CN115275505A - Low-closed-pore high-film-breaking aramid fiber lithium battery diaphragm and preparation method thereof - Google Patents
Low-closed-pore high-film-breaking aramid fiber lithium battery diaphragm and preparation method thereof Download PDFInfo
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- CN115275505A CN115275505A CN202210528969.0A CN202210528969A CN115275505A CN 115275505 A CN115275505 A CN 115275505A CN 202210528969 A CN202210528969 A CN 202210528969A CN 115275505 A CN115275505 A CN 115275505A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 31
- 239000011148 porous material Substances 0.000 title claims abstract description 24
- 229920006231 aramid fiber Polymers 0.000 title claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 85
- 239000000243 solution Substances 0.000 claims abstract description 71
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 45
- 238000005266 casting Methods 0.000 claims abstract description 32
- 239000012528 membrane Substances 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000000614 phase inversion technique Methods 0.000 claims abstract description 10
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 3
- 229920003235 aromatic polyamide Polymers 0.000 claims description 52
- 239000004760 aramid Substances 0.000 claims description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 18
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 14
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 13
- 229920000577 Nylon 6/66 Polymers 0.000 claims description 12
- TZYHIGCKINZLPD-UHFFFAOYSA-N azepan-2-one;hexane-1,6-diamine;hexanedioic acid Chemical compound NCCCCCCN.O=C1CCCCCN1.OC(=O)CCCCC(O)=O TZYHIGCKINZLPD-UHFFFAOYSA-N 0.000 claims description 12
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 12
- 239000006184 cosolvent Substances 0.000 claims description 12
- 239000005457 ice water Substances 0.000 claims description 12
- 229920001897 terpolymer Polymers 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 239000001110 calcium chloride Substances 0.000 claims description 10
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 10
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000007493 shaping process Methods 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 230000003472 neutralizing effect Effects 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 4
- 229920000299 Nylon 12 Polymers 0.000 claims description 4
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 4
- 229920000131 polyvinylidene Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 4
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 abstract description 5
- 238000005755 formation reaction Methods 0.000 abstract 1
- 238000004513 sizing Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 19
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002344 surface layer Substances 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/423—Polyamide resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/426—Fluorocarbon polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a low-closed-pore high-rupture-membrane aramid fiber lithium battery diaphragm and a preparation method thereof, wherein a polymerization solution of a heat-resistant high polymer and a polymerization solution of a low-melting-point polymer are prepared; mixing the polymerization solution of the low-melting-point polymer and the polymerization solution of the heat-resistant high polymer to obtain a mixed solution, adding a pore-forming agent into the mixed solution, and uniformly stirring to obtain a membrane casting solution; and coating the casting solution on a substrate, firstly carrying out steam bath, then soaking in water to carry out phase inversion method film formation, drying, cooling and sizing to obtain the low-closed-pore high-rupture-membrane aramid fiber lithium battery diaphragm. The invention can simultaneously and greatly improve the membrane rupture temperature of the membrane and reduce the pore-closing temperature, reduce the self-discharge phenomenon and doubly improve the safety performance of the battery.
Description
Technical Field
The invention belongs to the field of lithium battery materials, and particularly relates to a low-closed-pore high-film-breaking aramid fiber lithium battery diaphragm and a preparation method thereof.
Background
With the unexpected growth of new energy automobiles, the demand for power lithium battery separators continues to increase. People pay more and more attention to the endurance mileage and safety problems of power batteries. The diaphragm can prevent the contact between a positive electrode and a negative electrode, the polyolefin diaphragm is mostly adopted in the diaphragm of the conventional power lithium battery, and polyvinylidene fluoride (PVDF) modification or ceramic modification is usually carried out on the polyolefin diaphragm in order to improve the endurance mileage and heat resistance. The PVDF coating is used for improving the bonding performance of the diaphragm and the electrode, and the ceramic coating is used for improving the wettability and the heat resistance of the diaphragm and electrolyte. However, in the two modes, the base film is polyolefin, so that the heat resistance of the diaphragm can be improved only to a certain extent, and the diaphragm rupture temperature cannot be increased to more than 200 ℃.
When the battery generates heat release and counter-responds to self-heating, overcharging or short circuit outside the battery, a large amount of heat can be generated, at the moment, if the diaphragm forms micropore closure, then the continuous transmission of ions is blocked to form open circuit, the effect of protecting the battery can be achieved, and the temperature when the micropore closure is closed is the closed pore temperature. For lithium batteries, it is desirable that the closed cell temperature be low, so that the closed cells can be closed when the temperature rises, thereby preventing the occurrence of short circuits and improving the safety of the battery.
Disclosure of Invention
The invention aims to provide a low-closed-hole high-film-breaking aramid fiber lithium battery diaphragm and a preparation method thereof, which are used for overcoming the defects of the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a low-closed-pore high-film-breaking aramid fiber lithium battery diaphragm comprises the following steps:
(1) Preparing a polymerization solution of a heat-resistant polymer at a concentration of 1.0wt/% -20wt/%, and a polymerization solution of a low-melting polymer at a concentration of 0.5wt/% -30 wt%;
(2) Polymerizing liquid of low-melting point polymer and polymerizing liquid of heat-resistant polymer according to the proportion of 1:1, obtaining a mixed solution, adding a pore-forming agent into the mixed solution, and uniformly stirring to obtain a membrane casting solution;
(3) Coating the casting solution on a substrate, firstly carrying out steam bath, then immersing in water for film formation by a phase inversion method, drying, cooling and shaping to obtain a heat-resistant high polymer porous layer, wherein the heat-resistant high polymer porous layer is the low-closed-pore high-rupture-membrane aramid fiber lithium battery diaphragm.
Further, the heat-resistant high polymer is any one of meta-aramid, para-aramid and aramid 1314.
Further, when the heat-resistant polymer is meta-aramid, the preparation process of the polymerization solution of the heat-resistant polymer is as follows: adding a cosolvent into an organic solvent A under the protection of nitrogen, dissolving m-phenylenediamine, carrying out a reaction in an ice water bath, adding isophthaloyl dichloride while stirring, adding a neutralizer after the reaction is carried out for a preset time, and neutralizing to obtain a meta-aramid polymerization solution with the concentration of 1wt/% -20 wt/%;
when the heat-resistant high polymer is para-aramid, the preparation process of the polymerization liquid of the heat-resistant high polymer is as follows: adding a cosolvent into an organic solvent A under the protection of nitrogen, dissolving p-phenylenediamine, carrying out a reaction in an ice water bath, adding terephthaloyl chloride while stirring, adding a neutralizer after the reaction is carried out for a preset time, and neutralizing to obtain a p-aramid polymer solution with the concentration of 1wt/% -20 wt/%;
when the heat-resistant high polymer is aramid 1314, the preparation process of the polymerization liquid of the heat-resistant high polymer is as follows: adding a cosolvent into an organic solvent A under the protection of nitrogen to dissolve a mixture of p-phenylenediamine and m-phenylenediamine, wherein the mass ratio of the p-phenylenediamine to the m-phenylenediamine is (1-9): (9-1), carrying out the reaction in an ice-water bath, adding a mixture of terephthaloyl chloride and isophthaloyl chloride while stirring, wherein the mass ratio of the terephthaloyl chloride to the isophthaloyl chloride is (1-9): (9-1), adding a neutralizing agent for neutralization after the reaction is carried out for preset time to obtain an aramid 1314 polymerization solution with the concentration of 1 wt/percent-20 wt/percent.
Further, the organic solvent A is any one of N, N-dimethylacetamide, N-dimethylformamide and N-methylpyrrolidone; the cosolvent is lithium chloride or calcium chloride; the neutralizer is any one of sodium hydroxide, calcium hydroxide and potassium hydroxide.
Further, the low-melting-point high polymer is any one or combination of a plurality of materials selected from polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride-trifluoroethylene, ethylene-octene copolymer, ethylene-propylene copolymer, nylon 6/66/12 terpolymer, nylon 6/66/1010 terpolymer, nylon 6/66/610 terpolymer and polyethylene glycol succinate.
Further, the preparation process of the polymerization solution of the low-melting-point polymer comprises the following steps: dissolving the low-melting-point polymer in an organic solvent B to obtain a polymerization solution of the low-melting-point polymer;
the organic solvent B is any one or combination of more of tetrahydrofuran, acetone, dimethyl sulfoxide and tetramethylurea.
Further, the melting point of the low-melting-point polymer is 100-130 ℃.
Further, the pore-forming agent is any one or combination of more of calcium chloride, lithium chloride, polyvinylpyrrolidone and polyethylene glycol, and the addition amount of the pore-forming agent is 2 wt%/10 wt% of the mass of the mixed solution.
Further, the temperature of the steam bath is 30-60 ℃, and the humidity is 50% -100%.
The low-closed-hole high-rupture-membrane aramid fiber lithium battery diaphragm is 5-30 microns thick and 0.5-3 microns in pore diameter.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention adopts the heat-resistant high polymer as the porous base layer, can remove the limitation of the polyolefin diaphragm on the heat resistance, has no heat shrinkage phenomenon at the temperature of 250 ℃, and can greatly improve the heat resistance of the diaphragm; in addition, by adding the low-melting-point polymer, the diaphragm has low closed pore temperature, and double protection is provided for the safety performance of the lithium battery; meanwhile, the heat-resistant high polymer is used as a porous base layer, so that the porosity of the diaphragm can be improved, the wettability of electrolyte can be improved, the energy density of the battery can be improved, and the endurance mileage of the automobile can be improved.
Furthermore, the invention can improve the thermal stability of the diaphragm, and the high-temperature resistant polymer is used as the porous base layer, so that the heat resistance of the diaphragm can be greatly improved, the shrinkage value of the diaphragm at high temperature is reduced, and the thermal shrinkage value of the diaphragm at 250 ℃ for 1h is 0.
Furthermore, in the first charge and discharge process of the lithium battery, the electrode material and the electrolyte react on a solid-liquid interface to form a passivation layer, namely an SEI (solid electrolyte interface) film for short, covering the surface of the electrode material, so that the interaction between the electrolyte and the graphite cathode can be prevented. However, when the temperature rises above 100 ℃, the SEI film undergoes a decomposition reaction, causing an irreversible reaction between the electrolyte and the surface of the negative electrode, resulting in the formation of irreversible capacity and the generation of heat, which further increases the temperature. When the temperature exceeds 130 ℃, the SEI film can be completely broken down, side reactions occur when the electrode and the electrolyte are contacted, and when enough heat is accumulated, the electrolyte is decomposed and finally thermally runaway. Therefore, the invention selects the aramid fiber 1313, the aramid fiber 1414 and the aramid fiber 1314 as the membrane breaking temperature of the membrane, and improves the safety of the battery from the two aspects of the hole closing temperature and the membrane breaking temperature.
Furthermore, the invention can reduce the thermal closed pore temperature of the diaphragm, the melting point of the selected low-melting-point polymer is 100-130 ℃, and the diaphragm can generate closed pore behavior before the temperature reaches the temperature of the SEI film and is completely decomposed, thereby preventing the temperature from being rapidly increased and improving the safety of the battery.
Furthermore, the invention can improve the uniformity of micropores of the diaphragm, and the steam bath is added for pre-perforating before the casting film liquid enters the water tank for film formation, so that the rapid solidification of the casting film liquid entering the water tank is avoided, the uniformity of holes formed in the diaphragm and the pore size of the surface layer are influenced, and the air permeability of the diaphragm is improved.
Furthermore, the invention can improve the cycle performance of the battery, the heat-resistant high polymer is used as a base layer through phase-transition wet film formation, the aperture of the diaphragm is larger, and the low-melting-point polymer is added into the film casting solution, so that the aperture of the diaphragm can be improved, the self-discharge phenomenon of the battery is reduced, the attenuation phenomenon of the battery in the cycle process is reduced, and the cycle performance of the battery is improved.
Detailed Description
The invention is further described below.
A lithium battery diaphragm with low closed pores and high rupture strength is mainly composed of a heat-resistant high polymer porous layer, wherein the heat-resistant high polymer porous layer is prepared by a phase conversion method from a casting solution composed of a heat-resistant high polymer and a low-melting-point high polymer, the low-melting-point high polymer is uniformly dispersed in the heat-resistant high polymer, the thickness of the heat-resistant high polymer porous layer is 5-30 mu m, and the pore diameter is 0.5-3 mu m.
Wherein the heat-resistant high polymer is any one of meta-aramid, para-aramid and aramid 1314; the low-melting-point high polymer is any one or more than two of polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride-trifluoroethylene, ethylene-octene copolymer, ethylene-propylene copolymer, nylon 6/66/12 terpolymer, nylon 6/66/1010 terpolymer, nylon 6/66/610 terpolymer and polyethylene glycol succinate; the melting point of the low-melting-point high polymer is 100-130 ℃;
a preparation method of a lithium battery diaphragm with low closed pores and high rupture strength comprises the following steps:
(1) Preparing a polymerization solution of a heat-resistant polymer at a concentration of 1 to 20wt/%, and preparing a polymerization solution of a low-melting polymer at a concentration of 0.5 to 30 wt.%;
(2) Polymerizing liquid of low-melting point polymer and polymerizing liquid of heat-resistant polymer according to the proportion of 1:1 to obtain a mixed solution, adding a pore-forming agent into the mixed solution, wherein the addition amount of the pore-forming agent is 2wt% -10wt% of the mass of the mixed solution, and uniformly stirring to obtain a membrane casting solution;
(3) Coating the casting solution on a release film or a stainless steel strip by coating equipment, wherein the coating mode is any one of micro-gravure coating, scraper coating, slit extrusion and wire rod coating, the casting solution is firstly subjected to steam bath (the temperature of the steam bath is 30-60 ℃ and the humidity is 50-100%), then the casting solution is soaked in a water tank for phase inversion method film formation, and then the casting solution enters a drying box for drying, cooling and shaping, and then the drying box is wound to obtain a heat-resistant high polymer porous layer, and the heat-resistant high polymer porous layer is the low-closed-pore high-rupture-film aramid lithium battery diaphragm.
Wherein, the preparation of the polymerization solution of the heat-resistant polymer specifically comprises the following steps:
when the heat-resistant high polymer is meta-aramid, the preparation process of the polymerization liquid of the heat-resistant high polymer is as follows: adding a cosolvent into an organic solvent A under the protection of nitrogen, dissolving m-phenylenediamine, carrying out a reaction in an ice water bath, adding isophthaloyl dichloride while stirring, adding a neutralizer after the reaction is carried out for a preset time, and neutralizing to obtain a meta-aramid polymerization solution;
when the heat-resistant high polymer is para-aramid, the preparation process of the polymerization liquid of the heat-resistant high polymer is as follows: adding a cosolvent into an organic solvent A under the protection of nitrogen, dissolving p-phenylenediamine, carrying out a reaction in an ice water bath, adding terephthaloyl chloride while stirring, and adding a neutralizer for neutralization after the reaction is carried out for a preset time to obtain a para-aramid polymerization solution;
when the heat-resistant high polymer is aramid 1314, the preparation process of the polymerization liquid of the heat-resistant high polymer is as follows: adding a cosolvent into an organic solvent A under the protection of nitrogen to dissolve a mixture of p-phenylenediamine and m-phenylenediamine, wherein the mass ratio of the p-phenylenediamine to the m-phenylenediamine is (1-9): (9-1), carrying out the reaction in an ice-water bath, adding a mixture of terephthaloyl chloride and isophthaloyl chloride while stirring, wherein the mass ratio of the terephthaloyl chloride to the isophthaloyl chloride is (1-9): (9-1), adding a neutralizer for neutralization after the reaction is carried out for a preset time to obtain an aramid 1314 polymerization solution;
the preparation of the polymerization solution of the low-melting-point polymer comprises the following steps: and dissolving the low-melting-point polymer in an organic solvent B to obtain a polymerization solution of the low-melting-point polymer.
The organic solvent A is any one of N, N-dimethylacetamide, N, N-dimethylformamide and N-methylpyrrolidone; the cosolvent is any one of lithium chloride and calcium chloride; the neutralizer is any one of sodium hydroxide, calcium hydroxide and potassium hydroxide; the organic solvent B is one or more than two of tetrahydrofuran, acetone, dimethyl sulfoxide and tetramethylurea; the pore-forming agent is one or more than two of calcium chloride, lithium chloride, polyvinylpyrrolidone and polyethylene glycol, and the addition amount of the pore-forming agent is 2 wt%/10 wt% of the mixed solution.
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
The following detailed description is illustrative of the embodiments and is intended to provide further details of the invention. Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention.
Example 1
Preparing meta-aramid polymerization solution: liCl is added into 250ml of DMAc (N, N-dimethylacetamide) under the protection of nitrogen, 1.0814g of m-phenylenediamine is dissolved, the reaction is carried out in an ice-water bath, 2.0302g of isophthaloyl dichloride is slowly added while stirring, after the reaction is carried out for 30min, 0.074g of calcium hydroxide is added for neutralization, and the m-aramid polymer solution with the concentration of 1.0wt/% is obtained.
Preparing a casting solution: dissolving polyvinylidene fluoride-hexafluoropropylene in a mass fraction of 0.5wt% in 250ml of tetrahydrofuran, mixing with the meta-aramid polymerization solution to obtain a mixed solution, adding a pore-forming agent calcium chloride accounting for 2wt% of the mixed solution, and uniformly stirring to obtain a casting solution;
preparation of a porous layer of a heat-resistant high polymer: the casting solution is coated on a stainless steel strip by coating equipment and is subjected to steam bath at the temperature of 30 ℃ and the humidity of 50 percent. Then soaking the film in a water tank for film formation by a phase inversion method, drying the film in a drying oven, cooling and shaping the film, and rolling the film to the thickness of 5 mu m.
Example 2
Preparing a para-aramid polymerization solution: adding CaCl to 250ml of NMP (N-methylpyrrolidone) under nitrogen protection221.628g of p-phenylenediamine is dissolved, the reaction is carried out in an ice-water bath, 40.604g of terephthaloyl chloride is slowly added while stirring, 1.48g of calcium hydroxide is added for neutralization after the reaction is carried out for 30min, and the p-aramid polymerization solution with the concentration of 20wt/% is obtained.
Preparing a casting solution: dissolving an ethylene-octene copolymer in 250ml of tetrahydrofuran by mass percent of 30%, mixing with the para-aramid polymerization solution to obtain a mixed solution, adding a pore-forming agent lithium chloride by mass percent of 10% of the mixed solution, and uniformly stirring to obtain a casting solution;
preparation of a porous layer of a heat-resistant high polymer: the casting solution is coated on a stainless steel strip by coating equipment, and the stainless steel strip is subjected to steam bath at the temperature of 60 ℃ and the humidity of 100%. Then soaking the film in a water tank for film formation by a phase inversion method, drying the film in a drying oven, cooling and shaping the film, and rolling the film to a thickness of 30 mu m.
Example 3
Preparing an aramid 1314 polymerization solution: adding CaCl to 250ml of NMP (N-methylpyrrolidone) under nitrogen protection210.814g of a mixture of p-phenylenediamine and m-phenylenediamine (mass ratio: 1And m-phthaloyl chloride (mass ratio of 1.
Preparing a casting solution: dissolving polyethylene glycol succinate in 250ml of tetrahydrofuran by weight percent, mixing with the aramid 1314 polymerization solution to obtain a mixed solution, adding a pore-forming agent polyethylene glycol of which the mass is 5wt% of the mixed solution, and uniformly stirring to obtain a casting solution;
preparation of a porous layer of a heat-resistant high polymer: the casting solution is coated on a stainless steel strip by coating equipment, and the stainless steel strip is subjected to steam bath at the temperature of 45 ℃ and the humidity of 75%. Then soaking the film in a water tank for film formation by a phase inversion method, drying the film in a drying oven, cooling and shaping the film, and rolling the film to 15 mu m in thickness.
Example 4
Preparing an aramid 1314 polymerization solution: adding CaCl into 250ml of DMF (N, N-dimethylformamide) under the protection of nitrogen2And 10.814g of a mixture of p-phenylenediamine and m-phenylenediamine (mass ratio 1.
Preparing a casting solution: dissolving a nylon 6/66/12 terpolymer in 250ml of tetrahydrofuran by the mass fraction of 10wt%, mixing with the aramid 1314 polymerization solution to obtain a mixed solution, adding a pore-forming agent, namely, polyvinylpyrrolidone, of which the mass is 5wt% of the mixed solution, and uniformly stirring to obtain a casting solution;
preparation of a porous layer of a heat-resistant high polymer: the casting solution is coated on a stainless steel strip by coating equipment and is subjected to steam bath at the temperature of 45 ℃ and the humidity of 75 percent. Then soaking the film in a water tank for film formation by a phase inversion method, drying the film in a drying oven, cooling and shaping the film, and rolling the film to a thickness of 15 mu m.
Example 5
Preparing an aramid fiber 1314 polymerization solution: 250ml of NMP (N-methyl) under nitrogen protectionPyrrolidone) with CaCl2And 10.814g of a mixture of p-phenylenediamine and m-phenylenediamine (mass ratio 9.
Preparing a casting solution: dissolving a nylon 6/66/1010 terpolymer, a nylon 6/66/610 terpolymer and polyvinylidene fluoride-trifluoroethylene (mass ratio is 1;
preparation of a porous layer of a heat-resistant high polymer: the casting solution is coated on a stainless steel strip by coating equipment and is subjected to steam bath at the temperature of 45 ℃ and the humidity of 75 percent. Then soaking the film in a water tank for film formation by a phase inversion method, drying the film in a drying oven, cooling and shaping the film, and rolling the film to a thickness of 15 mu m.
Comparative example 1:
a 7 μm PE-based film is commercially available.
Comparative example 2:
preparing meta-aramid polymerization solution: liCl is added into 250ml of DMAc (N, N-dimethylacetamide) under the protection of nitrogen, 1.0814g of m-phenylenediamine is dissolved, the reaction is carried out in an ice-water bath, 2.0302g of isophthaloyl chloride is slowly added while stirring, after 30min of reaction, 0.074g of calcium hydroxide is added for neutralization, and the m-aramid polymerization solution with the concentration of 1.0wt/% is obtained.
Preparing a casting solution: and adding a pore-forming agent calcium chloride into the meta-aramid polymerized liquid, wherein the pore-forming agent calcium chloride accounts for 0.5wt% of the meta-aramid polymerized liquid by mass, and uniformly stirring to obtain a membrane casting solution.
Preparation of a porous layer of a heat-resistant high polymer: the casting solution is coated on a stainless steel strip by coating equipment, and is firstly subjected to steam bath, wherein the temperature of the steam bath is 30 ℃, and the humidity is 50%. Then soaking the film in a water tank for film formation by a phase inversion method, drying the film in a drying oven, cooling and shaping the film, and rolling the film to a thickness of 5 mu m.
TABLE 1 example and comparative example separator Performance
As can be seen from Table 1, compared with the PE-based film, the thermal hole-closing temperature of the diaphragm prepared in examples 1-5, to which the low-melting polymer was added, was reduced, and the film breaking temperature was increased to 250 ℃ or higher; the PE film becomes transparent at the temperature of 250 ℃ and shrinks; in the comparative example 2, only the heat-resistant high polymer porous layer is adopted, the low-melting-point polymer is not added, the diaphragm has no closed pore temperature, and the diaphragm can directly break after reaching a certain temperature.
It will be appreciated by those skilled in the art that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The embodiments disclosed above are therefore to be considered in all respects as illustrative and not restrictive. All changes which come within the scope of or equivalence to the invention are intended to be embraced therein.
Claims (10)
1. A preparation method of a low-closed-pore high-rupture-membrane aramid fiber lithium battery diaphragm is characterized by comprising the following steps of:
(1) Preparing a polymerization solution of a heat-resistant polymer at a concentration of 1.0wt/% -20wt/%, and a polymerization solution of a low-melting polymer at a concentration of 0.5wt/% -30 wt%;
(2) Polymerizing liquid of low-melting point polymer and polymerizing liquid of heat-resistant high polymer according to the ratio of 1:1, obtaining a mixed solution, adding a pore-forming agent into the mixed solution, and uniformly stirring to obtain a membrane casting solution;
(3) Coating the casting solution on a substrate, firstly carrying out steam bath, then soaking in water for film formation by a phase inversion method, drying, cooling and shaping to obtain a heat-resistant high polymer porous layer, wherein the heat-resistant high polymer porous layer is the low-closed-pore high-rupture aramid fiber lithium battery diaphragm.
2. The method for preparing the low-closed-cell high-rupture-membrane aramid lithium battery separator as claimed in claim 1, wherein the heat-resistant high polymer is any one of meta-aramid, para-aramid and aramid 1314.
3. The preparation method of the low-closed-cell high-rupture-membrane aramid lithium battery separator as claimed in claim 2, wherein when the heat-resistant high polymer is meta-aramid, the preparation process of the polymerization solution of the heat-resistant high polymer is as follows: adding a cosolvent into an organic solvent A under the protection of nitrogen, dissolving m-phenylenediamine, carrying out a reaction in an ice water bath, adding isophthaloyl dichloride while stirring, adding a neutralizer after the reaction is carried out for a preset time, and neutralizing to obtain a meta-aramid polymerization solution with the concentration of 1wt/% -20 wt/%;
when the heat-resistant high polymer is para-aramid, the preparation process of the polymerization liquid of the heat-resistant high polymer is as follows: adding a cosolvent into an organic solvent A under the protection of nitrogen, dissolving p-phenylenediamine, carrying out a reaction in an ice water bath, adding terephthaloyl chloride while stirring, adding a neutralizer after the reaction is carried out for a preset time, and neutralizing to obtain a p-aramid polymer solution with the concentration of 1wt/% -20 wt/%;
when the heat-resistant high polymer is aramid 1314, the preparation process of the polymerization liquid of the heat-resistant high polymer is as follows: adding a cosolvent into an organic solvent A under the protection of nitrogen to dissolve a mixture of p-phenylenediamine and m-phenylenediamine, wherein the mass ratio of the p-phenylenediamine to the m-phenylenediamine is (1-9): (9-1), carrying out the reaction in an ice-water bath, adding a mixture of terephthaloyl chloride and isophthaloyl chloride while stirring, wherein the mass ratio of the terephthaloyl chloride to the isophthaloyl chloride is (1-9): (9-1), adding a neutralizing agent for neutralization after the reaction is carried out for the preset time to obtain the aramid 1314 polymerization solution with the concentration of 1wt/% -20 wt/%.
4. The preparation method of the low-closed-cell high-rupture-membrane aramid lithium battery diaphragm as claimed in claim 3, wherein the organic solvent A is any one of N, N-dimethylacetamide, N-dimethylformamide and N-methylpyrrolidone; the cosolvent is lithium chloride or calcium chloride; the neutralizer is any one of sodium hydroxide, calcium hydroxide and potassium hydroxide.
5. The method for preparing the low-closed-cell high-rupture-membrane aramid lithium battery membrane as claimed in claim 1, wherein the low-melting-point high polymer is any one or more of polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride-trifluoroethylene, ethylene-octene copolymer, ethylene-propylene copolymer, nylon 6/66/12 terpolymer, nylon 6/66/1010 terpolymer, nylon 6/66/610 terpolymer and polyethylene glycol succinate.
6. The preparation method of the low-closed-pore high-rupture-membrane aramid lithium battery separator as claimed in claim 1, wherein the preparation process of the polymerization solution of the low-melting-point polymer is as follows: dissolving the low-melting-point polymer in an organic solvent B to obtain a polymerization solution of the low-melting-point polymer;
the organic solvent B is any one or combination of more of tetrahydrofuran, acetone, dimethyl sulfoxide and tetramethylurea.
7. The preparation method of the low-closed-cell high-rupture-membrane aramid lithium battery separator as claimed in claim 1, wherein the melting point of the low-melting-point polymer is 100-130 ℃.
8. The preparation method of the low-closed-pore high-rupture-membrane aramid lithium battery diaphragm as claimed in claim 1, wherein the pore-forming agent is any one or combination of calcium chloride, lithium chloride, polyvinylpyrrolidone and polyethylene glycol, and the addition amount of the pore-forming agent is 2 wt%/10 wt% of the mass of the mixed solution.
9. The preparation method of the low-closed-pore high-rupture-membrane aramid fiber lithium battery diaphragm as claimed in claim 1, wherein the temperature of the steam bath is 30-60 ℃, and the humidity is 50% -100%.
10. The low-closed-cell high-rupture-membrane aramid lithium battery diaphragm prepared by the preparation method of any one of claims 1 to 9 is characterized in that the thickness of the low-closed-cell high-rupture-membrane aramid lithium battery diaphragm is 5 to 30 micrometers, and the pore diameter of the low-closed-cell high-rupture-membrane aramid lithium battery diaphragm is 0.5 to 3 micrometers.
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