CN113131089A - Spider-web structure lithium ion battery diaphragm and preparation method thereof - Google Patents
Spider-web structure lithium ion battery diaphragm and preparation method thereof Download PDFInfo
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- CN113131089A CN113131089A CN201911394753.4A CN201911394753A CN113131089A CN 113131089 A CN113131089 A CN 113131089A CN 201911394753 A CN201911394753 A CN 201911394753A CN 113131089 A CN113131089 A CN 113131089A
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- lithium ion
- web structure
- ion battery
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920000098 polyolefin Polymers 0.000 claims abstract description 72
- 239000002861 polymer material Substances 0.000 claims abstract description 32
- -1 polyethylene Polymers 0.000 claims description 64
- 239000004698 Polyethylene Substances 0.000 claims description 63
- 239000002131 composite material Substances 0.000 claims description 47
- 238000002791 soaking Methods 0.000 claims description 42
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- 229920000573 polyethylene Polymers 0.000 claims description 32
- 239000004642 Polyimide Substances 0.000 claims description 26
- 229920001721 polyimide Polymers 0.000 claims description 26
- 239000004743 Polypropylene Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 25
- 229920001155 polypropylene Polymers 0.000 claims description 25
- 239000004952 Polyamide Substances 0.000 claims description 22
- 239000004962 Polyamide-imide Substances 0.000 claims description 22
- 229920002647 polyamide Polymers 0.000 claims description 22
- 229920002312 polyamide-imide Polymers 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 19
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 14
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 241000239290 Araneae Species 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 239000004697 Polyetherimide Substances 0.000 claims description 7
- 239000004793 Polystyrene Substances 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920005575 poly(amic acid) Polymers 0.000 claims description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 7
- 229920000927 poly(p-phenylene benzobisoxazole) Polymers 0.000 claims description 7
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 7
- 229920001601 polyetherimide Polymers 0.000 claims description 7
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 7
- 229920002223 polystyrene Polymers 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 239000012528 membrane Substances 0.000 abstract description 25
- 239000003792 electrolyte Substances 0.000 description 41
- 238000012360 testing method Methods 0.000 description 21
- 239000000203 mixture Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 9
- 238000009736 wetting Methods 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 5
- 238000005524 ceramic coating Methods 0.000 description 5
- 241000221931 Hypomyces rosellus Species 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- JJLHDJOAPXBNPR-UHFFFAOYSA-N phenyl(2-phenylethynyl)mercury Chemical compound C=1C=CC=CC=1[Hg]C#CC1=CC=CC=C1 JJLHDJOAPXBNPR-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a lithium ion battery diaphragm with a spider-web structure and a preparation method thereof, and aims to solve the technical problems of improving the thermal stability and the dimensional stability of the diaphragm, reducing the cost and improving the charge-discharge efficiency of a lithium ion battery. The lithium ion battery diaphragm with the spider-web structure takes a polyolefin film as a base film, the base film is coated with a high polymer material, the porosity of the polyolefin film is 30-60%, the high polymer material forms the spider-web structure on the surface of the polyolefin, and the high polymer material accounts for 20-80% of the mass of the lithium ion battery diaphragm with the spider-web structure. Compared with the prior art, the preparation method provided by the invention has the advantages that the thermal stability and the size stability of the polyolefin film are changed, the membrane is maintained for 1 hour at 130 ℃, the thermal shrinkage rate is 1%, maintained for 1 hour at 150 ℃, the thermal shrinkage rate is 3%, maintained for 1 hour at 200 ℃, and the thermal shrinkage rate is 5%, and the wettability of the polyolefin film is improved.
Description
Technical Field
The invention relates to a lithium ion battery material and a preparation method thereof, in particular to a diaphragm and a preparation method thereof.
Technical Field
At present, the diaphragm material of the lithium ion battery is mainly polyolefin, such as polyethylene and polypropylene. The polyolefin diaphragm has good chemical stability, but the thermal stability and the dimensional stability of the polyolefin diaphragm are poor, the thermal shrinkage rate of the polyolefin diaphragm is up to more than 30% at 130 ℃ for 1h, and when the temperature of the lithium ion battery is too high, volume shrinkage is easy to occur, so that the area of the diaphragm is reduced to cause short circuit of the lithium ion battery, and the lithium ion battery is overheated to explode or catch fire.
The prior art mainly comprises the following steps of carrying out thermal stability and dimensional stability modification on a lithium battery diaphragm: grafting heat-resistant groups on the surface of the film (diaphragm), crosslinking the film material, and adding a heat-resistant coating. The heat-resistant groups are grafted on the surface of the film and the film material is crosslinked, so that the thermal stability and the dimensional stability of the diaphragm can be effectively improved, but the operation steps are complex, the continuous production efficiency is low, the cost is high, the market requirements are not met, and the industrial production is difficult to realize; the heat-resistant coating ceramic material is added, but the ceramic material has the problems of easy detachment and easy water absorption, so that the cycle performance and the rate performance of the battery are poor.
Disclosure of Invention
The invention aims to provide a lithium ion battery diaphragm with a spider-web structure and a preparation method thereof, and aims to solve the technical problems of improving the thermal stability and the dimensional stability of the diaphragm, reducing the cost and improving the charge-discharge efficiency of a lithium ion battery.
The invention adopts the following technical scheme: a lithium ion battery diaphragm with a spider-web structure takes a polyolefin film as a base film, the base film is coated with a high polymer material, the porosity of the polyolefin film is 30-60%, the high polymer material forms the spider-web structure on the surface of the polyolefin, and the high polymer material accounts for 20-80% of the mass of the lithium ion battery diaphragm with the spider-web structure;
the polyolefin film is a polyethylene film, a polypropylene film, polyethylene terephthalate, a polyethylene-polypropylene composite film or a polypropylene-polyethylene-polypropylene composite film;
the high polymer material is more than one of polystyrene, polymethyl methacrylate, polyimide, polyetherimide, polyamide-imide, polyamide, polyamic acid, polyvinylidene fluoride, polyethylene terephthalate, polyvinylidene fluoride-hexafluoropropylene, polyvinyl alcohol, polyacrylonitrile, polyoxyethylene and poly (p-phenylene benzobisoxazole).
The thickness of the polyolefin film is 5-20 um.
The polymer material of the invention is polyimide, polyamideimide or polyamide.
The polyolefin film of the present invention is a polyethylene film.
A preparation method of a lithium ion battery diaphragm with a spider-web structure comprises the following steps:
firstly, preparing polymer solution
Dissolving 1-20 g of high polymer material in 100-1000 ml of organic solvent at room temperature, magnetically stirring at the speed of 300r/min, and stopping stirring after 0.5-72 h to obtain a high polymer solution with the mass concentration of 0.1-20%;
the high polymer material is more than one of polystyrene, polymethyl methacrylate, polyimide, polyetherimide, polyamide-imide, polyamide, polyamic acid, polyvinylidene fluoride, polyethylene terephthalate, polyvinylidene fluoride-hexafluoropropylene, polyvinyl alcohol, polyacrylonitrile, polyoxyethylene and poly (p-phenylene benzobisoxazole);
the organic solvent is an organic solvent or a mixed solvent capable of dissolving the high molecular material, and is more than one of N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, chloroform, tetrahydrofuran, dichloromethane, dichloroethane, dichloroethylene, methanol, ethanol, isopropanol, cyclohexane and ethyl acetate;
secondly, preparing the spider-web structure composite diaphragm
According to the mass of a high polymer material 20-80% of the mass of the spider-web structure lithium ion battery diaphragm, putting a polyolefin film with porosity of 30-60% and thickness of 5-20 mu m into a high polymer solution, and carrying out soaking, spraying, coating or deposition treatment to obtain a spider-web structure composite diaphragm on the polyolefin film;
the soaking is standing soaking, heating soaking, ultrasonic soaking and pressing soaking;
the standing and soaking step comprises the following steps: soaking the polyolefin film in a high molecular solution, and standing for 0.01-50 h;
the heating and soaking are as follows: soaking a polyolefin film in a high molecular solution, and directly soaking for 0.01-50 h at 40-100 ℃;
the ultrasonic soaking comprises the following steps: soaking a polyolefin film in a high molecular solution at room temperature of 50-2000W/cm2Ultrasonically treating the high molecular solution for 0.01-50 h;
the polyolefin film is a polyethylene film, a polypropylene film, polyethylene terephthalate, a polyethylene-polypropylene composite film or a polypropylene-polyethylene-polypropylene composite film;
three, dry the compound diaphragm
And performing forced air drying and vacuum drying to obtain the lithium ion battery diaphragm with the spider-web structure.
The method has the blowing temperature of 25-80 ℃ and the drying time of 0.1-10 h.
The method has the advantages that the vacuum drying temperature is 30-130 ℃, the vacuum degree is 0.1MPa, and the drying time is 0.1-50 h.
The polymer material of the method is polyimide, polyamide-imide or polyamide.
The polyolefin film of the process of the present invention is a polyethylene film.
The organic solvent in the method of the invention is N, N-dimethylformamide or dichloroethane.
Compared with the prior art, the preparation method has the advantages that the polyolefin film is used as the base film, the base film is coated with the high polymer material, the high polymer material presents a part of gathered and partially hollow spider-web structure, the thermal stability and the size stability of the polyolefin film are changed, the diaphragm is maintained for 1 hour at 130 ℃, the thermal shrinkage rate is 1%, is maintained for 1 hour at 150 ℃, the thermal shrinkage rate is 3%, is maintained for 1 hour at 200 ℃ and is 5%, and the wettability of the polyolefin film is improved.
Drawings
FIG. 1 is a SEM image of example 1.
Fig. 2 is a graph comparing charge capacity retention rates of example 1 with PE-based film, ceramic coated separator.
Fig. 3 is a graph comparing the discharge capacity retention rates of example 1 with PE-based film and ceramic-coated separator.
Figure 4 is a graph comparing coulombic efficiency of example 1 with PE-based, ceramic coated membranes.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples. The lithium ion battery diaphragm (diaphragm) with the cobweb structure takes a polyolefin film as a base film, the base film is coated with a high polymer material, the porosity of the polyolefin film is 30-60%, the thickness of the polyolefin film is 5-20 mu m, the polyolefin film and the high polymer material are effectively combined, the high polymer material has an incomplete coating structure on the surface of the polyolefin, the surface of the polyolefin film is partially gathered and partially hollow, the cobweb structure is formed, and the high polymer material accounts for 20-80% of the mass of the diaphragm.
The polyolefin film is a polyethylene film, a polypropylene film, polyethylene terephthalate, a polyethylene and polypropylene two-layer composite film (polyethylene-polypropylene composite film) or a polypropylene, polyethylene and polypropylene three-layer composite film (polypropylene-polyethylene-polypropylene composite film).
The high molecular material is more than one of polystyrene, polymethyl methacrylate, polyimide, polyetherimide, polyamide-imide, polyamide, polyamic acid, polyvinylidene fluoride, polyethylene terephthalate, polyvinylidene fluoride-hexafluoropropylene, polyvinyl alcohol, polyacrylonitrile, polyoxyethylene and poly (p-phenylene benzobisoxazole).
The preparation method of the lithium ion battery diaphragm with the spider-web structure comprises the following steps:
firstly, preparing polymer solution
Dissolving 1-20 g of polymer material in 100-1000 ml of organic solvent at room temperature (20 ℃), magnetically stirring at the speed of 300r/min, and stopping stirring after 0.5-72 h to obtain a polymer solution with the mass concentration of 0.1-20%.
The high molecular material is more than one of polystyrene, polymethyl methacrylate, polyimide, polyetherimide, polyamide-imide, polyamide, polyamic acid, polyvinylidene fluoride, polyethylene terephthalate, polyvinylidene fluoride-hexafluoropropylene, polyvinyl alcohol, polyacrylonitrile, polyoxyethylene and poly (p-phenylene benzobisoxazole).
The organic solvent is one or more of N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, chloroform, tetrahydrofuran, dichloromethane, dichloroethane, dichloroethylene, methanol, ethanol, isopropanol, cyclohexane and ethyl acetate.
The polymer solution provides modified polyolefin base film slurry and aims to improve the thermal stability and the dimensional stability of the lithium ion battery diaphragm.
Secondly, preparing the spider-web structure composite diaphragm
According to the weight of the high polymer material which is 20-80% of the diaphragm, the polyolefin film with the porosity of 30-60% and the thickness of 5-20 mu m is put into the high polymer solution to be processed by soaking, spraying, coating or deposition, and the spider-web structure composite diaphragm (composite diaphragm) is obtained on the polyolefin film.
The soaking is standing soaking, heating soaking, ultrasonic soaking, and pressure soaking.
Standing and soaking to obtain: soaking the polyolefin film in a high molecular solution, standing for 0.01-50 h, and taking out.
The heating and soaking process comprises the following steps: soaking the polyolefin film in a high molecular solution, and taking out the polyolefin film after 0.01-50 h at 40-100 ℃.
The ultrasonic soaking comprises the following steps: soaking a polyolefin film in a high molecular solution at room temperature of 50-2000W/cm2And (4) ultrasonically treating the polymer solution, and taking out after 0.01-50 h.
The pressure soaking adopts the pressure soaking in the prior art.
Spraying, coating and deposition are carried out using known techniques.
The polyolefin film is polyethylene film, polypropylene film, polyethylene terephthalate, polyethylene-polypropylene composite film or polypropylene-polyethylene-polypropylene composite film.
And soaking and coating to coat the slurry on the base membrane, and drying to obtain the composite diaphragm with the porous spider-web structure.
Three, dry the compound diaphragm
And performing forced air drying and vacuum drying to obtain the lithium ion battery diaphragm with the spider-web structure.
The blowing temperature is 25-80 ℃, and the drying time is 0.1-10 h.
The vacuum drying temperature is 30-130 ℃, the vacuum degree is 0.1MPa, and the drying time is 0.1-50 h.
And observing the spider-web structure lithium ion battery diaphragm structure by adopting an S4800-scanning electron microscope SEM.
The lithium ion battery separator with the spider-web structure, the polyethylene PE base film and the separator with the ceramic coating on the polyethylene PE base film obtained in the example were subjected to thermal stability, dimensional stability and electrolyte wettability tests by the following methods.
Coating 10cm x 10cm size of cobweb-structured lithium ion battery diaphragm with filter paper at room temperature, placing into oven at 130 deg.C, 150 deg.C and 200 deg.C, respectively, taking out after 1 hr, measuring length and width dimensions, and calculating thermal shrinkage rate with TD%Before testing-LAfter testing)/LBefore testingWherein TD% is transverse dimension shrinkage of the membrane, LBefore testingIs a high temperature measurementTransverse dimension before test, LAfter testingIs the transverse dimension after high temperature testing, MD% (L)Before testing-LAfter testing)/LBefore testingWherein, MD% is the longitudinal dimension shrinkage of the diaphragm, LBefore testingIs the longitudinal dimension, L, before high temperature testingAfter testingIs the longitudinal dimension after the high temperature test. After heat treatment at 130 ℃ for 1h, the thermal shrinkage rate of the length and width dimensions of the diaphragm is less than 5%, and the thermal stability and the dimensional stability are good.
Suspending a 5 cm-by-5 cm spider-web structure lithium ion battery diaphragm at room temperature, horizontally placing the diaphragm, and dropwise adding 5 mul of electrolyte, wherein the electrolyte comprises the following components in percentage by mass: ethyl cellulose EC: epoxy resin EMC: the wetting property of the composite diaphragm in the electrolyte is compared by measuring the diameter of the electrolyte after 1min of the liquid drop wetting of the electrolyte drop on the diaphragm after 1min of the liquid drop wetting, and evaluating the wetting property of the electrolyte drop after 1min of the liquid drop wetting.
The lithium ion battery separator with the spider-web structure, the polyethylene PE base film, and the separator with the ceramic-coated polyethylene PE base film obtained in the examples were used as the lithium ion battery separator for the test, and the ternary material NCA for the lithium ion battery was used as the positive electrode material, the lithium sheet was used as the negative electrode material, and the electrolyte was LB-002 (ethylene carbonate: dimethyl carbonate: diethyl carbonate: 1:1:1), and the CR2016 type coin battery was prepared. During testing, the upper limit of the voltage is set to be 4.3V, the lower limit of the voltage is set to be 2.5V, the testing temperature is room temperature, and the testing multiplying power is 0.5C, 3C, 5C and 8C. Battery charge capacity retention ratio: the charge capacity after a number of cycles is higher than the charge capacity of the first cycle test. Battery discharge capacity retention rate: the discharge capacity after a certain number of cycles is higher than that tested in the first cycle. Coulombic efficiency: discharge capacity per one time is specific to charge capacity.
Example 1
Firstly, preparing polyimide solution
1g of polyimide was added to 1000ml of N, N-dimethylformamide and stirred for 0.5 hour to obtain a transparent and uniform polyimide solution having a mass concentration of 0.1%.
Secondly, preparing the spider-web structure composite diaphragm
And (3) putting the polyethylene base film with the porosity of 50% and the thickness of 10 mu m into a polyimide solution with the mass concentration of 0.1% according to the polyimide accounting for 50% of the mass of the diaphragm, standing for 0.01h, and taking out to obtain the composite diaphragm.
Three, dry the compound diaphragm
And drying the membrane in a blast oven at 25 ℃ for 0.1h, and then drying the membrane in a vacuum oven at 30 ℃ for 0.1h to obtain the lithium ion battery membrane with the spider web structure.
As shown in fig. 1, the polyethylene film base film is filled with polyimide which is a high molecular material, the thickness of the polyolefin film is 9um, the polyimide has an incomplete coating structure on the polyolefin surface, and the surface is partially gathered and partially hollow to form a spider-web structure.
And testing the thermal stability, the dimensional stability and the electrolyte wettability of the lithium ion battery diaphragm with the cobweb structure.
The lithium ion battery separator with the spider-web structure obtained in example 1 was directly placed in an oven at 130 ℃ for heating, taken out after 1 hour, measured for size, and calculated for thermal shrinkage, which was 1%. Directly placing the mixture into a 150 ℃ oven for heating, taking out the mixture after 1h, measuring the composite size, and calculating the thermal shrinkage rate, wherein the thermal shrinkage rate is 3%. Directly placing the mixture into an oven at 200 ℃ for heating, taking out the mixture after 1h, measuring the size, and calculating the thermal shrinkage rate, wherein the thermal shrinkage rate is 5%.
The lithium ion battery diaphragm with the spider-web structure obtained in example 1 and the PE base film are respectively suspended and horizontally placed, 5 μ l of electrolyte is dripped, the diameter of a liquid drop is measured after 1min, and the wettability of the electrolyte is measured, wherein the impregnation diameter of the electrolyte of the lithium ion battery diaphragm with the spider-web structure obtained in example 1 is 5mm, the impregnation diameter of the electrolyte of the PE base film is 7mm, and the wettability of the electrolyte of example 1 is greater than that of the PE base film.
The spider-web-structure lithium ion battery separator obtained in example 1, the polyethylene PE base film, and the separator ceramic-coated on the polyethylene PE base film were used as lithium ion battery separators for testing to test the charge capacity retention rate, the discharge capacity retention rate, and the coulombic efficiency of the lithium ion battery.
As shown in FIG. 2, through 0.5C, 3C and 8C rate performance tests, the charge capacity retention rate of the spider-web structure lithium ion diaphragm is found to be superior to that of a ceramic coating diaphragm and that of a PE base film.
As shown in fig. 3, the discharge capacity retention rate of the spider-web structure lithium ion separator is found to be better than that of the ceramic coating separator and that of the PE base film by the 0.5C, 3C and 8C rate performance tests.
As shown in fig. 4, through 0.5C, 3C, 8C rate performance tests, it was found that the coulombic efficiency of the spider-web structure lithium ion separator was consistent with that of the ceramic coating separator and the PE base film at 0.5C charge and discharge, while the coulombic efficiency of the spider-web structure lithium ion separator was superior to that of the ceramic coating separator and that of the PE base film at 3C, 8C charge and discharge.
Example 2
Firstly, preparing polyamide imide solution
1g of polyamideimide was added to 1000ml of N, N-dimethylformamide and stirred for 0.5 hour to obtain a transparent and uniform polyamideimide solution having a mass concentration of 0.1%.
Secondly, preparing the spider-web structure composite diaphragm
The polyethylene base film with the porosity of 50 percent and the thickness of 10 mu m is put into the polyamide-imide solution with the mass concentration of 0.1 percent according to the polyamide-imide accounting for 20 percent of the mass of the diaphragm, and the power is 50W/cm2And then, taking out after ultrasonic treatment for 0.01h to obtain the composite diaphragm.
Three, dry the compound diaphragm
And drying the membrane in a blast oven at 25 ℃ for 0.1h, and then drying the membrane in a vacuum oven at 30 ℃ for 0.1h to obtain the lithium ion battery membrane with the spider web structure.
The lithium ion battery separator with the spider-web structure obtained in example 2 was directly placed in an oven at 130 ℃ for heating, taken out after 1 hour, measured for size, and calculated for thermal shrinkage, which was 1%. Directly placing the mixture into a 150 ℃ oven for heating, taking out the mixture after 1h, measuring the composite size, and calculating the thermal shrinkage rate, wherein the thermal shrinkage rate is 3%. And (3) heating in an oven at 200 ℃, taking out after 1h, measuring the size, and calculating the thermal shrinkage rate, wherein the thermal shrinkage rate is 5%.
The lithium ion battery diaphragm with the spider-web structure, the polyimide PI and the polyethylene PE composite film obtained in the example 2 are respectively suspended and horizontally placed, 5 mu l of electrolyte is dropwise added, the diameter of a liquid drop is measured after 1min, and the wettability of the electrolyte is measured, wherein the impregnation diameter of the electrolyte of the lithium ion battery diaphragm with the spider-web structure obtained in the example 2 is 5mm, the impregnation diameter of the electrolyte of the polyethylene PE base film is 7mm, and the wettability of the electrolyte of the example 2 is greater than that of the PI and PE composite film.
Example 3
Firstly, preparing polyamide solution
1g of polyamide was added to 1000ml of N, N-dimethylformamide and stirred for 0.5 hour to obtain a transparent and uniform polyamide solution having a mass concentration of 0.1%.
Secondly, preparing the spider-web structure composite diaphragm
And (2) putting the polyethylene base film with the porosity of 50% and the thickness of 10 mu m into a polyamide solution with the mass concentration of 0.1% according to that the polyamide accounts for 80% of the mass of the diaphragm, directly heating at 40 ℃ for 0.01h, and taking out to obtain the composite diaphragm.
Three, dry the compound diaphragm
And drying the membrane in a blast oven at 25 ℃ for 0.1h, and then drying the membrane in a vacuum oven at 30 ℃ for 0.1h to obtain the lithium ion battery membrane with the spider web structure.
The lithium ion battery separator with the spider-web structure obtained in example 3 was directly placed in an oven at 130 ℃ for heating, taken out after 1 hour, measured for size, and calculated for thermal shrinkage, which was 1%. Directly placing the mixture into a 150 ℃ oven for heating, taking out the mixture after 1h, measuring the composite size, and calculating the thermal shrinkage rate, wherein the thermal shrinkage rate is 3%. And (3) heating in an oven at 200 ℃, taking out after 1h, measuring the size, and calculating the thermal shrinkage rate, wherein the thermal shrinkage rate is 5%.
The lithium ion battery diaphragm with the spider-web structure obtained in example 3 and the PE base film are respectively suspended and horizontally placed, 5 μ l of electrolyte is dripped, the diameter of a liquid drop is measured after 1min, the wettability of the electrolyte is measured, the impregnation diameter of the electrolyte of the lithium ion battery diaphragm with the spider-web structure obtained in example 3 is 7mm, the impregnation diameter of the electrolyte of the PE base film is 5mm, and the wettability of the electrolyte of example 3 is greater than that of the PE base film.
Example 4
Firstly, preparing polyamide imide solution
1g of polyamideimide was added to 100ml of dichloroethane, and after stirring for 0.5 hour, a transparent and uniform polyamideimide solution having a mass concentration of 1% was obtained.
Secondly, preparing the spider-web structure composite diaphragm
And (2) putting the polyethylene base film with the porosity of 30% and the thickness of 10 mu m into a polyamide-imide solution with the mass concentration of 1% according to the mass percent of the polyamide-imide as the diaphragm, standing for 0.01h, and taking out to obtain the composite diaphragm.
Three, dry the compound diaphragm
And drying the membrane in a blast oven at 25 ℃ for 0.1h, and then drying the membrane in a vacuum oven at 30 ℃ for 0.1h to obtain the lithium ion battery membrane with the spider web structure.
The lithium ion battery separator with the spider-web structure obtained in example 4 was directly placed in an oven at 130 ℃ for heating, taken out after 1 hour, measured for size, and calculated for thermal shrinkage, which was 5%. Directly placing the mixture into a 150 ℃ oven for heating, taking out the mixture after 1h, measuring the composite size, and calculating the thermal shrinkage rate, wherein the thermal shrinkage rate is 5%.
The lithium ion battery diaphragm with the spider-web structure, the polyimide PI and the polyethylene PE composite membrane obtained in the example 4 are respectively suspended and horizontally placed, 5 mu l of electrolyte is dripped, the diameter of a liquid drop is measured after 1min, the wettability of the electrolyte is measured, the wetting diameter of the electrolyte of the lithium ion battery diaphragm with the spider-web structure obtained in the example 4 is 5mm, the wetting diameter of the electrolyte of the PI and PE composite membrane is 7mm, and the wettability of the electrolyte of the example 4 is greater than that of the PE base membrane.
Example 5
Firstly, preparing polyimide solution
2g of polyimide was added to 100ml of N, N-dimethylformamide and stirred for 0.5 hour to obtain a transparent and uniform polyimide solution having a mass concentration of 2%.
Secondly, preparing the spider-web structure composite diaphragm
And (3) putting the polyethylene base film with the porosity of 60% and the thickness of 10 mu m into a polyimide solution with the mass concentration of 2% according to the polyimide accounting for 50% of the mass of the diaphragm, standing for 0.01h, and taking out to obtain the diaphragm.
Three, dry the compound diaphragm
And drying the membrane in a blast oven at 25 ℃ for 0.1h, and then drying the membrane in a vacuum oven at 30 ℃ for 0.1h to obtain the lithium ion battery membrane with the spider web structure.
The lithium ion battery separator with the spider-web structure obtained in example 5 was directly placed in an oven at 130 ℃ for heating, taken out after 1 hour, measured for size, and calculated for thermal shrinkage, which was 1%. Directly placing the mixture into a 150 ℃ oven for heating, taking out the mixture after 1h, measuring the composite size, and calculating the thermal shrinkage rate, wherein the thermal shrinkage rate is 3%. And (3) heating in an oven at 200 ℃, taking out after 1h, measuring the size, and calculating the thermal shrinkage rate, wherein the thermal shrinkage rate is 5%.
The lithium ion battery diaphragm with the spider-web structure obtained in example 5 and the PE base film are respectively suspended and horizontally placed, 5 μ l of electrolyte is dripped, the diameter of a liquid drop is measured after 1min, and the wettability of the electrolyte is measured, wherein the impregnation diameter of the electrolyte of the lithium ion battery diaphragm with the spider-web structure obtained in example 5 is 5mm, the impregnation diameter of the electrolyte of the PE base film is 7mm, and the wettability of the electrolyte of example 5 is greater than that of the PE base film.
Example 6
Firstly, preparing polyamide solution
8g of polyamide was added to 100ml of N, N-dimethylformamide and stirred for 0.5 hour to obtain a transparent and uniform polyamide solution having a mass concentration of 8%.
Secondly, preparing the spider-web structure composite diaphragm
And (2) putting the polyethylene base film with the porosity of 50% and the thickness of 10 mu m into a polyamide solution with the mass concentration of 8% according to the condition that the polyamide accounts for 50% of the mass of the diaphragm, standing for 0.01h, and taking out to obtain the PPEM diaphragm.
Three, dry the compound diaphragm
And drying the membrane in a blast oven at 25 ℃ for 0.1h, and then drying the membrane in a vacuum oven at 30 ℃ for 0.1h to obtain the lithium ion battery membrane with the spider web structure.
The lithium ion battery separator with the spider-web structure obtained in example 6 was directly placed in an oven at 130 ℃ for heating, taken out after 1 hour, measured for size, and calculated for thermal shrinkage, which was 1%. Directly placing the mixture into a 150 ℃ oven for heating, taking out the mixture after 1h, measuring the composite size, and calculating the thermal shrinkage rate, wherein the thermal shrinkage rate is 3%. And (3) heating in an oven at 200 ℃, taking out after 1h, measuring the size, and calculating the thermal shrinkage rate, wherein the thermal shrinkage rate is 5%.
The lithium ion battery diaphragm with the spider-web structure obtained in example 6 and the PE base film were respectively suspended and horizontally placed, 5 μ l of electrolyte was dropped, the diameter of the drop was measured after 1min, and the electrolyte wettability was measured, the electrolyte wetting diameter of the lithium ion battery diaphragm with the spider-web structure obtained in example 1 was 5mm, the electrolyte wetting diameter of the polyethylene PE base film was 7mm, and the electrolyte wettability of example 6 was greater than that of the PE base film.
In the embodiment of the present invention, polyimide, polyamideimide, or polyamide is used as the polymer material. N, N-dimethylformamide and dichloroethane are used as the organic solvent. The polyolefin film employs a polyethylene film.
Among the high molecular materials, polystyrene, polymethyl methacrylate, polyetherimide, polyamic acid, polyvinylidene fluoride, polyethylene terephthalate, polyvinylidene fluoride-hexafluoropropylene, polyvinyl alcohol, polyacrylonitrile, polyoxyethylene, and poly (p-phenylene benzobisoxazole) have the same chemical corrosion resistance and electrochemical stability as polyimide, polyamideimide, and polyamide, and thus are suitable for use in the present invention.
Among the organic solvents, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, chloroform, tetrahydrofuran, dichloromethane, dichloroethylene, methanol, ethanol, isopropanol, cyclohexane and ethyl acetate, and N, N-dimethylformamide and dichloroethane have the characteristics that after the solvents are dried and volatilized, a hollow structure can be left, and a cobweb-shaped composite diaphragm is formed, so that the composite diaphragm is suitable for the invention.
Among the polyolefin films, the polypropylene film, polyethylene terephthalate, polyethylene-polypropylene composite film or polypropylene-polyethylene-polypropylene composite film has the same organic solvent resistance as the polyethylene film, and thus can be stabilized when passing through the solvent in the slurry tank, and is therefore suitable for use in the present invention.
The lithium ion battery diaphragm with the spider-web structure takes the polyolefin film as a base film, is coated and doped with the high polymer material, has excellent affinity with the polyolefin diaphragm, and is effectively coated on the polyolefin film, so that the thermal stability and the dimensional stability of the polyolefin film are changed. In addition, the network polymer layer formed on the surface of the polyolefin film after the polyolefin film is treated by the polymer solution further improves the thermal stability and the dimensional stability of the separator, and the wettability of the polyolefin film is further improved due to the presence of the surface high-performance polymer layer.
According to the preparation method, the high-molecular coating layer is formed on the surface of the fibrous olefin in the polyolefin film through soaking, so that the thermal stability and the dimensional stability of the polyolefin film are changed, and the disappearance of the internal gaps of the polyolefin film cannot be caused due to the low concentration of the high-molecular solution. After the polyolefin film is treated by the polymer solution and taken out, a network polymer layer is formed on the surface, so that the thermal stability and the dimensional stability of the polyolefin film are further improved. Due to the existence of the surface macromolecule layer, the wettability of the polyolefin film is improved.
The lithium ion battery diaphragm with the spider-web structure prepared by the method has good thermal stability, dimensional stability and electrolyte wettability, the lithium ion battery diaphragm with the spider-web structure maintains 1 hour at 130 ℃, the thermal shrinkage rate is 1 percent, maintains 1 hour at 150 ℃, the thermal shrinkage rate is 3 percent, maintains 1 hour at 200 ℃, and the thermal shrinkage rate is 5 percent. The reticular structure formed on the surface can further improve the thermal stability of the diaphragm and has a certain promotion effect on the electrolyte infiltrating the diaphragm. The high polymer material is coated on the polyolefin film, so that the phenomenon of pore blocking of the polyolefin diaphragm cannot occur, and the transmission of lithium ions is not influenced.
The preparation method has the advantages of mild conditions, simple operation, easy control, low cost and easy realization of industrial production.
Claims (10)
1. A spider web structure lithium ion battery diaphragm which characterized in that: the lithium ion battery diaphragm with the spider-web structure takes a polyolefin film as a base film, the base film is coated with a high polymer material, the porosity of the polyolefin film is 30-60%, the high polymer material forms the spider-web structure on the surface of the polyolefin, and the high polymer material accounts for 20-80% of the mass of the lithium ion battery diaphragm with the spider-web structure;
the polyolefin film is a polyethylene film, a polypropylene film, polyethylene terephthalate, a polyethylene-polypropylene composite film or a polypropylene-polyethylene-polypropylene composite film;
the high polymer material is more than one of polystyrene, polymethyl methacrylate, polyimide, polyetherimide, polyamide-imide, polyamide, polyamic acid, polyvinylidene fluoride, polyethylene terephthalate, polyvinylidene fluoride-hexafluoropropylene, polyvinyl alcohol, polyacrylonitrile, polyoxyethylene and poly (p-phenylene benzobisoxazole).
2. The spider web structure lithium ion battery separator according to claim 1, wherein: the thickness of the polyolefin film is 5-20 um.
3. The spider web structure lithium ion battery separator according to claim 1, wherein: the high polymer material is polyimide, polyamide-imide or polyamide.
4. The spider web structure lithium ion battery separator according to claim 1, wherein: the polyolefin film is a polyethylene film.
5. A preparation method of a lithium ion battery diaphragm with a spider-web structure comprises the following steps:
firstly, preparing polymer solution
Dissolving 1-20 g of high polymer material in 100-1000 ml of organic solvent at room temperature, magnetically stirring at the speed of 300r/min, and stopping stirring after 0.5-72 h to obtain a high polymer solution with the mass concentration of 0.1-20%;
the high polymer material is more than one of polystyrene, polymethyl methacrylate, polyimide, polyetherimide, polyamide-imide, polyamide, polyamic acid, polyvinylidene fluoride, polyethylene terephthalate, polyvinylidene fluoride-hexafluoropropylene, polyvinyl alcohol, polyacrylonitrile, polyoxyethylene and poly (p-phenylene benzobisoxazole);
the organic solvent is an organic solvent or a mixed solvent capable of dissolving the high molecular material, and is more than one of N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, chloroform, tetrahydrofuran, dichloromethane, dichloroethane, dichloroethylene, methanol, ethanol, isopropanol, cyclohexane and ethyl acetate;
secondly, preparing the spider-web structure composite diaphragm
According to the mass of a high polymer material 20-80% of the mass of the spider-web structure lithium ion battery diaphragm, putting a polyolefin film with porosity of 30-60% and thickness of 5-20 mu m into a high polymer solution, and carrying out soaking, spraying, coating or deposition treatment to obtain a spider-web structure composite diaphragm on the polyolefin film;
the soaking is standing soaking, heating soaking, ultrasonic soaking and pressing soaking;
the standing and soaking step comprises the following steps: soaking the polyolefin film in a high molecular solution, and standing for 0.01-50 h;
the heating and soaking are as follows: soaking a polyolefin film in a high molecular solution, and directly soaking for 0.01-50 h at 40-100 ℃;
the ultrasonic soaking comprises the following steps: soaking a polyolefin film in a high molecular solution at room temperature of 50-2000W/cm2Ultrasonically treating the high molecular solution for 0.01-50 h;
the polyolefin film is a polyethylene film, a polypropylene film, polyethylene terephthalate, a polyethylene-polypropylene composite film or a polypropylene-polyethylene-polypropylene composite film;
three, dry the compound diaphragm
And performing forced air drying and vacuum drying to obtain the lithium ion battery diaphragm with the spider-web structure.
6. The method for producing a lithium ion battery separator having a spider-web structure according to claim 5, characterized in that: the blowing temperature is 25-80 ℃, and the drying time is 0.1-10 h.
7. The method for producing a lithium ion battery separator having a spider-web structure according to claim 5, characterized in that: the vacuum drying temperature is 30-130 ℃, the vacuum degree is 0.1MPa, and the drying time is 0.1-50 h.
8. The method for producing a lithium ion battery separator having a spider-web structure according to claim 5, characterized in that: the high polymer material is polyimide, polyamide-imide or polyamide.
9. The method for producing a lithium ion battery separator having a spider-web structure according to claim 5, characterized in that: the polyolefin film is a polyethylene film.
10. The method for producing a lithium ion battery separator having a spider-web structure according to claim 5, characterized in that: the organic solvent is N, N-dimethylformamide or dichloroethane.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115224439A (en) * | 2022-08-11 | 2022-10-21 | 长园泽晖新能源材料研究院(珠海)有限公司 | High-performance lithium ion battery diaphragm and preparation method thereof |
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| CN109659468A (en) * | 2017-10-11 | 2019-04-19 | 中国科学院大连化学物理研究所 | A kind of composite diaphragm and its preparation and application with hot off function |
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