CN113964450A - Battery diaphragm coating liquid and preparation method thereof, battery diaphragm and battery - Google Patents
Battery diaphragm coating liquid and preparation method thereof, battery diaphragm and battery Download PDFInfo
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- CN113964450A CN113964450A CN202010692547.8A CN202010692547A CN113964450A CN 113964450 A CN113964450 A CN 113964450A CN 202010692547 A CN202010692547 A CN 202010692547A CN 113964450 A CN113964450 A CN 113964450A
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- 239000011248 coating agent Substances 0.000 title claims abstract description 108
- 238000000576 coating method Methods 0.000 title claims abstract description 108
- 239000007788 liquid Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000919 ceramic Substances 0.000 claims abstract description 112
- 239000002070 nanowire Substances 0.000 claims abstract description 100
- 239000007822 coupling agent Substances 0.000 claims abstract description 55
- 239000000853 adhesive Substances 0.000 claims abstract description 38
- 230000001070 adhesive effect Effects 0.000 claims abstract description 38
- 239000002245 particle Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims description 60
- -1 sodium styrene-butadiene naphthalene sulfonate Chemical compound 0.000 claims description 43
- 239000000843 powder Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 28
- 239000000080 wetting agent Substances 0.000 claims description 28
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 17
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 12
- 229920005610 lignin Polymers 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 229910001593 boehmite Inorganic materials 0.000 claims description 9
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 9
- 229920000058 polyacrylate Polymers 0.000 claims description 9
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 9
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 229910052580 B4C Inorganic materials 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229920001046 Nanocellulose Polymers 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 4
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims description 3
- ILHIHKRJJMKBEE-UHFFFAOYSA-N hydroperoxyethane Chemical compound CCOO ILHIHKRJJMKBEE-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000005750 Copper hydroxide Substances 0.000 claims description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- UQHHJJGYDVXSOG-UHFFFAOYSA-N S(=O)(=O)(O)O.OCC[Na] Chemical compound S(=O)(=O)(O)O.OCC[Na] UQHHJJGYDVXSOG-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 239000002042 Silver nanowire Substances 0.000 claims 1
- 239000012982 microporous membrane Substances 0.000 abstract description 54
- 238000005859 coupling reaction Methods 0.000 abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 238000010168 coupling process Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 239000004698 Polyethylene Substances 0.000 description 38
- 229920000573 polyethylene Polymers 0.000 description 38
- 238000003756 stirring Methods 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 18
- 239000002131 composite material Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 11
- 229920000098 polyolefin Polymers 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 230000006872 improvement Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
Abstract
The invention provides a battery diaphragm coating liquid, a preparation method thereof, a battery diaphragm and a battery. The battery diaphragm coating liquid simultaneously contains ceramics, nanowires, a coupling agent and an adhesive, intermolecular force exists between the ceramics and the adhesive, intermolecular force and hydrogen bonds exist between the nanowires and the adhesive, hydrogen bonds exist between the nanowires and between the ceramics and the nanowires, and the intermolecular force and the hydrogen bonds exist between the ceramics and the nanowires, and the coupling agent respectively performs coupling reaction with the ceramics and the nanowires, so that chemical bonds are formed between the coupling agent and the ceramics and between the coupling agent and the nanowires, so that the coupling agent has a bridging effect on the nanowires and ceramic particles, a structure of … ceramics-coupling agent-nanowires-ceramics-coupling agent-nanowires … is formed, the acting forces among various molecules are mutually enhanced, and better heat resistance is finally realized. The battery diaphragm prepared by coating the battery diaphragm coating liquid on the microporous membrane material has better thermal stability.
Description
Technical Field
The invention relates to the field of battery diaphragms, in particular to a battery diaphragm coating liquid and a preparation method thereof, a battery diaphragm and a battery.
Background
The lithium ion battery is mainly composed of four materials, including a positive electrode material, a negative electrode material, a diaphragm and electrolyte. As one of the important components, the separator plays a very important role in the performance of the lithium ion battery. Separator (battery separator) refers to a layer of separator material disposed between the positive and negative electrodes of a battery, commonly referred to as the battery separator. The main functions of the battery separator are: isolating the positive and negative electrodes and preventing electrons in the cell from freely passing through, while allowing ions in the electrolyte to freely pass between the positive and negative electrodes.
The ion conduction capability of the battery diaphragm is directly related to the overall performance of the lithium ion battery, the battery can limit the rise of current under the condition of overcharge or temperature rise under the action of isolating the positive electrode and the negative electrode, the explosion caused by the short circuit of the battery is prevented, the micropore self-closing protection effect is realized, and the safety protection effect is realized on battery users and equipment.
Because the polyolefin microporous membrane has the advantages of low price, better mechanical strength and chemical stability, good comprehensive performance, low cost and the like, the polyolefin microporous membrane is widely used as a battery diaphragm. However, polyolefin microporous membranes have a problem of insufficient thermal stability, thus limiting their further applications in lithium ion batteries. The existing improvement means is to compound a ceramic material on the surface of a polyolefin microporous membrane to improve the heat resistance of the polyolefin microporous membrane, however, the improvement of the heat resistance effect of a battery diaphragm by ceramic coating is limited, and the heat shrinkage performance of the existing ceramic coated diaphragm still cannot meet the requirement with the continuous improvement of the energy density of a power battery.
Disclosure of Invention
The invention aims to provide a battery diaphragm coating liquid, a preparation method thereof, a battery diaphragm and a battery, so as to solve the problem of heat resistance of the battery diaphragm.
In order to achieve the above object, the present invention first provides a battery separator coating liquid, including ceramic powder, nanowires, a coupling agent, an adhesive and a solvent;
the addition amount of the ceramic powder accounts for 10-90 wt% of the whole system of the battery diaphragm coating liquid;
the mass ratio of the nanowires to the ceramic powder is (0.1-20): 100, respectively; preferably, the mass ratio of the nanowires to the ceramic powder is (0.1-15): 100, respectively;
the addition amount of the coupling agent accounts for 0.1-1 wt% of the total amount of the nanowires and the ceramic powder;
the addition amount of the adhesive accounts for 1-10 wt% of the total amount of the nanowires and the ceramic powder.
Specifically, in the battery diaphragm coating liquid, a coupling agent respectively performs coupling reaction with the ceramic and the nanowire, and chemical bonds are formed between the coupling agent and the ceramic and between the coupling agent and the nanowire, namely the coupling agent has a bridging effect on the nanowire and the ceramic particles to form a structure of … ceramic-coupling agent-nanowire-ceramic-coupling agent-nanowire …, and the structure has high thermal stability.
The adhesive can bond all components in the coating liquid, is favorable for forming a coating layer tightly connected with the microporous membrane material during coating and film forming, and is an indispensable component in the coating liquid.
In some embodiments of the invention, the coupling reaction is: and the hydroxyl on the surface of the nanowire and the hydroxyl on the surface of the ceramic particle are subjected to condensation reaction with the hydroxyl in the coupling agent molecule respectively, so that stable chemical bonds are formed between the coupling agent and the nanowire and between the coupling agent and the ceramic particle respectively, and the thermal stability of the coating is further improved.
In some embodiments of the present invention, the ceramic powder comprises one or more of aluminum oxide, boehmite, titanium dioxide, attapulgite and barium sulfate; the particle size of the ceramic powder is 20-2000 nm; preferably, the particle size of the ceramic powder is 20-1500 nm; more preferably, the particle size of the ceramic powder is 20-800 nm.
In some embodiments of the present invention, the nanowire comprises one or more of a carbon nanotube, a nano silver wire, a boron carbide nanowire, a nanocellulose, a copper hydroxide nanowire, a silicon monoxide nanowire and a hydroxyapatite nanowire; the diameter of the nanowire is 1-1000 nm, and the length of the nanowire is 0.05-100 mu m.
In some embodiments of the invention, the coupling agent comprises one or more of a lignin coupling agent and a titanate coupling agent;
optionally, the adhesive comprises one or more of polyvinyl alcohol, polyacrylonitrile, polyacrylic acid, polyacrylate, polymethyl acrylate, styrene butadiene rubber, carboxymethyl cellulose, polyvinylidene fluoride, polyvinylpyrrolidone and polyimide;
optionally, the solvent comprises water.
Since the water molecule contains a hydroxyl group and is favorable for dissociating a substance participating in the coupling reaction to generate the hydroxyl group, the coupling reaction is favorably carried out.
In some embodiments of the invention, the battery diaphragm coating liquid further comprises a wetting agent, and the addition amount of the wetting agent accounts for 0.01 wt% -1 wt% of the whole system of the battery diaphragm coating liquid; the wetting agent comprises at least one of fluorinated alkyl ethoxy alcohol ether, fatty alcohol-polyoxyethylene ether, sodium styrene-butadiene naphthalene sulfonate, hydroxyethyl sodium sulfate and lauryl sodium sulfate.
The invention also provides a preparation method of the battery diaphragm coating liquid, which comprises the following steps:
step 1, providing a mixed solution, wherein the mixed solution comprises ceramic powder, nanowires and a solvent;
step 2, adding a coupling agent into the mixed solution, uniformly mixing, and reacting at the temperature of 60-95 ℃;
step 3, adding an adhesive into the reaction product obtained in the step 2, and uniformly mixing;
preferably, the step 3 further comprises: adding a wetting agent into the reaction product obtained in the step 2.
Specifically, in the step 2, the coupling reaction between the coupling agent and the ceramic or nanowire can be smoothly carried out at the reaction temperature of 60-95 ℃.
In some embodiments of the invention, in the step 2, the reaction time is 0.5 to 5 hours; preferably, the step 2 is carried out in a vacuum environment with the vacuum degree of 0.01-0.1 Mpa.
The lack of oxygen in the vacuum environment is beneficial to the smooth proceeding of the coupling reaction.
In some embodiments of the present invention, in the step 1, the preparation method of the mixed solution includes:
step 11, uniformly mixing ceramic powder and water to obtain a ceramic dispersion solution;
and step 12, adding the nanowires into the ceramic dispersion solution, and uniformly mixing to obtain a mixed solution.
The invention also provides a battery diaphragm which is prepared by coating the battery diaphragm coating liquid on the surface of the microporous membrane material, drying and curing.
Optionally, the microporous membrane material is a polyolefin microporous membrane, such as a polyethylene microporous membrane, a polypropylene microporous membrane, and the like.
Alternatively, the polyolefin microporous membrane has a thickness of 3 to 20 μm, for example, 3 μm, 5 μm, 8 μm, 10 μm, 15 μm, 20 μm, or the like.
Optionally, the battery diaphragm coating liquid is coated on one side surface or two side surfaces of the microporous membrane material;
optionally, the coating thickness of the battery separator coating liquid is 0.1-2 μm, such as 0.1 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm, and the like.
The invention also provides a battery comprising the battery diaphragm.
Optionally, the battery is a lithium ion battery.
The invention has the beneficial effects that:
the battery diaphragm coating liquid simultaneously contains ceramics, nanowires, a coupling agent and an adhesive, intermolecular force exists between the ceramics and the adhesive, intermolecular force and hydrogen bonds exist between the nanowires and the adhesive, hydrogen bonds exist between the nanowires and between the ceramics, intermolecular force and hydrogen bonds exist between the nanowires, and the coupling agent respectively performs coupling reaction with the ceramics and the nanowires, so that chemical bonds are formed between the coupling agent and the ceramics and between the coupling agent and the nanowires, so that the coupling agent has a bridging effect on the nanowires and the ceramic particles to form a structure of … ceramic-coupling agent-nanowire-ceramic-coupling agent- …, besides, the nanowires can fill gaps between the ceramic particles, interaction points between the nanowires and the ceramic particles are increased, and the acting forces among various molecules are mutually enhanced, finally, better heat resistance is realized.
The battery diaphragm prepared by coating the battery diaphragm coating liquid on the microporous membrane material has better thermal stability.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by weight" means the basic unit of measure indicating the relationship of the mass ratio of the plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If the parts by weight of the component A are a parts and the parts by weight of the component B are B parts, the ratio of the mass of the component A to the mass of the component B is expressed as a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is not to be understood that, unlike the parts by weight, the sum of the parts by weight of all components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
Embodiments of the present invention will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
(1) Stirring and mixing aluminum oxide and deionized water, and dispersing in a high-speed dispersion machine to obtain a ceramic dispersion solution;
the particle size of the alumina is 20nm, the dispersion speed is 1000rpm, and the solid content of the alumina in the dispersion liquid is 40 wt%.
(2) Adding hydroxyapatite nano-wires into the ceramic dispersion liquid, and then stirring at a high speed to fully disperse the hydroxyapatite nano-wires and the ceramic dispersion liquid. The diameter of the hydroxyapatite nanowire is 10nm, the length of the hydroxyapatite nanowire is 10 microns, the stirring speed is 1000rpm, and the hydroxyapatite nanowire accounts for 1 wt% of the ceramic.
(3) Adding a lignin coupling agent into the dispersion liquid, and then carrying out reaction at high temperature in vacuum. The addition amount of the lignin coupling agent is 0.2 wt% of the total amount of the nano wire and the ceramic powder, the vacuum degree is 0.1Mpa, the temperature is 95 ℃, and the reaction time is 5 h.
(4) And adding the aqueous adhesive polyacrylate and the aqueous wetting agent fatty alcohol-polyoxyethylene ether into the solution after the reaction, mixing, and stirring by using a stirrer to obtain the coating liquid.
The adding amount of the water-based adhesive accounts for 1 wt% of the total amount of the nanowires and the ceramic powder; the addition amount of the water-based wetting agent accounts for 0.1 wt% of the whole system of the battery diaphragm coating liquid.
(5) Uniformly coating the coating liquid prepared in the step (4) on the two side surfaces of a polyethylene microporous membrane in a roll coating mode, and then drying and curing at the temperature of 60 ℃; and cooling to room temperature to obtain the composite diaphragm consisting of the polyethylene microporous membrane and the coating loaded on the surface of the polyethylene microporous membrane. Wherein, the thickness of the polyethylene microporous membrane is 14 μm, and the thickness of the single-side coating is 1 μm.
Example 2
(1) Stirring and mixing aluminum oxide and deionized water, and dispersing in a high-speed dispersion machine to obtain a ceramic dispersion solution;
the particle size of the alumina was 1000nm, the dispersion speed was 5000rpm, and the solid content of the ceramic in the ceramic dispersion was 40 wt%.
(2) Adding hydroxyapatite nano-wires into the ceramic dispersion liquid, and then stirring at a high speed to fully disperse the hydroxyapatite nano-wires and the ceramic dispersion liquid. The diameter of the hydroxyapatite nanowire is 100nm, the length of the hydroxyapatite nanowire is 60 mu m, the stirring speed is 5000rpm, and the hydroxyapatite nanowire accounts for 20 wt% of the ceramic.
(3) Adding a lignin coupling agent into the dispersion liquid, and then carrying out reaction at high temperature in vacuum. The addition amount of the lignin coupling agent is 1 wt% of the total amount of the nano wire and the ceramic powder, the vacuum degree is 0.1Mpa, the temperature is 60 ℃, and the reaction time is 0.5 h.
(4) And adding the aqueous adhesive polyacrylate and the aqueous wetting agent fatty alcohol-polyoxyethylene ether into the solution after the reaction, mixing, and stirring by using a stirrer to obtain the coating liquid.
The adding amount of the water-based adhesive accounts for 6 wt% of the total amount of the nanowires and the ceramic powder; the addition amount of the water-based wetting agent accounts for 0.5 wt% of the whole system of the battery diaphragm coating liquid.
(5) Uniformly coating the coating liquid prepared in the step (4) on the two side surfaces of the polyethylene microporous membrane in a roll coating mode, and then drying and curing at the temperature of 90 ℃; and cooling to room temperature to obtain the composite diaphragm consisting of the polyethylene microporous membrane and the coating loaded on the surface of the polyethylene microporous membrane. Wherein, the thickness of the polyethylene microporous membrane is 14 μm, and the thickness of the single-side coating is 1 μm.
Example 3
(1) Stirring and mixing boehmite and deionized water, and dispersing in a high-speed dispersion machine to obtain a ceramic dispersion solution;
the particle size of boehmite was 2000nm, the dispersion speed was 10000rpm, and the solid content of ceramic in the ceramic dispersion was 40 wt%.
(2) Adding nano cellulose into the ceramic dispersion liquid, and then stirring at a high speed to fully disperse the nano cellulose and the ceramic dispersion liquid. The diameter of the nano-cellulose is 1000nm, the length is 100 μm, the stirring speed is 2000rpm, and the weight ratio of the nano-cellulose to the ceramic is 10 wt%.
(3) Adding a lignin coupling agent into the dispersion liquid, and then carrying out reaction at high temperature in vacuum. The addition amount of the lignin coupling agent is 0.1 wt% of the total amount of the nano wire and the ceramic powder, the vacuum degree is 0.01Mpa, the temperature is 60 ℃, and the reaction time is 5 h.
(4) And adding the aqueous adhesive polyvinyl alcohol and the aqueous wetting agent sodium styrene-butadiene-naphthalene sulfonate into the solution after the reaction, mixing, and stirring by using a stirrer to obtain the coating liquid.
The adding amount of the water-based adhesive accounts for 3 wt% of the total amount of the nanowires and the ceramic powder; the addition amount of the water-based wetting agent accounts for 0.4 wt% of the whole system of the battery diaphragm coating liquid.
(5) Uniformly coating the coating liquid prepared in the step (4) on the two side surfaces of the polyethylene microporous membrane in a roll coating mode, and then drying and curing at the temperature of 70 ℃; and cooling to room temperature to obtain the composite diaphragm consisting of the polyethylene microporous membrane and the coating loaded on the surface of the polyethylene microporous membrane. Wherein, the thickness of the polyethylene microporous membrane is 14 μm, and the thickness of the single-side coating is 1 μm.
Example 4
(1) Stirring and mixing titanium dioxide and deionized water, and dispersing in a high-speed dispersion machine to obtain a ceramic dispersion solution;
the particle size of boehmite was 500nm, the dispersion speed was 2000rpm, and the solid content of ceramic in the ceramic dispersion was 60 wt%.
(2) Adding carbon nanotubes into the ceramic dispersion, and stirring at high speed to fully disperse the carbon nanotubes and the carbon nanotubes. The diameter of the carbon nano tube is 20nm, the length is 30 μm, the stirring speed is 10000rpm, and the weight ratio of the carbon nano tube in the ceramic is 0.1 wt%.
(3) Adding titanate coupling agent into the dispersion liquid, and then reacting at high temperature in vacuum. The addition amount of the titanate coupling agent is 0.8 wt% of the total amount of the nano-wire and the ceramic powder, the vacuum degree is 0.05Mpa, the temperature is 70 ℃, and the reaction time is 2 h.
(4) And adding the aqueous adhesive polyacrylate and the aqueous wetting agent fatty alcohol-polyoxyethylene ether into the solution after the reaction, mixing, and stirring by using a stirrer to obtain the coating liquid.
The adding amount of the water-based adhesive accounts for 10 wt% of the total amount of the nanowires and the ceramic powder; the addition amount of the water-based wetting agent accounts for 1 wt% of the whole system of the battery diaphragm coating liquid.
(5) Uniformly coating the coating liquid prepared in the step (4) on one side surface of a polyethylene microporous membrane in a roll coating mode, and then drying and curing at the temperature of 80 ℃; and cooling to room temperature to obtain the composite diaphragm consisting of the polyethylene microporous membrane and the coating loaded on the surface of the polyethylene microporous membrane. Wherein, the thickness of the polyethylene microporous membrane is 14 μm, and the thickness of the coating is 1 μm.
Example 5
(1) Stirring and mixing boehmite and deionized water, and dispersing in a high-speed dispersion machine to obtain a ceramic dispersion solution;
the particle size of boehmite was 1500nm, the dispersion speed was 7000rpm, and the solid content of ceramic in the ceramic dispersion was 50 wt%.
(2) Adding boron carbide nanowires into the ceramic dispersion liquid, and then stirring at a high speed to fully disperse the two. The diameter of the boron carbide nanowire is 200nm, the length of the boron carbide nanowire is 50 microns, the stirring speed is 8000rpm, and the weight ratio of the boron carbide nanowire in the ceramic is 5 wt%.
(3) Adding titanate coupling agent into the dispersion liquid, and then reacting at high temperature in vacuum. The addition amount of the titanate coupling agent is 0.6 wt% of the total amount of the nano wire and the ceramic powder, the vacuum degree is 0.07Mpa, the temperature is 65 ℃, and the reaction time is 1 h.
(4) And adding the aqueous adhesive polymethyl acrylate and the aqueous wetting agent fluoroalkyl ethoxy alcohol ether into the reacted solution, mixing, and stirring by using a stirrer to obtain the coating liquid.
The adding amount of the water-based adhesive accounts for 8 wt% of the total amount of the nanowires and the ceramic powder; the addition amount of the water-based wetting agent accounts for 0.7 wt% of the whole system of the battery diaphragm coating liquid.
(5) Uniformly coating the coating liquid prepared in the step (4) on one side surface of a polyethylene microporous membrane in a roll coating mode, and then drying and curing at the temperature of 75 ℃; and cooling to room temperature to obtain the composite diaphragm consisting of the polyethylene microporous membrane and the coating loaded on the surface of the polyethylene microporous membrane. Wherein, the thickness of the polyethylene microporous membrane is 14 μm, and the thickness of the coating is 1 μm.
Comparative example 1
(1) Stirring and mixing aluminum oxide and deionized water, and dispersing in a high-speed dispersion machine to obtain a ceramic dispersion solution;
the particle size of the alumina is 20nm, the dispersion speed is 1000rpm, and the solid content of the alumina in the dispersion liquid is 40 wt%.
(2) And adding the aqueous adhesive polyacrylate and the aqueous wetting agent fatty alcohol-polyoxyethylene ether into the solution, mixing, and stirring by using a stirrer to obtain the coating liquid.
The adding amount of the water-based adhesive accounts for 1 wt% of the total amount of the nanowires and the ceramic powder; the addition amount of the water-based wetting agent accounts for 0.1 wt% of the whole system of the battery diaphragm coating liquid.
(3) Uniformly coating the coating liquid prepared in the step (2) on the two side surfaces of a polyethylene microporous membrane in a roll coating mode, and then drying and curing at the temperature of 60 ℃; and cooling to room temperature to obtain the composite diaphragm consisting of the polyethylene microporous membrane and the coating loaded on the surface of the polyethylene microporous membrane. Wherein, the thickness of the polyethylene microporous membrane is 14 μm, and the thickness of the single-side coating is 1 μm.
Comparative example 2
(1) Stirring and mixing aluminum oxide and deionized water, and dispersing in a high-speed dispersion machine to obtain a ceramic dispersion solution;
the particle size of the alumina was 1000nm, the dispersion speed was 5000rpm, and the solid content of the ceramic in the ceramic dispersion was 40 wt%.
(2) And adding the aqueous adhesive polyacrylate and the aqueous wetting agent fatty alcohol-polyoxyethylene ether into the solution, mixing, and stirring by using a stirrer to obtain the coating liquid.
The adding amount of the water-based adhesive accounts for 6 wt% of the total amount of the ceramic powder; the addition amount of the water-based wetting agent accounts for 0.5 wt% of the whole system of the battery diaphragm coating liquid.
(3) Uniformly coating the coating liquid prepared in the step (2) on the two side surfaces of a polyethylene microporous membrane in a roll coating mode, and then drying and curing at the temperature of 90 ℃; and cooling to room temperature to obtain the composite diaphragm consisting of the polyethylene microporous membrane and the coating loaded on the surface of the polyethylene microporous membrane. Wherein the thickness of the polyolefin microporous membrane is 14 μm, and the thickness of the single-side coating is 1 μm.
Comparative example 3
(1) Stirring and mixing boehmite and deionized water, and dispersing in a high-speed dispersion machine to obtain a ceramic dispersion solution;
the particle size of boehmite was 2000nm, the dispersion speed was 10000rpm, and the solid content of ceramic in the ceramic dispersion was 40 wt%.
(2) And adding the aqueous adhesive polyvinyl alcohol and the aqueous wetting agent sodium styrene-butadiene naphthalene sulfonate into the solution, mixing, and stirring by using a stirrer to obtain the coating liquid.
The adding amount of the water-based adhesive accounts for 3 wt% of the total amount of the ceramic powder; the addition amount of the water-based wetting agent accounts for 0.4 wt% of the whole system of the battery diaphragm coating liquid.
(3) Uniformly coating the coating liquid prepared in the step (2) on the two side surfaces of a polyethylene microporous membrane in a roll coating mode, and then drying and curing at the temperature of 70 ℃; and cooling to room temperature to obtain the composite diaphragm consisting of the polyethylene microporous membrane and the coating loaded on the surface of the polyethylene microporous membrane. Wherein the thickness of the polyolefin microporous membrane is 14 μm, and the thickness of the single-side coating is 1 μm.
Comparative example 4
(1) Stirring and mixing aluminum oxide and deionized water, and dispersing in a high-speed dispersion machine to obtain a ceramic dispersion solution;
the particle size of the alumina is 100nm, the dispersion speed is 1000rpm, and the solid content of the alumina in the dispersion liquid is 40 wt%.
(2) Adding hydroxyapatite nano-wires into the ceramic dispersion liquid, and then stirring at a high speed to fully disperse the hydroxyapatite nano-wires and the ceramic dispersion liquid. The diameter of the hydroxyapatite nanowire is 10nm, the length of the hydroxyapatite nanowire is 10 microns, the stirring speed is 1000rpm, and the hydroxyapatite nanowire accounts for 1% of the weight of the ceramic.
(3) And adding the aqueous adhesive polyacrylate and the aqueous wetting agent fatty alcohol-polyoxyethylene ether into the solution after the reaction, mixing, and stirring by using a stirrer to obtain the coating liquid.
The adding amount of the water-based adhesive accounts for 1 wt% of the total amount of the nanowires and the ceramic powder; the addition amount of the water-based wetting agent accounts for 0.1 wt% of the whole system of the battery diaphragm coating liquid.
(4) Uniformly coating the coating liquid prepared in the step (4) on the two side surfaces of a polyethylene microporous membrane in a roll coating mode, and then drying and curing at the temperature of 60 ℃; and cooling to room temperature to obtain the composite diaphragm consisting of the polyethylene microporous membrane and the coating loaded on the surface of the polyethylene microporous membrane. Wherein the thickness of the polyolefin microporous membrane is 14 μm, and the thickness of the single-side coating is 1 μm.
Comparative example 5
(1) Stirring and mixing aluminum oxide and deionized water, and dispersing in a high-speed dispersion machine to obtain a ceramic dispersion solution;
the particle size of the alumina was 1500nm, the dispersion speed was 7000rpm, and the solid content of the ceramic in the ceramic dispersion was 40 wt%.
(2) Adding a lignin coupling agent into the dispersion liquid, and then carrying out reaction at high temperature in vacuum. The addition amount of the lignin coupling agent is 0.2 wt% of the ceramic powder, the vacuum degree is 0.1Mpa, the temperature is 95 ℃, and the reaction time is 5 h.
(3) And adding the aqueous adhesive polyacrylate and the aqueous wetting agent fatty alcohol-polyoxyethylene ether into the solution after the reaction, mixing, and stirring by using a stirrer to obtain the coating liquid.
The adding amount of the water-based adhesive accounts for 1 wt% of the total amount of the ceramic powder; the addition amount of the water-based wetting agent accounts for 0.1 wt% of the whole system of the battery diaphragm coating liquid.
(4) Uniformly coating the coating liquid prepared in the step (3) on the two side surfaces of the polyethylene microporous membrane in a roll coating mode, and then drying and curing at the temperature of 60 ℃; and cooling to room temperature to obtain the composite diaphragm consisting of the polyethylene microporous membrane and the coating loaded on the surface of the polyethylene microporous membrane. Wherein the thickness of the polyolefin microporous membrane is 14 μm, and the thickness of the single-side coating is 1 μm.
As can be seen by comparing examples 1-5 and comparative examples 1-5 above:
comparative example 1 compares to example 1, no nanowires were added, and no coupling agent was added.
Comparative example 2 compares to example 2, no nanowires were added, and no coupling agent was added.
Comparative example 3 compares to example 3, no nanowires were added, and no coupling agent was added.
Comparative example 4 compared to example 1, no coupling agent was added.
Comparative example 5 compared to example 1, no nanowires were added.
The composite separators prepared in the above examples 1 to 5 and comparative examples 1 to 5 and the base film (polyethylene microporous film) were tested, and the thermal stability of the separator was measured according to the GB/T21650.1-2008 standard, and the results are shown in the following table:
as can be seen from the above table, the thermal stability of the composite separators prepared in examples 1 to 5 is significantly superior to that of the composite separators prepared in comparative examples 1 to 5. In the case of single-side coating of examples 4 and 5 of the present application, the thermal stability of the resulting composite separator was still superior to that of the composite separators prepared in comparative examples 1 to 5 by double-side coating.
Of comparative examples 1 to 5, comparative example 5 in which the coupling agent was added but the nanowire was not added and comparative example 4 in which the nanowire was added but the coupling agent was not added both had inferior thermal stability, and comparative examples 1 to 3 in which the nanowire and the coupling agent were not added were inferior in thermal stability.
The coating liquid prepared in the embodiments 1 to 5 contains ceramic, nanowires, coupling agent and adhesive at the same time, intermolecular forces exist between the ceramic and the adhesive, intermolecular forces and hydrogen bonds exist between the nanowires and the adhesive, hydrogen bonds exist between the nanowires and between the ceramic and the nanowires, and intermolecular forces and hydrogen bonds exist between the ceramic and the nanowires, and the coupling agent respectively performs coupling reaction with the ceramic and the nanowires, so that chemical bonds are formed between the coupling agent and the ceramic and between the coupling agent and the nanowires, so that the coupling agent has a bridging effect on the nanowires and the ceramic particles, and a structure of … ceramic-coupling agent-nanowire-ceramic-coupling agent … is formed, besides, the nanowires can fill gaps between the ceramic particles, interaction points between the nanowires and the ceramic particles are increased, and various intermolecular forces are mutually enhanced, finally, better heat resistance is realized.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. The battery diaphragm coating liquid is characterized by comprising ceramic powder, nanowires, a coupling agent, an adhesive and a solvent;
the addition amount of the ceramic powder accounts for 10-90 wt% of the whole system of the battery diaphragm coating liquid;
the mass ratio of the nanowires to the ceramic powder is (0.1-20): 100, respectively;
the addition amount of the coupling agent accounts for 0.1-1 wt% of the total amount of the nanowires and the ceramic powder;
the addition amount of the adhesive accounts for 1-10 wt% of the total amount of the nanowires and the ceramic powder.
2. The battery separator coating liquid according to claim 1, wherein the ceramic powder comprises one or more of aluminum oxide, boehmite, titanium dioxide, attapulgite, and barium sulfate; the particle size of the ceramic powder is 20-2000 nm.
3. The battery separator coating solution according to claim 1, wherein the nanowires comprise one or more of carbon nanotubes, silver nanowires, boron carbide nanowires, nanocellulose, copper hydroxide nanowires, silicon monoxide nanowires, and hydroxyapatite nanowires; the diameter of the nanowire is 1-1000 nm, and the length of the nanowire is 0.05-100 mu m.
4. The battery separator coating solution according to claim 1, wherein the coupling agent comprises one or more of a lignin coupling agent and a titanate coupling agent;
optionally, the adhesive comprises one or more of polyvinyl alcohol, polyacrylonitrile, polyacrylic acid, polyacrylate, polymethyl acrylate, styrene butadiene rubber, carboxymethyl cellulose, polyvinylidene fluoride, polyvinylpyrrolidone and polyimide;
optionally, the solvent comprises water.
5. The battery separator coating liquid as defined in claim 1, further comprising a wetting agent, wherein the amount of the wetting agent added is 0.01 wt% to 1 wt% of the entire system of the battery separator coating liquid; the wetting agent comprises at least one of fluorinated alkyl ethoxy alcohol ether, fatty alcohol-polyoxyethylene ether, sodium styrene-butadiene naphthalene sulfonate, hydroxyethyl sodium sulfate and lauryl sodium sulfate.
6. A method for preparing the battery separator coating liquid as defined in any one of claims 1 to 5, comprising:
step 1, providing a mixed solution, wherein the mixed solution comprises ceramic powder, nanowires and a solvent;
step 2, adding a coupling agent into the mixed solution, uniformly mixing, and reacting at the temperature of 60-95 ℃;
step 3, adding an adhesive into the reaction product obtained in the step 2, and uniformly mixing;
preferably, the step 3 further comprises: adding a wetting agent into the reaction product obtained in the step 2.
7. The method according to claim 6, wherein in the step 2, the reaction time is 0.5 to 5 hours; preferably, the step 2 is carried out in a vacuum environment with the vacuum degree of 0.01-0.1 Mpa.
8. The method according to claim 6, wherein the method for preparing the mixed solution in step 1 comprises:
step 11, uniformly mixing ceramic powder and water to obtain a ceramic dispersion solution;
and step 12, adding the nanowires into the ceramic dispersion solution, and uniformly mixing to obtain a mixed solution.
9. A battery separator obtained by applying the battery separator coating liquid according to any one of claims 1 to 5 to the surface of a microporous film material, drying and curing.
10. A battery comprising the battery separator of claim 9.
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