CN112701420A - Multifunctional diaphragm for lithium battery, preparation method and application - Google Patents
Multifunctional diaphragm for lithium battery, preparation method and application Download PDFInfo
- Publication number
- CN112701420A CN112701420A CN202110091408.4A CN202110091408A CN112701420A CN 112701420 A CN112701420 A CN 112701420A CN 202110091408 A CN202110091408 A CN 202110091408A CN 112701420 A CN112701420 A CN 112701420A
- Authority
- CN
- China
- Prior art keywords
- multifunctional
- organic
- diaphragm
- lithium battery
- separator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 69
- 239000011256 inorganic filler Substances 0.000 claims abstract description 40
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 40
- 239000000654 additive Substances 0.000 claims abstract description 38
- 230000000996 additive effect Effects 0.000 claims abstract description 35
- 239000011230 binding agent Substances 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 27
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 72
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 72
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 34
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 25
- MXZROAOUCUVNHX-UHFFFAOYSA-N 2-Aminopropanol Chemical compound CCC(N)O MXZROAOUCUVNHX-UHFFFAOYSA-N 0.000 claims description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims description 20
- 239000002131 composite material Substances 0.000 claims description 20
- 229920001223 polyethylene glycol Polymers 0.000 claims description 20
- 238000001523 electrospinning Methods 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000009987 spinning Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 3
- 238000011161 development Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 20
- 239000000126 substance Substances 0.000 description 15
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 11
- 229910001593 boehmite Inorganic materials 0.000 description 9
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- -1 polyoxyethylene Polymers 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 238000010041 electrostatic spinning Methods 0.000 description 5
- 230000006870 function Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 206010040954 Skin wrinkling Diseases 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002103 nanocoating Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229910006636 γ-AlOOH Inorganic materials 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 1
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000008096 xylene Substances 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
Abstract
The invention relates to the technical field of battery manufacturing, and particularly discloses a multifunctional diaphragm for a lithium battery, a preparation method and application, wherein the multifunctional diaphragm for the lithium battery comprises a diaphragm material to be coated and an organic-inorganic compound coated on the side surface of the diaphragm material; wherein the organic-inorganic compound comprises the following raw materials: nano inorganic filler, binder, organic multifunctional group, additive and proper amount of solvent; according to the invention, through the use of multiple raw materials, the prepared multifunctional diaphragm for the lithium battery can be used as a multifunctional diaphragm for a high-performance lithium ion battery, so that conditions are created for the performance exertion of high voltage, high safety, high power, high electrochemical stability, high first efficiency and long service life of the lithium ion battery, the development requirement of the current high-performance lithium ion battery can be met, and the problem that most of the existing lithium ion battery diaphragms have single function is solved; the preparation method is suitable for industrial production and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of battery manufacturing, in particular to a multifunctional diaphragm for a lithium battery, a preparation method and application.
Background
With the development of the current lithium ion battery (lithium battery) technology, the application field of the lithium ion battery is more and more extensive, and from small portable equipment, intelligent middle-end equipment, energy storage base stations and emergency power supplies to large power batteries, electric ships, electric airplanes and the like, the application scenes of the lithium ion battery are more and more, and the lithium ion battery not only comprises a high-temperature state and a low-temperature state, but also comprises a high-power state and a long-endurance state. Therefore, the demand for high performance lithium ion batteries is higher and higher, and more technical bottlenecks are challenging.
In the structure of the lithium battery, the diaphragm is one of the key inner layer assemblies, has the function of preventing the short circuit caused by the direct contact of the anode and the cathode, and simultaneously provides a channel for the transmission of lithium ions during the charge and discharge of the lithium ion battery. The performance of the separator directly affects the overall performance of the battery. However, the commonly used commercial lithium ion battery diaphragm has the problems of poor antistatic capability, low mechanical strength, low electrolyte wettability, low lithium ion transmission rate, poor thermal stability, increased contact distance with a pole piece after long-term circulation and the like, and the performance of the high-performance lithium ion battery is limited. Therefore, it is important to improve the overall performance of the separator, provide the separator with more additional functions, and match the requirements of high-performance lithium ion batteries.
Therefore, the above technical solutions have the following disadvantages in practical application: the existing lithium ion battery diaphragm has single function, can only meet the development requirement in a single direction, most diaphragms in the high-power field have very high porosity, but the diaphragm cannot simultaneously meet the requirements of high energy density and high safety, and meanwhile, the diaphragm has poor antistatic capability and cannot meet the manufacturing requirement of high-speed winding; the diaphragm used in the high energy density field can not meet the requirements of high power and high safety, and the thermal stability and the lithium ion conduction capability of the diaphragm are limited, so that the diaphragm can not meet the industrial requirements.
Disclosure of Invention
The invention aims to provide a multifunctional diaphragm for a lithium battery, which solves the problem that most of the existing lithium ion battery diaphragms proposed in the background art have single function.
In order to achieve the purpose, the invention provides the following technical scheme:
a multifunctional separator for a lithium battery includes a separator material to be coated and an organic-inorganic composite coated on a side of the separator material; wherein the organic-inorganic composite comprises the following raw materials: nano inorganic filler, adhesive, organic multifunctional group, additive and proper amount of solvent.
Another object of an embodiment of the present invention is to provide a method for preparing a multifunctional separator for a lithium battery, including the following steps:
weighing nano inorganic filler, binder and organic multifunctional group according to a proportion, uniformly mixing, adding additive and a proper amount of solvent, and uniformly mixing to obtain an organic-inorganic compound;
and carrying out electrospinning on the organic-inorganic composite on the side surface of the diaphragm material to be coated, and drying to obtain the multifunctional diaphragm for the lithium battery.
Another object of an embodiment of the present invention is to provide a multifunctional separator for a lithium battery, which is prepared by the above method for preparing a multifunctional separator for a lithium battery.
Another object of the embodiments of the present invention is to provide an application of the above multifunctional separator for a lithium battery in the preparation of a lithium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
the multifunctional diaphragm for the lithium battery comprises a diaphragm material to be coated and an organic-inorganic compound coated on the side surface of the diaphragm material; wherein the organic-inorganic compound comprises the following raw materials: nano inorganic filler, binder, organic multifunctional group, additive and proper amount of solvent; through the use of various raw materials, the prepared multifunctional diaphragm for the lithium battery can be used as a multifunctional diaphragm for a high-performance lithium ion battery, so that conditions are created for the performance exertion of high voltage, high safety, high power, high electrochemical stability, high first efficiency and long service life of the lithium ion battery, the development requirement of the current high-performance lithium ion battery can be met, and the problem that most of the existing lithium ion battery diaphragms have single function is solved; the preparation method is suitable for industrial production and has wide application prospect.
Drawings
FIG. 1 is a diagram illustrating a porosity profile of a membrane according to an embodiment of the present invention.
FIG. 2 is a graph showing the results of the liquid absorption rate of the diaphragm according to an embodiment of the present invention.
Fig. 3 is a graph illustrating a result of thermal shrinkage of the separator according to an embodiment of the present invention.
Fig. 4 is a graph showing the comparison of swelling before and after cycling of the battery according to an embodiment of the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The embodiment of the invention provides a multifunctional diaphragm for a lithium battery, which comprises a diaphragm material to be coated and an organic-inorganic compound coated on the side surface of the diaphragm material; wherein the organic-inorganic composite comprises the following raw materials: nano inorganic filler, adhesive, organic multifunctional group, additive and proper amount of solvent.
As another preferred embodiment of the present invention, the nano inorganic filler is selected from the group consisting of boehmite (main component is γ -AlOOH), aluminum trifluoride (AlF)3) Any one or more of them.
As another preferred embodiment of the present invention, the binder is polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), and a commercially available product can be specifically used.
As another preferred embodiment of the present invention, the organic multifunctional group is selected from any one or more of polyethylene oxide (PEO), acetamide (ATEA).
As another preferred embodiment of the present invention, the additive is selected from any one or more of aminopropanol (DLA) and polyethylene glycol (PEG).
As another preferred embodiment of the present invention, the solvent is added to the organic-inorganic composite in such an amount that the solid content of the organic-inorganic composite is 22wt% to 26 wt%.
In another preferred embodiment of the present invention, the solvent is specifically an organic solvent, and may be any one of alcohol, acetonitrile, pyridine, N-methylpyrrolidone, phenol, benzene, toluene, xylene, pentane, hexane, octane, cyclohexane, cyclohexanone, chlorobenzene, dichlorobenzene, dichloromethane, methanol, isopropanol, diethyl ether, propylene oxide, ethyl acetate, acetone, methyl butanone, dimethylformamide, ethylene glycol monobutyl ether, and the like.
As another preferred embodiment of the present invention, the solvent is selected from any one or more of N-methylpyrrolidone (NMP), Dimethylformamide (DMF), Acetonitrile (ACN).
As another preferred embodiment of the present invention, when the solvent includes N-methylpyrrolidone, dimethylformamide, acetonitrile, the mass ratio of N-methylpyrrolidone, dimethylformamide, acetonitrile is 5 to 8: 1: 1-3.
Preferably, when the solvent comprises N-methylpyrrolidone, dimethylformamide and acetonitrile, the mass ratio of N-methylpyrrolidone to dimethylformamide to acetonitrile is 7: 1: 2.
as another preferred embodiment of the present invention, the multifunctional separator for a lithium battery is formed by coating an organic-inorganic composite on the positive and negative sides of a separator material to be coated, respectively;
wherein the cathode corresponds to the cathode of the lithium ion battery, and the coated substance is an organic-inorganic compound consisting of nano inorganic filler (boehmite), binder (PVDF-HFP), organic multifunctional group (polyoxyethylene and acetamide), solvent (N-methyl pyrrolidone, dimethyl formamide and acetonitrile) and additive (aminopropanol and polyethylene glycol);
the anode corresponds to the anode of the lithium ion battery, and the coated substance is an organic-inorganic compound consisting of nano inorganic filler (aluminum trifluoride), binder (PVDF-HFP), organic multifunctional group (polyethylene oxide and acetamide), solvent (N-methyl pyrrolidone, dimethylformamide and acetonitrile) and additive (aminopropanol and polyethylene glycol).
As another preferred embodiment of the present invention, the mass ratio of the nano inorganic filler, the binder, the organic multifunctional group and the additive is 1: 5-12: 0.2-0.8: 0.1-0.6.
As another preferred embodiment of the present invention, the mass ratio of the nano inorganic filler, the binder, the organic multifunctional group and the additive is 1: 7-9: 0.5-0.7: 0.3-0.5.
Preferably, the mass ratio of the nano inorganic filler, the binder, the organic multifunctional group and the additive is 1: 8: 0.6: 0.4.
more preferably, in the raw materials of the organic-inorganic composite, the mass ratio of the nano inorganic filler, the binder, the polyethylene oxide, the acetamide, the aminopropanol and the polyethylene glycol is 1: 8: 0.3: 0.3: 0.2: 0.2.
the embodiment of the invention also provides a preparation method of the multifunctional diaphragm for the lithium battery, which comprises the following steps:
weighing nano inorganic filler, binder and organic multifunctional group according to a proportion, uniformly mixing, adding additive and a proper amount of solvent, and uniformly mixing to obtain an organic-inorganic compound;
and carrying out electrospinning on the organic-inorganic composite on the side surface of the diaphragm material to be coated, and drying to obtain the multifunctional diaphragm for the lithium battery.
As another preferred embodiment of the invention, the material flow rate during electrospinning is 10-20 mL/h.
As another preferred embodiment of the present invention, in the electrospinning, the cathode side of the separator material to be coated corresponds to the cathode of the lithium ion battery, and the coated substance is an organic-inorganic composite composed of nano inorganic filler (boehmite), binder (PVDF-HFP), organic multifunctional group (polyethylene oxide, acetamide), solvent (N-methyl pyrrolidone, dimethyl formamide, acetonitrile), additive (aminopropanol, polyethylene glycol); the flow rate is 10-20 mL/h.
As another preferred embodiment of the present invention, in the electrospinning, the positive surface of the separator material to be coated corresponds to the anode of the lithium ion battery, and the coated substance is an organic-inorganic composite composed of nano inorganic filler (aluminum trifluoride), binder (PVDF-HFP), organic multifunctional group (polyethylene oxide, acetamide), solvent (N-methyl pyrrolidone, dimethyl formamide, acetonitrile), additive (aminopropanol, polyethylene glycol); the flow rate is 10-15 mL/h.
As another preferred embodiment of the invention, the spinning distance during electrospinning is 30-35cm, the voltage is 28-30kv, the processing temperature is 23-25 ℃, the relative humidity is 42% -47%, and the coating thickness is 250-300 nm.
As another preferred embodiment of the present invention, in the method for preparing the multifunctional separator for a lithium battery, the drying is performed at 70 to 75 ℃ for 12 to 15 hours under vacuum conditions such that the porosity of the dried organic-inorganic composite is about 55 to 60%.
The embodiment of the invention also provides the multifunctional diaphragm for the lithium battery, which is prepared by the preparation method of the multifunctional diaphragm for the lithium battery.
The embodiment of the invention also provides an application of the multifunctional diaphragm for the lithium battery in the preparation of the lithium ion battery.
The technical effects of the multifunctional separator for a lithium battery according to the present invention will be further described below by referring to specific examples. The test parameters and addition ratios of the present invention are not limited to the scope of the following examples, and the materials used in the present invention are not limited to the above materials, and can be modified or changed according to the following description, and all the materials with the same modification and change and the same improvement mechanism should fall within the protection scope of the appended claims.
Example 1
A preparation method of a multifunctional diaphragm for a lithium battery comprises the following steps:
the mass ratio of (1): 8: 0.3: 0.3: 0.2: 0.2, respectively preparing a certain amount of nano inorganic filler (boehmite), binder (PVDF-HFP), organic multifunctional group (polyethylene oxide), organic multifunctional group (acetamide), additive (aminopropanol), additive (polyethylene glycol) and a certain amount of solvent (N-methylpyrrolidone, dimethylformamide and acetonitrile) for later use.
Secondly, mixing the raw materials in a mass ratio of 1: 8: 0.3: 0.3: 0.2: 0.2, respectively preparing a certain amount of nano inorganic filler (aluminum trifluoride), binder (PVDF-HFP), organic multifunctional group (polyethylene oxide), organic multifunctional group (acetamide), additive (aminopropanol), additive (polyethylene glycol) and a certain amount of solvent (N-methylpyrrolidone, dimethylformamide and acetonitrile) for later use.
Thirdly, firstly adding a certain amount of boehmite, PVDF-HFP, PEO and ATEA according to the mass ratio of the step I, opening and revolving at the rotating speed of 25-35rpm for 15-25 minutes, then sequentially adding aminopropanol and polyethylene glycol according to the mass ratio of the step I, simultaneously adding a certain amount of solvent (NMP: DMF: ACN = 7: 1: 2) to keep the solid content of the slurry at 22-26 wt%, opening and revolving at the rotating speed of 1000-1200rpm and the revolving speed of 25-35rpm, opening vacuum, stirring for 120-140 minutes, and slowly stirring for later use after shipment to obtain the organic-inorganic composite material C1.
Fourthly, firstly adding a certain amount of aluminum trifluoride, PVDF-HFP, PEO and ATEA according to the mass ratio of the step two, opening the revolution at the rotating speed of 25-35rpm for 15-25 minutes, then sequentially adding aminopropanol and polyethylene glycol according to the mass ratio of the step two, simultaneously adding a certain amount of solvent (NMP: DMF: ACN = 7: 1: 2) according to the mass ratio of the step two, keeping the solid content of the slurry at 22-26 wt%, opening the rotation and the revolution at the rotation speed of 1000-1200rpm and the revolution speed of 25-35rpm, opening the vacuum, stirring for 120-140 minutes, and slowly stirring after shipment to obtain the organic-inorganic composite A1.
Fifthly, respectively filling the C1 and A1 slurry obtained in the third step and the fourth step into a syringe of electrostatic spinning equipment, firstly electro-spinning C1 to the cathode surface of a high-porosity diaphragm (namely, the diaphragm material, specifically a commercial diaphragm sold in the market) with the thickness of 12 mu m by using the electrostatic spinning equipment, and then electro-spinning A1 to the anode surface, wherein the flow of C1 is 10-20mL/h, the flow of A1 is 10-15 mL/h, the spinning distance during electro-spinning is 30-35cm, the voltage is 28-30kv, the processing temperature is 23-25 ℃, the relative humidity is 42-47%, and the coating thickness of the cathode and the anode surfaces is 250-300nm finally.
Drying at 70-75 deg.c for 12-15 hr to obtain porous material with porosity of 55-60%.
And seventhly, finally obtaining the multifunctional diaphragm for the lithium battery, namely the multifunctional diaphragm for the high-performance lithium ion battery, which is recorded as MF.
Example 2
The same as example 1 except that polyethylene oxide alone is used as the organic multifunctional group as compared with example 1.
Example 3
The same as example 1 except that the organic multifunctional group used was acetamide alone, as compared with example 1.
Example 4
The procedure was as in example 1 except that only aminopropanol was used as the additive, as compared with example 1.
Example 5
The same as example 1 except that polyethylene glycol alone was used as an additive, as compared with example 1.
Example 6
The procedure is as in example 1 except that the solids content of the slurry is maintained at 22wt% after a certain amount of solvent, as compared to example 1.
Example 7
The procedure is as in example 1 except that the solids content of the slurry is maintained at 26wt% after a certain amount of solvent, as compared to example 1.
Example 8
The procedure of example 1 was repeated, except that N-methylpyrrolidone was used as the solvent in example 1.
Example 9
The procedure of example 1 was repeated, except that the solvent used in example 1 was only N-methylpyrrolidone, dimethylformamide or the like.
Example 10
The procedure of example 1 was repeated except that acetonitrile was used as the solvent in comparison with example 1.
Example 11
Compared to example 1, the difference is: the mass ratio of the N-methylpyrrolidone to the dimethylformamide to the acetonitrile is 5: 1: 1. the rest is the same as in example 1.
Example 12
Compared to example 1, the difference is: the mass ratio of the N-methylpyrrolidone to the dimethylformamide to the acetonitrile is 8: 1: 1. the rest is the same as in example 1.
Example 13
Compared to example 1, the difference is: the mass ratio of the N-methylpyrrolidone to the dimethylformamide to the acetonitrile is 8: 1: 3. the rest is the same as in example 1.
Example 14
Compared to example 1, the difference is: the mass ratio of the nano inorganic filler, the binder, the organic multifunctional group and the additive is 1: 5: 0.2: 0.1. the rest is the same as in example 1.
Example 15
Compared to example 1, the difference is: the mass ratio of the nano inorganic filler, the binder, the organic multifunctional group and the additive is 1: 12: 0.2: 0.1. the rest is the same as in example 1.
Example 16
Compared to example 1, the difference is: the mass ratio of the nano inorganic filler, the binder, the organic multifunctional group and the additive is 1: 10: 0.8: 0.6. the rest is the same as in example 1.
Example 17
Compared to example 1, the difference is: the mass ratio of the nano inorganic filler, the binder, the organic multifunctional group and the additive is 1: 7: 0.5: 0.3. the rest is the same as in example 1.
Example 18
Compared to example 1, the difference is: the mass ratio of the nano inorganic filler, the binder, the organic multifunctional group and the additive is 1: 9: 0.5: 0.5. the rest is the same as in example 1.
Example 19
Compared to example 1, the difference is: the mass ratio of the nano inorganic filler, the binder, the organic multifunctional group and the additive is 1: 9: 0.7: 0.3. the rest is the same as in example 1.
Example 20
The same procedure as in example 1 was repeated, except that the flow rate of C1 was 10 mL/h, the flow rate of A1 was 10 mL/h, the spinning distance during electrospinning was 30cm, the voltage was 28kv, the treatment temperature was 23 ℃, the relative humidity was 42%, and the final coating thickness on the male and female surfaces was 250nm, as compared with example 1.
Example 21
The same procedure as in example 1 was repeated, except that the flow rate of C1 was 20mL/h, the flow rate of A1 was 15 mL/h, the spinning distance during electrospinning was 35cm, the voltage was 30kv, the treatment temperature was 25 ℃, the relative humidity was 47%, and the final coating thickness on the male and female surfaces was 300nm, as compared with example 1.
Example 22
The same procedure as in example 1 was repeated, except that the flow rate of C1 was 15 mL/h, the flow rate of A1 was 12 mL/h, the spinning distance during electrospinning was 32cm, the voltage was 29kv, the treatment temperature was 24 ℃ and the relative humidity was 45%, and the final coating thickness on the male and female surfaces was 270nm, as compared with example 1.
Example 23
The same procedure as in example 1 was repeated, except that the drying was carried out in a vacuum oven at 70 ℃ for 12 hours, as compared with example 1.
Example 24
The procedure of example 1 was repeated, except that the drying was carried out at 75 ℃ for 15 hours in a vacuum oven.
Performance verification
In order to verify the performance of the multifunctional separator for a lithium battery according to the present invention, the multifunctional separator (MF) for a lithium battery of example 1 and a commercial separator (abbreviated as CS, available from shanghai new material science and technology limited), were subjected to a separator test, which specifically included:
(1) and (3) porosity testing: the porosity distribution diagrams of the multifunctional diaphragm (MF) and the commercialized diaphragm (CS) for the lithium battery are shown in figure 1, and can be obtained from figure 1 by testing the multifunctional diaphragm (MF) and the commercialized diaphragm (CS) for the lithium battery by adopting an n-butanol absorption method, wherein the porosity of the multifunctional diaphragm (MF) and the porosity of the commercialized diaphragm (CS) for the lithium battery are 55.16% and 45.8% respectively, the multifunctional diaphragm for the lithium battery has high porosity, and the porosity distribution of the multifunctional diaphragm is uniform. The multifunctional diaphragm has the advantages that due to the control of substances coated on the positive and negative surfaces of the multifunctional diaphragm, inorganic fillers on the positive and negative surfaces have small particle size, large specific surface area and large pore volume, conditions are created for the diaphragm with high porosity, and meanwhile, the use of the additive (aminopropanol and polyethylene glycol) can avoid the agglomeration of nano inorganic fillers, organic multifunctional groups and binders in the multifunctional diaphragm, so that the uniform dispersion of all substances is ensured, and meanwhile, the porosity of the multifunctional diaphragm is controlled, and the uniformity of the porosity is ensured. Meanwhile, the electrostatic spinning technology used in the invention creates a uniform and stable coating, and lays a foundation for the uniform porosity of the diaphragm.
(2) And (3) testing the liquid absorption rate: the multifunctional diaphragm (MF) and the commercial diaphragm (CS) for the lithium battery are respectively soaked in the electrolyte, the diaphragms before and after soaking are respectively weighed after 2 hours, the liquid absorption rates are respectively calculated, the obtained result of the liquid absorption rates of the diaphragms is shown in figure 2, and the result can be obtained from figure 2. The multifunctional diaphragm has the advantages that the inorganic nano coating, the organic multifunctional group and the binder on the positive and negative surfaces have larger specific surface area and three-dimensional space structure, and can promote the absorption and the retention of the electrolyte.
(3) Thermal shrinkage test: the multifunctional diaphragm (MF) and the commercial diaphragm (CS) for the lithium battery are respectively placed in an oven at 160 ℃ for 2 hours, the longitudinal shrinkage ratio of the diaphragm is tested, the obtained result of the thermal shrinkage ratio of the diaphragm is shown in figure 3, and the result can be obtained from figure 3.
(4) And (3) ion conductivity test: the multifunctional diaphragm (MF) and the commercialized diaphragm (CS) for the lithium battery were assembled into a pouch battery (the same existing pouch battery assembly process was adopted), and an ionic conductivity test was performed using an electrochemical workstation, and the obtained ionic conductivity results are shown in table 1.
Table 1 ionic conductivity results table
| Group | MF | CS |
| Ionic Conductivity s/cm | 8.56*10-3 | 9.8*10-4 |
As can be seen from table 1, the multifunctional separator of the present invention has high ionic conductivity, which is also in accordance with the result obtained in fig. 2, and not only benefits from the inorganic nano-coating, organic multifunctional group, and binder on the positive and negative surfaces of the multifunctional separator of the present invention, but also their large specific surface area and three-dimensional structure, which facilitate the absorption and retention of the electrolyte, and create conditions for the transmission of lithium ions. Meanwhile, the PVDF-HFP (polyvinylidene fluoride-hexafluoropropylene) shared by the positive and negative surfaces can well adhere the diaphragm and the pole piece together, so that the diaphragm has the capacity of absorbing and retaining electrolyte, the internal resistance of the lithium ion battery is reduced, and the ionic conductivity is further improved; in organic multifunctional groups (polyoxyethylene and acetamide), PEO can improve ion transmission capability, ATEA can reasonably distribute flux of lithium ions, so that the lithium ions can be uniformly deposited, the problems of polarization, temperature rise, DCR increase and the like caused by uneven distribution are reduced, and the comprehensive action of the substances greatly promotes the conduction of the lithium ions.
(5) And (3) testing electrical properties: the multifunctional diaphragm (MF) and the commercialized diaphragm (CS) for the lithium battery are respectively assembled into a soft-package battery (the same existing soft-package battery assembly process is adopted), the battery is charged at a rate of 0.5C, the battery is discharged at a rate of 1C, the electrochemical performance is compared, the battery thickness after 500 times and 1000 times of cycle comparison is compared, and the obtained first effect and cycle performance results are shown in table 2.
Table 2 first effect and cycle performance results table
| Group | MF | CS |
| First effect | 91.30% | 89.50% |
| Capacity retention ratio (1000 cylcle) | 87.60% | 81.30% |
From Table 2, it can be obtainedThe multifunctional membrane of the invention has electrical properties superior to commercial membranes, and achieves better first effect and cycle performance, which benefits from the composite effect of the multifunctional coating of the invention. First, the data of fig. 1, 2, 3 and tables 1 and 2 also show that the multifunctional separator of the present invention has high porosity, high liquid absorption rate, and high ionic conductivity, which all provide for good cycle performance. In the coating, the adhesive (PVDF-HFP) used in the invention can well adhere the diaphragm and the pole piece together, so that the transmission distance of lithium ions is reduced, and the battery has better cycle performance; the AlF of the anode coating surface of the multifunctional diaphragm of the invention3The lithium ion battery electrolyte has lower surface energy and stronger Lewis acidity, can inhibit the decomposition of liquid electrolyte for the lithium ion battery to a greater extent, simultaneously improves the affinity with the electrolyte, simultaneously prevents the growth of lithium dendrite, can improve the cycle performance of the battery, and can also improve the first effect; in organic multifunctional groups (polyethylene oxide and acetamide), PEO can improve ion transmission capability, ATEA can reasonably distribute the flux of lithium ions, so that the lithium ions can be uniformly deposited, the problems of polarization, temperature rise, DCR increase and the like caused by uneven distribution are reduced, the exertion of the electrical property of the lithium ion battery can be greatly promoted, and the first efficiency and the cycle performance of the battery are improved.
(6) Battery expansion rate: the multifunctional separator (MF) and the Commercialized Separator (CS) for the lithium battery were assembled into the pouch battery, respectively (using the same existing pouch battery assembly process), and the battery expansion rate was tested using an electrochemical workstation, and the obtained battery expansion rate results are shown in fig. 4 and table 3.
TABLE 3 results of cell expansion
| Group | MF | |
| Fresh Cell | ||
| 0% | 0% | |
| 500 Cycle | 3.60% | 5.70% |
| 1000 Cycle | 6.30% | 10.50% |
Wherein, fig. 4 is a comparison result table of expansion before and after battery cycle, and table 3 is data counted according to the result in fig. 4, which can be obtained from table 3, the lithium ion battery under the multifunctional diaphragm of the present invention has a lower expansion rate, so that the adhesive (PVDF-HFP) used in the multifunctional diaphragm of the present invention can well adhere the diaphragm and the pole piece together, which can relieve the expansion of the cathode and anode pole pieces in the charging and discharging process, and meanwhile, the organic multifunctional group and the nano inorganic filler also provide space for the expansion of the cathode and anode, thereby greatly reducing the expansion of the whole battery and improving the reliability of the battery.
The above results fully prove that the multifunctional diaphragm for the high-performance lithium ion battery and the preparation method thereof can create conditions for the performance development of the high-voltage, high-safety, high-power, high-electrochemical stability, high first-efficiency and long-service life of the lithium ion battery, obtain the expected effect of the invention, and can meet the development requirement of the current high-performance lithium ion battery.
In summary, the above embodiments of the present invention provide a multifunctional diaphragm for a lithium battery and a technology of a preparation method thereof, and the multifunctional diaphragm for a lithium battery can provide solutions for improving high first efficiency, long cycle, high energy density, high power, high safety, high capacity, and the like of a high-performance lithium ion battery, and can meet application requirements of high performance, high processing efficiency, and high capacity in the current lithium battery industry. The multifunctional diaphragm is a high-Porosity Polypropylene (PP) diaphragm, specifically, the high-porosity PP diaphragm is used as a base film, and multifunctional organic-inorganic composite is respectively coated on the positive and negative surfaces of the diaphragm, wherein the negative surface corresponds to the cathode of the lithium ion battery, the coated substances are nano inorganic filler (boehmite), binder (PVDF-HFP), organic multifunctional group (polyoxyethylene, acetamide), solvent (N-methyl pyrrolidone, dimethyl formamide, acetonitrile) and additive (aminopropanol, polyethylene glycol), the positive surface corresponds to the anode of the lithium ion battery, and the coated substances are nano inorganic filler (aluminum trifluoride), binder (PVDF-HFP), organic multifunctional group (polyoxyethylene, acetamide), solvent (N-methyl pyrrolidone, dimethyl formamide), Acetonitrile), additives (aminopropanol, polyethylene glycol). The cathode nano inorganic filler (boehmite) has small particle size, large specific surface area, large pore volume, high temperature resistance and high voltage resistance, and can create conditions for the performance exertion of high specific energy and high voltage and high nickel material when being coated on the cathode side of the diaphragm, thereby ensuring that the application scenes of high lithium ion flux, high voltage and high heat have no hidden trouble; the anode nano inorganic filler (aluminum trifluoride) has better chemical stability and mechanical property, and the aluminum trifluoride has lower surface energy and stronger Lewis acidity, can inhibit the decomposition of liquid electrolyte for the lithium ion battery to a greater extent, simultaneously improves the affinity with the electrolyte, simultaneously prevents the growth of lithium dendrite, and can improve the rate capability, the cycle performance and the safety performance of the battery to a certain extent. Meanwhile, the PVDF-HFP (polyvinylidene fluoride-hexafluoropropylene) shared by the positive and negative surfaces can well adhere the diaphragm and the pole piece together, so that the diaphragm has the capacity of absorbing and retaining electrolyte, the internal resistance of the lithium ion battery is reduced, and the ionic conductivity is further improved; in organic multifunctional groups (polyethylene oxide and acetamide), PEO has better flexibility, can improve the processability, and simultaneously improve the ion transmission capability, ATEA can reasonably distribute the flux of lithium ions, so that the lithium ions can be uniformly deposited, the problems of polarization, temperature rise, DCR increase and the like caused by uneven distribution are reduced, meanwhile, the matching addition of PEO and ATEA can also reduce static electricity, reduce the wrinkling risk of the diaphragm during high-speed winding, and improve the processing efficiency of the battery; the use of the additive (aminopropanol, polyethylene glycol) can avoid the agglomeration of the nano inorganic filler, the organic multifunctional group and the binder, ensure the uniform dispersion of all substances and control the porosity of the multifunctional diaphragm. The invention adopts the electrostatic spinning method to respectively coat the multifunctional organic-inorganic compound with uniform thickness and the thickness range of 250-300nm on the two sides of the cathode and the anode of the diaphragm, avoids the situation of porosity reduction caused by uneven thickness and can meet the technical requirements of the multifunctional diaphragm for the high-performance lithium ion battery. The invention starts from the application scene of the lithium ion battery, from the electrochemical reaction of the lithium ion battery, from the manufacturing process of the lithium ion battery and from the capacity demand of the lithium ion battery, can create conditions for the performance exertion of the lithium ion battery with high voltage, high safety, high power, high electrochemical stability, high first efficiency and long service life, meets the development requirement of the current high-performance lithium ion battery, and has wide application prospect.
It should be noted that the key points and protection points of the present invention are mainly the following aspects:
1. the cathode and the anode surfaces of the diaphragm are respectively coated with multifunctional organic-inorganic compounds, wherein the cathode surface corresponds to a cathode of a lithium ion battery, the coated substances are nano inorganic fillers (boehmite gamma-AlOOH), binders (PVDF-HFP), organic multifunctional groups (polyoxyethylene and acetamide), solvents (N-methylpyrrolidone, dimethylformamide and acetonitrile) and additives (aminopropanol and polyethylene glycol), the anode surface corresponds to an anode of the lithium ion battery, and the coated substances are nano inorganic fillers (aluminum trifluoride), binders (PVDF-HFP), organic multifunctional groups (polyoxyethylene and acetamide), solvents (N-methylpyrrolidone, dimethylformamide and acetonitrile) and additives (aminopropanol and polyethylene glycol).
2. The cathode nano inorganic filler (boehmite gamma-AlOOH) has small particle size, large specific surface area, large pore volume, high temperature resistance and high voltage resistance, and can create conditions for the performance exertion of high specific energy, high voltage and high nickel material when being coated on the cathode side of the diaphragm, thereby ensuring that the application scenes of high lithium ion flux, high voltage and high heat have no hidden trouble.
3. The anode nano inorganic filler (aluminum trifluoride) has good chemical stability and mechanical property, and AlF3 has low surface energy and strong Lewis acidity, can inhibit the decomposition of liquid electrolyte for a lithium ion battery to a large extent, simultaneously improves the affinity with the electrolyte, simultaneously prevents the growth of lithium dendrite, and can improve the rate capability, the cycle performance and the safety performance of the battery to a certain extent.
4. The PVDF-HFP binder shared by the positive and negative surfaces can well adhere the diaphragm and the pole piece together, can enable the diaphragm to have the capacity of absorbing and retaining electrolyte, reduces the internal resistance of the lithium ion battery, and further improves the ionic conductivity.
5. In the organic multifunctional groups (PEO and ATEA), PEO has better flexibility, the processability can be improved, the ion transmission capability is improved, ATEA can reasonably distribute the flux of lithium ions, so that the lithium ions can be uniformly deposited, the problems of polarization, temperature rise, DCR increase and the like caused by uneven distribution are reduced, meanwhile, the static electricity can be reduced by the matched addition of PEO and ATEA, the wrinkle risk of a diaphragm during high-speed winding is reduced, and the processing efficiency of a battery is improved.
6. The use of the additive (amino propanol, polyethylene glycol) can avoid the agglomeration of the nano inorganic filler, the organic multifunctional group and the binder, ensure the uniform dispersion of all substances and control the porosity of the multifunctional diaphragm.
7. The invention adopts the electrostatic spinning method to respectively coat the multifunctional organic-inorganic compound with uniform thickness and the thickness range of 250-300nm on the two sides of the cathode and the anode of the diaphragm, thereby avoiding the situation of porosity reduction caused by uneven thickness and meeting the technical requirements of the multifunctional diaphragm for the high-performance lithium ion battery; moreover, the materials and the preparation process of the multifunctional separator for lithium batteries according to the present invention each have substitution of similarly functional materials, and each step and any arbitrary combination of the steps are within the scope of the present invention.
The above description has been made in detail on the preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and the application of the present invention is not limited to the above examples, and is not limited to the above addition ratio, and can be modified or changed according to the above description, the lithium ion battery of the present invention is not limited to the cylindrical, square aluminum case, soft package battery, and all the related modifications and changes and materials having the same modification mechanism should fall within the protection scope of the appended claims. Accordingly, various modifications can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (10)
1. A multifunctional separator for a lithium battery, comprising a separator material to be coated and an organic-inorganic composite coated on a side of the separator material; wherein the organic-inorganic composite comprises the following raw materials: nano inorganic filler, binder, organic multifunctional group, additive and proper amount of solvent; the organic multifunctional group is selected from one or more of polyethylene oxide and acetamide; the additive is selected from one or more of aminopropanol and polyethylene glycol.
2. The multifunctional separator for a lithium battery as claimed in claim 1, wherein the solvent is added to the organic-inorganic composite in such an amount that the solid content of the organic-inorganic composite is 22 to 26wt% in the raw material of the multifunctional separator for a lithium battery.
3. The multifunctional separator for a lithium battery according to claim 1, wherein the solvent is selected from any one or more of N-methylpyrrolidone, dimethylformamide, and acetonitrile.
4. The multifunctional separator for a lithium battery as claimed in claim 1, wherein the mass ratio of the nano inorganic filler, the binder, the organic multifunctional group and the additive is 1: 5-12: 0.2-0.8: 0.1-0.6.
5. The multifunctional separator for a lithium battery as claimed in claim 4, wherein the mass ratio of the nano inorganic filler, the binder, the organic multifunctional group and the additive is 1: 7-9: 0.5-0.7: 0.3-0.5.
6. A method for preparing a multifunctional separator for a lithium battery as claimed in any one of claims 1 to 5, comprising the steps of:
weighing nano inorganic filler, binder and organic multifunctional group according to a proportion, uniformly mixing, adding additive and a proper amount of solvent, and uniformly mixing to obtain an organic-inorganic compound;
and carrying out electrospinning on the organic-inorganic composite on the side surface of the diaphragm material to be coated, and drying to obtain the multifunctional diaphragm for the lithium battery.
7. The method for preparing a multifunctional separator for a lithium battery as claimed in claim 6, wherein in the method for preparing a multifunctional separator for a lithium battery, the material flow rate during electrospinning is 10 to 20 mL/h.
8. The method as claimed in claim 6, wherein the spinning distance is 30-35cm, the voltage is 28-30kv, the processing temperature is 23-25 ℃, the relative humidity is 42-47%, and the coating thickness is 250-300 nm.
9. A multifunctional separator for a lithium battery prepared by the method for preparing a multifunctional separator for a lithium battery as claimed in claim 6, 7 or 8.
10. Use of the multifunctional separator for lithium battery as claimed in claim 1 or 2 or 3 or 4 or 5 or 9 for the preparation of a lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110091408.4A CN112701420A (en) | 2021-01-23 | 2021-01-23 | Multifunctional diaphragm for lithium battery, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110091408.4A CN112701420A (en) | 2021-01-23 | 2021-01-23 | Multifunctional diaphragm for lithium battery, preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112701420A true CN112701420A (en) | 2021-04-23 |
Family
ID=75515941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110091408.4A Pending CN112701420A (en) | 2021-01-23 | 2021-01-23 | Multifunctional diaphragm for lithium battery, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112701420A (en) |
Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1547216A (en) * | 2003-12-11 | 2004-11-17 | 北京理工大学 | A novel composite electrolyte material |
| CN102779964A (en) * | 2012-08-08 | 2012-11-14 | 龙能科技（苏州）有限公司 | Method for preparing multilayer composite membrane for secondary battery by using electrostatic spinning coating method |
| CN202817076U (en) * | 2012-10-15 | 2013-03-20 | 山西皇城相府中道能源有限公司 | Cylindrical lithium-ion power battery |
| CN104681764A (en) * | 2015-02-10 | 2015-06-03 | 龙岩紫荆创新研究院 | Composite lithium ion battery ceramic diaphragm and preparation method thereof |
| CN104953070A (en) * | 2015-05-06 | 2015-09-30 | 东莞市魔方新能源科技有限公司 | Isolating membrane for lithium ion secondary battery |
| CN105794019A (en) * | 2013-12-06 | 2016-07-20 | 大金工业株式会社 | Secondary battery separator and secondary battery |
| CN105958000A (en) * | 2016-07-11 | 2016-09-21 | 东莞市魔方新能源科技有限公司 | Lithium ion battery composite membrane and preparation method thereof |
| CN106252565A (en) * | 2016-09-23 | 2016-12-21 | 佛山市金辉高科光电材料有限公司 | Lithium ion battery separator that a kind of composite coated processes and preparation method thereof |
| CN106654362A (en) * | 2016-12-07 | 2017-05-10 | 珠海光宇电池有限公司 | Composite solid electrolyte membrane, preparation method and lithium-ion battery |
| CN108034318A (en) * | 2017-12-05 | 2018-05-15 | 上海恩捷新材料科技股份有限公司 | A kind of low moisture lithium ion battery separator |
| CN108565382A (en) * | 2018-04-28 | 2018-09-21 | 上海恩捷新材料科技股份有限公司 | A kind of aqueous coating lithium ion battery separator and preparation method thereof |
| CN109755448A (en) * | 2018-12-28 | 2019-05-14 | 北京中能东道绿驰科技有限公司 | A kind of lithium battery diaphragm and preparation method thereof with benefit lithium coating |
| CN110148778A (en) * | 2019-06-21 | 2019-08-20 | 广州华新科智造技术有限公司 | Solid electrolyte film material and preparation method thereof and battery |
| CN110571393A (en) * | 2019-07-29 | 2019-12-13 | 河北金力新能源科技股份有限公司 | slurry for lithium battery diaphragm, preparation method of slurry, lithium battery diaphragm and lithium battery |
| CN110970590A (en) * | 2019-12-18 | 2020-04-07 | 江苏厚生新能源科技有限公司 | Ceramic coating slurry, preparation method thereof, lithium battery diaphragm and lithium ion battery |
| CN111009683A (en) * | 2019-11-12 | 2020-04-14 | 北京泰丰先行新能源科技有限公司 | Asymmetric semi-solid electrolyte, preparation method and metal lithium secondary battery |
| CN111293262A (en) * | 2020-03-18 | 2020-06-16 | 溧阳天目先导电池材料科技有限公司 | Composite diaphragm capable of reducing thermal runaway risk of lithium battery, preparation method and lithium battery |
| CN111370631A (en) * | 2020-03-17 | 2020-07-03 | 绍兴望竹新能源科技有限公司 | Battery diaphragm of lithium battery |
-
2021
- 2021-01-23 CN CN202110091408.4A patent/CN112701420A/en active Pending
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1547216A (en) * | 2003-12-11 | 2004-11-17 | 北京理工大学 | A novel composite electrolyte material |
| CN102779964A (en) * | 2012-08-08 | 2012-11-14 | 龙能科技（苏州）有限公司 | Method for preparing multilayer composite membrane for secondary battery by using electrostatic spinning coating method |
| CN202817076U (en) * | 2012-10-15 | 2013-03-20 | 山西皇城相府中道能源有限公司 | Cylindrical lithium-ion power battery |
| CN105794019A (en) * | 2013-12-06 | 2016-07-20 | 大金工业株式会社 | Secondary battery separator and secondary battery |
| CN104681764A (en) * | 2015-02-10 | 2015-06-03 | 龙岩紫荆创新研究院 | Composite lithium ion battery ceramic diaphragm and preparation method thereof |
| CN104953070A (en) * | 2015-05-06 | 2015-09-30 | 东莞市魔方新能源科技有限公司 | Isolating membrane for lithium ion secondary battery |
| CN105958000A (en) * | 2016-07-11 | 2016-09-21 | 东莞市魔方新能源科技有限公司 | Lithium ion battery composite membrane and preparation method thereof |
| CN106252565A (en) * | 2016-09-23 | 2016-12-21 | 佛山市金辉高科光电材料有限公司 | Lithium ion battery separator that a kind of composite coated processes and preparation method thereof |
| CN106654362A (en) * | 2016-12-07 | 2017-05-10 | 珠海光宇电池有限公司 | Composite solid electrolyte membrane, preparation method and lithium-ion battery |
| CN108034318A (en) * | 2017-12-05 | 2018-05-15 | 上海恩捷新材料科技股份有限公司 | A kind of low moisture lithium ion battery separator |
| CN108565382A (en) * | 2018-04-28 | 2018-09-21 | 上海恩捷新材料科技股份有限公司 | A kind of aqueous coating lithium ion battery separator and preparation method thereof |
| CN109755448A (en) * | 2018-12-28 | 2019-05-14 | 北京中能东道绿驰科技有限公司 | A kind of lithium battery diaphragm and preparation method thereof with benefit lithium coating |
| CN110148778A (en) * | 2019-06-21 | 2019-08-20 | 广州华新科智造技术有限公司 | Solid electrolyte film material and preparation method thereof and battery |
| CN110571393A (en) * | 2019-07-29 | 2019-12-13 | 河北金力新能源科技股份有限公司 | slurry for lithium battery diaphragm, preparation method of slurry, lithium battery diaphragm and lithium battery |
| CN111009683A (en) * | 2019-11-12 | 2020-04-14 | 北京泰丰先行新能源科技有限公司 | Asymmetric semi-solid electrolyte, preparation method and metal lithium secondary battery |
| CN110970590A (en) * | 2019-12-18 | 2020-04-07 | 江苏厚生新能源科技有限公司 | Ceramic coating slurry, preparation method thereof, lithium battery diaphragm and lithium ion battery |
| CN111370631A (en) * | 2020-03-17 | 2020-07-03 | 绍兴望竹新能源科技有限公司 | Battery diaphragm of lithium battery |
| CN111293262A (en) * | 2020-03-18 | 2020-06-16 | 溧阳天目先导电池材料科技有限公司 | Composite diaphragm capable of reducing thermal runaway risk of lithium battery, preparation method and lithium battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP4050710A1 (en) | Diaphragm and high-voltage battery comprising same | |
| KR101940249B1 (en) | A anode active material with enhanced power property and an electrode comprising the same for an electrochemical device | |
| CN101662042B (en) | Polymer lithium ion battery and preparation method of diaphragm thereof | |
| WO2016161920A1 (en) | Composite separator and preparation method therefor, and lithium-ion battery | |
| CN102694150A (en) | Method for preparing lithium-ion secondary battery pole piece | |
| CN105679984A (en) | Non-porous separator and application thereof | |
| CN114552122B (en) | Separator, preparation method thereof and secondary battery | |
| CN114649560A (en) | Zn-MOF/PAN @ PAN composite membrane material and preparation method and application thereof | |
| CN112382759B (en) | Preparation method of nitrogen-doped porous carbon-coated silicon composite nanofiber | |
| CN111293256B (en) | Ceramic particle, diaphragm comprising ceramic particle and battery | |
| CN111816839A (en) | Lithium ion battery electrode, preparation method and application thereof, and lithium ion battery | |
| CN116014072A (en) | Battery cell | |
| CN109119637B (en) | Current collector coating, pole piece, lithium ion battery and preparation method thereof | |
| WO2024087389A1 (en) | Secondary battery and electrical device | |
| CN117832747A (en) | Lithium ion battery diaphragm, preparation method thereof and lithium ion battery comprising lithium ion battery diaphragm | |
| CN112701420A (en) | Multifunctional diaphragm for lithium battery, preparation method and application | |
| CN114400300A (en) | Lithium iron phosphate positive plate, preparation method and battery | |
| CN108987803B (en) | Lithium metal negative electrode film-forming electrolyte for lithium-sulfur battery and additive thereof | |
| CN114583094A (en) | Lithium ion battery capable of improving low-temperature performance and preparation method thereof | |
| CN112103464A (en) | Method for preparing anode material polar plate for lithium ion battery | |
| CN112331857A (en) | Positive pole piece for improving safety of lithium ion battery and high-safety lithium ion battery | |
| KR101776281B1 (en) | A lithium secondary battery with improved power property | |
| CN117335095B (en) | Gradient cross-linked diaphragm of lithium-sulfur battery, preparation method of gradient cross-linked diaphragm and lithium-sulfur battery | |
| CN115911753B (en) | Preparation method of composite lithium-sulfur battery diaphragm material with polyphenylene sulfide as substrate | |
| KR101677794B1 (en) | Organic/inorganic composite separator for secondary battery, method of manufacturing the same, and secondary battery using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210423 |
|
| RJ01 | Rejection of invention patent application after publication |