such as base pyrrolidones, DMF, DMA etc..The equal solvent can individually make
With can also mix two or more use.
Aromatic amine curing agent in the composition epoxy resin of the present invention contains aromatic amines compound and is at 25 DEG C
Liquid, the aromatic amines compound have amino of at least two Direct Bondings on aromatic rings in a molecule.As upper
Aromatic amine curing agent is stated, for example, diethyl diaminotoluene, double (4- amino -3- ethylphenyls) methane, poly- can be enumerated
1,4- butanediols double (PABA esters) etc..In these, preferably diethyl diaminotoluene, double (4- amino -3- ethyls
Phenyl) methane.
In above-mentioned method, by polymer and epoxy preparation into after solution, you can film layer is prepared by electrostatic spinning,
It can use known in those skilled in the art using electrospinning device progress.After the completion of electrostatic spinning, receiver
Surface receives the filament containing solvent, after solvent volatilization, i.e., in receiver remained on surface spinning fibre, that is, obtains described quiet
Electrospun membrane.Wherein, the internal diameter of the electrospinning device shower nozzle is 0.2~1mm, and the flow velocity of shower nozzle interpolymer solution is 0.6
~2.0 mL/h.The condition of electrostatic spinning includes：Voltage is 5~20KV, and it is 6 ~ 15cm to receive distance, and shower nozzle translational speed is 5
~6mm/s, the rotating speed of receiver is 300~600 rpm.The total time of electrostatic spinning can enter according to the size of required polymer film
Row is corresponding to be selected, and under preferable case, the time of electrostatic spinning is 3~6 h, and the thickness of the spinning film of formation is 80~150 μm.
The temperature and time of the elevated cure of spinning film can will be adjusted according to actual conditions, can typically selected
At 40~70 DEG C, time range is between 10min~60min.
Polymer film provided by the invention, its fracture strength are more than 13Mpa, and elongation at break is more than 190%, and porosity exists
More than 75%.It can be used widely as the polymeric matrix of gel polymer electrolyte.
Embodiment 1
The preparation method of poly-lithium battery barrier film, comprises the following steps：
1st step, by weight, 25 parts of the epoxy resin that polipropene 25 part and glyoxaline ion liquid are modified is dissolved in ethanol
In 15 parts, the first mixture is obtained；
2nd step, 0.5 part of surfactant anhydrous sorbitol, antioxidant 2,6- di-t-butyls-right are added in the first mixture
1 part of cresols, 2 parts of lubricating fluid paraffin, 3 parts of filler titanium oxide powder, after being well mixed, add aromatic amine curing agent 15
Part, stir, obtain the second mixture；
3rd step, the second mixture is then obtained into spinning film by electrostatic spinning；
4th step, by the elevated cure of spinning film, obtain polymer film.
The preparation method for the epoxy resin that glyoxaline ion liquid is modified comprises the following steps：
S1 is by weight, anti-by 0.06 part of 15 parts of tung oil, 25 parts of ten alcohol of isomery, base catalyst potassium hydroxide generation alcoholysis
Should, reaction temperature is 130 DEG C, reaction time 1h, obtains the first reactant；
S2,35 parts of acetic anhydride, 6 parts of glyoxaline ion liquid, 0.2 part of polymerization inhibitor are then added, is reacted, reaction temperature is 50
DEG C, reaction time 1h, obtain the second reactant；
S3, the second reactant, 5 parts of α-methacrylic acid, 3 parts of cyclohexyl acrylate are added to 100 parts of bisphenol F epoxy resin
In, reacted, reaction temperature is 110 DEG C, 1 hour reaction time, obtains the epoxy resin of glyoxaline ion liquid modification.
Embodiment 2
The preparation method of poly-lithium battery barrier film, comprises the following steps：
1st step, by weight, 25~30 parts of the epoxy resin that 35 parts of polypropylene and glyoxaline ion liquid are modified is dissolved in
In 20 parts of ethanol, the first mixture is obtained；
2nd step, 1 part of addition surfactant anhydrous sorbitol, antioxidant 2 in the first mixture, 6- di-t-butyls-to first
4 parts of phenol, 4 parts of lubricating fluid paraffin, 5 parts of filler titanium oxide powder, after being well mixed, add aromatic amine curing agent 18
Part, stir, obtain the second mixture；
3rd step, the second mixture is then obtained into spinning film by electrostatic spinning；
4th step, by the elevated cure of spinning film, obtain polymer film.
The preparation method for the epoxy resin that glyoxaline ion liquid is modified comprises the following steps：
S1 is by weight, anti-by 0.1 part of 20 parts of tung oil, 30 parts of ten alcohol of isomery, base catalyst potassium hydroxide generation alcoholysis
Should, reaction temperature is 120 DEG C, reaction time 10h, obtains the first reactant；
S2,45 parts of acetic anhydride, 12 parts of glyoxaline ion liquid, 0.6 part of polymerization inhibitor are then added, is reacted, reaction temperature is
110 DEG C, reaction time 10h, obtain the second reactant；
S3, the second reactant, 10 parts of α-methacrylic acid, 5 parts of cyclohexyl acrylate are added to bisphenol F epoxy resin 150
In part, reacted, reaction temperature is 90 DEG C, 3 hours reaction time, obtains the epoxy resin of glyoxaline ion liquid modification.
Embodiment 3
The preparation method of poly-lithium battery barrier film, comprises the following steps：
1st step, by weight, 25~30 parts of the epoxy resin that 30 parts of polypropylene and glyoxaline ion liquid are modified is dissolved in
In 18 parts of ethanol, the first mixture is obtained；
2nd step, 0.6 part of surfactant anhydrous sorbitol, antioxidant 2,6- di-t-butyls-right are added in the first mixture
2 parts of cresols, 3 parts of lubricating fluid paraffin, 4 parts of filler titanium oxide powder, after being well mixed, add aromatic amine curing agent 16
Part, stir, obtain the second mixture；
3rd step, the second mixture is then obtained into spinning film by electrostatic spinning；
4th step, by the elevated cure of spinning film, obtain polymer film.
The preparation method for the epoxy resin that glyoxaline ion liquid is modified comprises the following steps：
S1 is by weight, anti-by 0.08 part of 16 parts of tung oil, 28 parts of ten alcohol of isomery, base catalyst potassium hydroxide generation alcoholysis
Should, reaction temperature is 190 DEG C, reaction time 3h, obtains the first reactant；
S2,40 parts of acetic anhydride, 8 parts of glyoxaline ion liquid, 0.4 part of polymerization inhibitor are then added, is reacted, reaction temperature is 90
DEG C, reaction time 3h, obtain the second reactant；
S3, the second reactant, 6 parts of α-methacrylic acid, 4 parts of cyclohexyl acrylate are added to 120 parts of bisphenol F epoxy resin
In, reacted, reaction temperature is 110 DEG C, 2 hours reaction time, obtains the epoxy resin of glyoxaline ion liquid modification.
Reference examples 1
Difference with embodiment 3 is：It is not modified in the preparation of epoxy resin by glyoxaline ion liquid.
The preparation method of poly-lithium battery barrier film, comprises the following steps：
1st step, by weight, 25~30 parts of the epoxy resin that 30 parts of polypropylene and glyoxaline ion liquid are modified is dissolved in
In 18 parts of ethanol, the first mixture is obtained；
2nd step, 0.6 part of surfactant anhydrous sorbitol, antioxidant 2,6- di-t-butyls-right are added in the first mixture
2 parts of cresols, 3 parts of lubricating fluid paraffin, 4 parts of filler titanium oxide powder, after being well mixed, add aromatic amine curing agent 16
Part, stir, obtain the second mixture；
3rd step, the second mixture is then obtained into spinning film by electrostatic spinning；
4th step, by the elevated cure of spinning film, obtain polymer film.
The preparation method for the epoxy resin that glyoxaline ion liquid is modified comprises the following steps：
S1 is by weight, anti-by 0.08 part of 16 parts of tung oil, 28 parts of ten alcohol of isomery, base catalyst potassium hydroxide generation alcoholysis
Should, reaction temperature is 190 DEG C, reaction time 3h, obtains the first reactant；
S2,40 parts of acetic anhydride, 0.4 part of polymerization inhibitor are then added, is reacted, reaction temperature is 90 DEG C, reaction time 3h, is obtained
Second reactant；
S3, the second reactant, 6 parts of α-methacrylic acid, 4 parts of cyclohexyl acrylate are added to 120 parts of bisphenol F epoxy resin
In, reacted, reaction temperature is 110 DEG C, 2 hours reaction time, obtains the epoxy resin of glyoxaline ion liquid modification.
Reference examples 2
Difference with embodiment 3 is：Barrier film is prepared using rolling process, and does not use method of electrostatic spinning.
The preparation method of poly-lithium battery barrier film, comprises the following steps：
1st step, by weight, 25~30 parts of the epoxy resin that 30 parts of polypropylene and glyoxaline ion liquid are modified is dissolved in
In 18 parts of ethanol, the first mixture is obtained；
2nd step, 0.6 part of surfactant anhydrous sorbitol, antioxidant 2,6- di-t-butyls-right are added in the first mixture
2 parts of cresols, 3 parts of lubricating fluid paraffin, 4 parts of filler titanium oxide powder, after being well mixed, add aromatic amine curing agent 16
Part, stir, obtain the second mixture；
3rd step, then the second mixture is prepared by rolling process；
4th step, the barrier film elevated cure that the 3rd step is obtained, obtains polymer film.
The preparation method for the epoxy resin that glyoxaline ion liquid is modified comprises the following steps：
S1 is by weight, anti-by 0.08 part of 16 parts of tung oil, 28 parts of ten alcohol of isomery, base catalyst potassium hydroxide generation alcoholysis
Should, reaction temperature is 190 DEG C, reaction time 3h, obtains the first reactant；
S2,40 parts of acetic anhydride, 8 parts of glyoxaline ion liquid, 0.4 part of polymerization inhibitor are then added, is reacted, reaction temperature is 90
DEG C, reaction time 3h, obtain the second reactant；
S3, the second reactant, 6 parts of α-methacrylic acid, 4 parts of cyclohexyl acrylate are added to 120 parts of bisphenol F epoxy resin
In, reacted, reaction temperature is 110 DEG C, 2 hours reaction time, obtains the epoxy resin of glyoxaline ion liquid modification.
Performance test
1st, Mechanics Performance Testing：
Mechanics Performance Testing is carried out to polymer film in embodiment and reference examples.Using the pull test instrument of routine（Shenzhen monarch
It is auspicious）, sample is dumbbell shaped, and its size is 4mm × 10mm, and the strain rate of instrument is 20mm/min.The fracture strength of test and
The result of elongation at break is as shown in the table.
2nd, porosity is tested：
The test of porosity is carried out to embodiment and reference examples polymer film.Porosity test is carried out according to equation below：P(%)
= (M-M0)/(ρBuOH×πr2·d) ×100%；
Wherein, P is porosity, and M0 is the quality of dry film, and M is that the quality after 2h is soaked in n-butanol, and r is the radius of film, and d is
The thickness of film.Test result such as following table.
3rd, pick up is tested：
Embodiment and reference examples polymer film is dried, it is immersed in electrolyte after weighing up quality（Lithium salts is LiPF6, concentration is
1mol/L, solvent EC, EMC, DEC, mass concentration ratio 2:3:1）Middle 24h, then take out the liquid that film surface is blotted with filter paper
Body, corresponding gel polymer electrolyte is obtained, weigh quality now, operation is all entered in the glove box full of argon gas
OK.
Pick up %=(Wi-W)/W × 100% is calculated according to formula；
Wherein, W is the quality of dry film；Wi is that dry film has soaked the quality after 24h in the electrolytic solution.Test result such as following table.
4th, electrical conductivity is tested：
Embodiment and reference examples polymer film are placed on two stainless steels（SS）Between electrode, the electrolyte of sufficient amount is absorbed（Lithium
Salt is LiPF6, concentration 1M/L, solvent EC, EMC, DEC, mass concentration ratio 2:3:1）, obtain corresponding gelatin polymer
Electrolyte, it is sealed against after 2016 type button cells, carries out AC impedance experiment, be linearly that gel gathers with the intersection point of real axis
The bulk resistance of polymer electrolyte, it is hereby achieved that the ionic conductivity of gel polymer electrolyte：σ=L/ (AR), wherein
L represents the thickness of gel polymer electrolyte, and A is the contact area of stainless steel plate and film, and R is the body electricity of polymer dielectric
Resistance).It is as follows to obtain gel polymer electrolyte electrical conductivity.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Reference examples 1 | Reference examples 2 | |
| Fracture strength MPa | 14.1 | 14.2 | 14.5 | 11.2 | 11.6 |
| Elongation at break % | 185 | 180 | 195 | 162 | 154 |
| Porosity % | 83 | 84 | 85 | 75 | 76 |
| Pick up % | 690 | 680 | 710 | 580 | 620 |
| Electrical conductivity mS/cm | 1.6 | 1.4 | 1.6 | 1.1 | 1.2 |
As can be seen from the above table, polymer film provided by the invention, its fracture strength are more than 13Mpa, and elongation at break is more than
190%, porosity is more than 75%., can be with after adding glyoxaline ion liquid in the preparation of modified epoxy in embodiment 3
The group with positive charge is produced in the phase where polymer, these groups, can when spin processes prepare membrane for polymer
Interaction is produced in the presence of electrostatic, makes the barrier film that electrostatic spinning process obtains that there is higher porosity；And pass through reality
Example 3 and reference examples 2 are applied as can be seen that the barrier film obtained using conventional rolling process can not be poly- with glyoxaline ion liquid modification
Compound produces electrostatic interaction, and therefore, barrier film porosity does not significantly improve.
Claims (9)
1. a kind of preparation method of poly-lithium battery barrier film, it is characterised in that comprise the following steps：
1st step, by weight, 25~30 parts of the epoxy resin that 25~35 parts of polymer and glyoxaline ion liquid are modified are molten
Solution obtains the first mixture in 15~20 parts of solvent；
2nd step, 0.5~1 part of surfactant, 1~4 part of antioxidant are added in the first mixture, 2~4 parts of lubricant, is filled out
3~5 parts of material, after being well mixed, 15~18 parts of aromatic amine curing agent is added, is stirred, obtains the second mixture；
3rd step, the second mixture is then obtained into spinning film by electrostatic spinning；
4th step, by the elevated cure of spinning film, obtain polymer film.
2. the preparation method of poly-lithium battery barrier film according to claim 1, it is characterised in that live on described surface
Property agent be lecithin, fatty glyceride, fatty acid sorbitan, APES, high-carbon fatty alcohol polyoxyethylene ether,
Polyoxyethylene carboxylate, fatty acid methyl ester ethoxylate, polyoxyethylene block copolymer, glycerine pentaerythrite, dehydration mountain
One or more of mixtures in pears alcohol, sucrose fatty ester, alkylolamides, polyacrylamide；Described antioxidant
It is the compound of Hinered phenols.
3. the preparation method of poly-lithium battery barrier film according to claim 1, it is characterised in that described lubricant
Selected from atoleine, solid paraffin, microcrystalline wax and Tissuemat E.
4. the preparation method of poly-lithium battery barrier film according to claim 1, it is characterised in that described imidazoles
The preparation method of ion liquid modified epoxy resin comprises the following steps：S1, by weight, by 15~20 parts of tung oil, fat
25~30 parts of fat alcohol, acid or 0.06~0.1 part of generation alcoholysis reaction of base catalyst, obtain the first reactant；S2, Ran Houjia
Enter 35~45 parts of organic acid anhydride, 6~12 parts of glyoxaline ion liquid, 0.2~0.6 part of polymerization inhibitor, reacted, it is anti-to obtain second
Answer thing；S3, the second reactant, 5~10 parts of α-methacrylic acid, 3~5 parts of cyclohexyl acrylate are added to Bisphenol F epoxy
In 100~150 parts of resin, reacted, obtain the epoxy resin of glyoxaline ion liquid modification.
5. the preparation method of poly-lithium battery barrier film according to claim 4, it is characterised in that fatty alcohol is selected from different
One or more of mixture in structure tridecanol, the alcohol of isomery ten, the alcohol of isomery seven, polyethylene glycol or polypropylene glycol；Organic acid anhydride
One or several kinds of mixtures in maleic anhydride, acetic anhydride, phthalic anhydride.
6. the preparation method of poly-lithium battery barrier film according to claim 4, it is characterised in that base catalyst is
Sodium hydroxide, potassium hydroxide, calcium hydroxide, caustic alcohol, potassium ethoxide, sodium methoxide, potassium methoxide or calcium oxalate；Acidic catalyst is sulphur
Acid, hydrochloric acid, nitric acid or sulfonic acid.
7. the preparation method of poly-lithium battery barrier film according to claim 1, it is characterised in that in described S1,
Reaction temperature is 180~220 DEG C, 1~10h of reaction time；In described S2, reaction temperature is 50~120 DEG C, the reaction time 1
~10h；In described S3, reaction temperature is 110~120 DEG C, 1~3 hour reaction time.
8. the barrier film obtained by the preparation method of the poly-lithium battery barrier film described in any one of claim 1~7.
9. include the lithium battery of the barrier film described in claim 8.
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| CN110350164A (en) * | 2019-06-24 | 2019-10-18 | 湖南省正源储能材料与器件研究所 | A kind of compound nickelic tertiary cathode material of multiphase and preparation method thereof |
| CN115911562A (en) * | 2022-12-30 | 2023-04-04 | 湖南法恩莱特新能源科技有限公司 | Long-life high-safety lithium battery and preparation method thereof |
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| CN103824988A (en) * | 2014-02-24 | 2014-05-28 | 东华大学 | Composite nanofiber lithium battery diaphragm and making method thereof |
| CN104752658A (en) * | 2013-12-27 | 2015-07-01 | 中国科学院青岛生物能源与过程研究所 | Flame-retardant cellulose diaphragm of lithium battery prepared through electrostatic spinning |
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| CN103556234A (en) * | 2013-10-24 | 2014-02-05 | 杭州师范大学 | Anti-static high-beta-crystal-content polyvinylidene fluoride nanometer composite fiber film and preparation method thereof |
| CN104752658A (en) * | 2013-12-27 | 2015-07-01 | 中国科学院青岛生物能源与过程研究所 | Flame-retardant cellulose diaphragm of lithium battery prepared through electrostatic spinning |
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| CN115911562A (en) * | 2022-12-30 | 2023-04-04 | 湖南法恩莱特新能源科技有限公司 | Long-life high-safety lithium battery and preparation method thereof |
| CN115911562B (en) * | 2022-12-30 | 2023-11-28 | 湖南法恩莱特新能源科技有限公司 | Long-life high-safety lithium battery and preparation method thereof |
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