CN112751137A - Method for arranging diaphragm gluing layer - Google Patents
Method for arranging diaphragm gluing layer Download PDFInfo
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- CN112751137A CN112751137A CN202011613618.7A CN202011613618A CN112751137A CN 112751137 A CN112751137 A CN 112751137A CN 202011613618 A CN202011613618 A CN 202011613618A CN 112751137 A CN112751137 A CN 112751137A
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- gluing
- diaphragm
- slurry
- solvent
- combination
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- 238000004026 adhesive bonding Methods 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 60
- 239000002904 solvent Substances 0.000 claims abstract description 44
- 239000002002 slurry Substances 0.000 claims abstract description 43
- 229920000642 polymer Polymers 0.000 claims abstract description 39
- 239000004094 surface-active agent Substances 0.000 claims abstract description 32
- 238000001125 extrusion Methods 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 27
- -1 polyoxyethylene cetyl ether Polymers 0.000 claims description 24
- 238000005524 ceramic coating Methods 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 21
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 229910010293 ceramic material Inorganic materials 0.000 claims description 17
- 239000012528 membrane Substances 0.000 claims description 17
- 239000011230 binding agent Substances 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 239000004642 Polyimide Substances 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 15
- 229920001721 polyimide Polymers 0.000 claims description 15
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 13
- 239000004698 Polyethylene Substances 0.000 claims description 13
- 229920000573 polyethylene Polymers 0.000 claims description 13
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 12
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 12
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 12
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 12
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 12
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 229910001593 boehmite Inorganic materials 0.000 claims description 10
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- 229920000428 triblock copolymer Polymers 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 2
- 238000004513 sizing Methods 0.000 abstract description 25
- 239000003795 chemical substances by application Substances 0.000 abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- 230000010220 ion permeability Effects 0.000 abstract description 4
- 239000003292 glue Substances 0.000 description 30
- 239000010410 layer Substances 0.000 description 25
- 239000011247 coating layer Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 8
- 239000005060 rubber Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Cell Separators (AREA)
Abstract
The invention provides a method for arranging a diaphragm gluing layer, which comprises the following steps: extruding the gluing slurry at intervals on the surface of the diaphragm substrate to complete the setting of the diaphragm gluing layer; the distance of the interval is 40-80 mm; the single-point gluing amount of the extrusion is 0.1-1.5g/m2. The gluing sizing agent comprises the following components in percentage by mass: 30-80% of polymer, 5-20% of surfactant and the balance of gluing solvent. The method provided by the invention can ensure the bonding strength between the diaphragm and the anode and/or the cathode, and can also ensure the lithium ion permeability of the diaphragm.
Description
Technical Field
The invention belongs to the technical field of batteries, relates to a method for arranging a diaphragm, and particularly relates to a method for arranging a diaphragm gluing layer.
Background
The lithium battery mainly comprises a positive electrode material, a negative electrode material, a diaphragm, electrolyte, packaging materials and the like. The isolating membrane plays an important role in realizing electronic insulation and ion transmission between the positive electrode and the negative electrode. A high-quality separator should have excellent electrochemical stability, high-quality liquid retention to an electrolyte, good safety performance, and the like.
In order to improve the safety performance of the diaphragm, diaphragm processes of the composite polyolefin type diaphragm substrate, including diaphragms with different ceramic coating structures and low-melting-point and high-adhesion polymer glue coating layers, have been developed. The glued diaphragm can obviously improve the mechanical strength of the battery in the hot pressing process of the battery assembly section, and obviously improve the cycle/safety performance of the battery.
CN 204564452U discloses a laminated battery pack and supercapacitor diaphragm glue spreader, which comprises a driving motor, wherein the driving motor drives a sizing roller, the sizing roller drives a rubber roller through a belt wheel, a sizing groove is arranged below the sizing roller, a paper placing platform is arranged on one side of the sizing groove and the rubber roller, a material receiving flat plate is arranged on the other side of the sizing groove and the rubber roller, and the tangent line of the sizing roller and the rubber roller corresponds to the plane of the paper placing platform; wherein a paper feeding wheel is arranged between the plane of the paper placing platform and the sizing roller and the rubber roller.
CN 103028535a discloses a membrane gluing method, which comprises fully soaking a glued membrane in a volatile solvent, gluing the soaked membrane, and drying the glued membrane, thereby completing the gluing operation. The membrane gluing method is additionally provided with the step of infiltrating the glued membrane on the basis of the traditional gluing mode, so that the pores of the membrane are filled with volatile solvents; and gluing the soaked diaphragm, wherein the solution in the diaphragm can be emitted from the diaphragm to perform pore forming during drying.
CN 204307779U discloses a gluing device for a lithium ion battery diaphragm, which has a glue solution tank and a glue spreader, wherein the glue solution tank is used for accommodating glue solution, the glue spreader is located below the lithium ion battery diaphragm, and a plurality of raised lines are formed on the outer circumferential surface of the glue spreader at intervals in the circumferential direction of the outer circumferential surface. When the diaphragm moves, the glue spreader is driven to rotate, the convex strips, which are adhered with glue liquid and enter the glue liquid groove, of the glue spreader rotate to the upper end to coat the diaphragm, so that strip glue coating layers at intervals are formed on the diaphragm, and the diaphragm is coated with glue at intervals. Therefore, the part of the diaphragm which is not coated with glue is utilized to improve the passing property of lithium ions, and the diaphragm is uniformly coated with glue to ensure the adhesion between the diaphragm and the electrode.
In the arrangement mode of the glue coating layer, the surface glue coating amount is not easy to control during spraying, and the glue layer on the surface of the finished product is not uniformly distributed, so that the interface bonding and the dynamic characteristics of the finished product battery cell are reduced; the good interfacial adhesion of the finished product battery cell in the assembly section can be ensured during roller coating, but the subsequent liquid injection has poor infiltration effect on the electrolyte. Therefore, it is necessary to provide a method for arranging a diaphragm glue coating layer, which ensures the adhesive property and has a good electrolyte infiltration effect.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the method for arranging the diaphragm glue coating layer, which not only can ensure the bonding strength between the diaphragm and the anode and/or the cathode, but also can ensure the lithium ion permeability of the diaphragm and has good wettability.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for arranging a diaphragm gluing layer, which comprises the following steps:
extruding the gluing slurry at intervals on the surface of the diaphragm substrate to complete the setting of the diaphragm gluing layer;
the distance of the interval is 40-80 mm; the single-point gluing amount of the extrusion is 0.1-1.5g/m2。
Preferably, the speed of extrusion is 20-80 mm/s.
The extrusion intervals according to the invention are 40-80mm, for example 40mm, 45mm, 50mm, 55mm, 60mm, 65mm, 70mm, 75mm or 70mm, but are not limited to the values listed, and other values not listed in the range of values are equally applicable.
The interval extrusion means that the distance between any two adjacent gluing positions is equal.
The single-point gluing amount of the extrusion is 0.1-1.5g/m2For example, it may be 0.1g/m2、0.2g/m2、0.3g/m2、0.4g/m2、0.5g/m2、0.6g/m2、0.7g/m2、0.8g/m2、0.9g/m2、1g/m2、1.1g/m2、1.2g/m2、1.3g/m2、1.4g/m2Or 1.5g/m2But are not limited to the recited values, and other values within the numerical range not recited are equally applicable.
The extrusion speed according to the invention is 20 to 80mm/s, and may be, for example, 20mm/s, 30mm/s, 40mm/s, 50mm/s, 60mm/s, 70mm/s or 80mm/s, but is not limited to the values listed, and other values within the range are equally applicable.
According to the invention, the diaphragm glue coating layer can be better connected with the positive plate and/or the negative plate by controlling the spacing distance, the single-point glue coating amount and the extrusion speed, so that the stability of the diaphragm after forming the battery cell is ensured; and the wetting property of the diaphragm can be ensured on the premise of ensuring the caking property by controlling the spacing distance, the single-point gluing amount and the extrusion speed.
Preferably, the gumming slurry comprises, in mass percent:
30-80 wt% of polymer
5-20 wt% of surfactant
The balance being the gluing solvent.
The mass percentage of polymer in the gumming slurry according to the invention is 30-80 wt%, for example 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt% or 80 wt%, but is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
The mass percentage of surfactant in the gumming slurry according to the invention is 5-20 wt%, for example 5 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt% or 20 wt%, but is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the polymer comprises any one of or a combination of at least two of carboxymethyl cellulose, polymethyl methacrylate, polyimide, or polyoxyethylene; typical but non-limiting combinations include a combination of carboxymethylcellulose and polymethylmethacrylate, a combination of polymethylmethacrylate and polyimide, a combination of polyimide and polyoxyethylene, a combination of carboxymethylcellulose, polymethylmethacrylate and polyimide, a combination of polymethylmethacrylate, polyimide and polyoxyethylene, or a combination of carboxymethylcellulose, polymethylmethacrylate, polyimide and polyoxyethylene.
The combination of polymers according to the invention is not only a blend of at least two polymers, but also includes the combination of at least two polymers to form a homopolymer.
Preferably, the number average molecular weight of the polymer is 10000-.
Preferably, the surfactant comprises any one of polyoxyethylene cetyl ether, polyoxyethylene octylphenol ether-10 or polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer or a combination of at least two of the above;
preferably, the surfactant has a number average molecular weight of 3000-10000, which may be, for example, 3000, 4000, 5000, 6000, 7000, 8000, 9000 or 10000, but is not limited to the recited values, and other unrecited values within the range of values are equally applicable.
Preferably, the gumming solvent comprises any one or a combination of at least two of water, acetone, ethanol, dichloromethane, methanol, diethyl ether or pentane; typical but non-limiting combinations include acetone and ethanol, ethanol and dichloromethane, dichloromethane and methanol, methanol and diethyl ether, diethyl ether and pentane, ethanol, dichloromethane and methanol, dichloromethane, methanol and diethyl ether, methanol, diethyl ether and pentane, or water, acetone, ethanol, dichloromethane, methanol, diethyl ether and pentane.
Preferably, the sizing slurry further comprises 0.01 to 10 wt% of a viscosity modifier, and the mass percentage of the viscosity modifier in the sizing slurry is 0.01 to 10 wt%, for example, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 5 wt%, or 10 wt%, but not limited to the recited values, and other values in the range of values are also applicable.
Preferably, the viscosity modifier comprises ethylene glycol and/or glycerol.
Preferably, the gumming slurry is prepared by the following method: mixing a polymer, a surfactant and a gluing solvent according to the formula ratio to obtain a mixture, and treating the mixture by ultrasonic waves to uniformly mix the mixture to obtain the gluing slurry.
Preferably, the mixture also comprises a viscosity regulator.
Preferably, the time of the ultrasonic treatment is 2 to 6 hours, for example, 2 hours, 3 hours, 4 hours, 5 hours or 6 hours, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
The invention provides the dispersion uniformity of the polymer and the surfactant in the mixture by an ultrasonic treatment mode. The present invention does not specifically limit the frequency of ultrasonic treatment, and those skilled in the art can set the frequency appropriately as needed.
Preferably, the separator substrate is a separator substrate provided with a ceramic coating.
Preferably, the thickness of the ceramic coating is 5 to 40 μm, and may be, for example, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm or 40 μm, but is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the ceramic slurry for the ceramic coating comprises the following components in percentage by mass:
40-70 wt% of ceramic material
5-20 wt% of binder
The balance being coating solvent.
The ceramic material in the ceramic coating according to the invention may be present in an amount of 40 to 70 wt.%, for example 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.% or 70 wt.%, but is not limited to the values listed, and other values not listed in the numerical ranges are equally applicable.
Preferably, the ceramic material has an average particle size of 1 to 10 μm, which may be, for example, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm, but is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the ceramic material comprises any one or a combination of at least two of silica, alumina, boehmite, magnesia, titania, or zinc oxide, typical but non-limiting combinations include combinations of silica and alumina, alumina and boehmite, boehmite and magnesia, magnesia and titania, titania and zinc oxide, silica, alumina and boehmite, magnesia and titania, boehmite, magnesia, titania and zinc oxide, or silica, alumina, boehmite, magnesia, titania and zinc oxide.
Preferably, the binder comprises any one of or a combination of at least two of carboxymethyl cellulose, polyvinylidene fluoride, styrene-butadiene rubber, polyimide or polyethylene; typical but non-limiting combinations include a combination of carboxymethylcellulose and polyvinylidene fluoride, a combination of polyvinylidene fluoride and styrene butadiene rubber, a combination of styrene butadiene rubber and polyimide, a combination of polyimide and polyethylene, a combination of carboxymethylcellulose, polyvinylidene fluoride and styrene butadiene rubber, a combination of polyvinylidene fluoride, styrene butadiene rubber and polyimide, a combination of styrene butadiene rubber, polyimide and polyethylene, or a combination of carboxymethylcellulose, polyvinylidene fluoride, styrene butadiene rubber, polyimide and polyethylene.
Preferably, the number average molecular weight of the binder is 10000-.
The combination of polymers according to the invention is not only a blend of at least two polymers, but also includes the combination of at least two polymers to form a homopolymer.
Preferably, the coating solvent comprises any one of water, acetone, ethanol, dichloromethane, methanol, diethyl ether or pentane or a combination of at least two thereof; typical but non-limiting combinations include acetone and ethanol, ethanol and dichloromethane, dichloromethane and methanol, methanol and diethyl ether, diethyl ether and pentane, ethanol, dichloromethane and methanol, dichloromethane, methanol and diethyl ether, methanol, diethyl ether and pentane, or water, acetone, ethanol, dichloromethane, methanol, diethyl ether and pentane.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method provided by the invention can not only ensure the bonding strength between the diaphragm and the anode and/or the cathode, but also ensure the lithium ion permeability of the diaphragm;
(2) the invention adopts the extrusion printing method to set the glue coating layer, and can realize the rapid printing and coating operation by continuously and rapidly repeating the process of moving the spray head and extruding the slurry from the spray head; moreover, the shape of the gluing point can be changed by changing the shape of the spray head, so that the specific identification can be carried out on the battery;
(3) the diaphragm obtained by the method has good wettability, the resistance value of the battery obtained by using the diaphragm is reduced, and the cycle performance is obviously improved.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a method for arranging a diaphragm rubberized layer, which comprises the following steps:
extruding the gluing slurry at intervals on the surface of the diaphragm substrate to complete the setting of the diaphragm gluing layer;
the distance of the gap is 60 mm; the single-point gluing amount of the extrusion is 0.8g/m2The extrusion speed was 50 mm/s.
The gluing sizing agent comprises the following components in percentage by mass: 50 wt% of polymer, 12 wt% of surfactant and the balance of gelatinizing solvent.
The polymer is polymethyl methacrylate with the number average molecular weight of 30000; the surfactant is a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer with the number average molecular weight of 6000; the gluing solvent is water.
The gluing sizing agent also comprises 5 wt% of a viscosity regulator, and the viscosity regulator is glycerol.
The gluing slurry is prepared by the following method: mixing a polymer, a surfactant, a viscosity regulator and a solvent according to the formula ratio to obtain a mixture, and carrying out ultrasonic treatment on the mixture for 4 hours to uniformly mix the mixture to obtain the gluing slurry.
Example 2
The embodiment provides a method for arranging a diaphragm rubberized layer, which comprises the following steps:
extruding the gluing slurry at intervals on the surface of the diaphragm substrate to complete the setting of the diaphragm gluing layer;
the distance of the gap is 50 mm; the single-point gluing amount of the extrusion is 0.4g/m2The extrusion speed was 30 mm/s.
The gluing sizing agent comprises the following components in percentage by mass: 40 wt% of polymer, 15 wt% of surfactant and the balance of gluing solvent.
The polymer is polymethyl methacrylate with the number average molecular weight of 10000; the surfactant is a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer with the number average molecular weight of 3000; the gluing solvent is water.
The gluing sizing agent also comprises 5 wt% of a viscosity regulator, and the viscosity regulator is ethylene glycol.
The gluing slurry is prepared by the following method: mixing a polymer, a surfactant, a viscosity regulator and a solvent according to the formula ratio to obtain a mixture, and carrying out ultrasonic treatment on the mixture for 2 hours to uniformly mix the mixture to obtain the gluing slurry.
Example 3
The embodiment provides a method for arranging a diaphragm rubberized layer, which comprises the following steps:
extruding the gluing slurry at intervals on the surface of the diaphragm substrate to complete the setting of the diaphragm gluing layer;
the distance of the gap is 70 mm; the single-point gluing amount of the extrusion is 1.2g/m2The extrusion speed was 60 mm/s.
The gluing sizing agent comprises the following components in percentage by mass: 60 wt% of polymer, 10 wt% of surfactant and the balance of gluing solvent.
The polymer is polymethyl methacrylate with the number average molecular weight of 50000; the surfactant is a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer with the number average molecular weight of 10000; the gluing solvent is water.
The gluing sizing agent also comprises 5 wt% of a viscosity regulator, and the viscosity regulator is ethylene glycol.
The gluing slurry is prepared by the following method: mixing a polymer, a surfactant, a viscosity regulator and a solvent according to the formula ratio to obtain a mixture, and carrying out ultrasonic treatment on the mixture for 6 hours to uniformly mix the mixture to obtain the gluing slurry.
Example 4
The embodiment provides a method for arranging a diaphragm rubberized layer, which comprises the following steps:
extruding the gluing slurry at intervals on the surface of the diaphragm substrate to complete the setting of the diaphragm gluing layer;
the distance of the gap is 40 mm; the single-point gluing amount of the extrusion is 0.1g/m2The extrusion speed was 20 mm/s.
The gluing sizing agent comprises the following components in percentage by mass: 30 wt% of polymer, 20 wt% of surfactant and the balance of gluing solvent.
The polymer is polymethyl methacrylate with the number average molecular weight of 30000; the surfactant is a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer with the number average molecular weight of 6000; the gluing solvent is water.
The gluing sizing agent also comprises 10 wt% of a viscosity regulator, and the viscosity regulator is ethylene glycol.
The gluing slurry is prepared by the following method: mixing a polymer, a surfactant, a viscosity regulator and a solvent according to the formula ratio to obtain a mixture, and carrying out ultrasonic treatment for 3 hours to uniformly mix the mixture to obtain the gluing slurry.
Example 5
The embodiment provides a method for arranging a diaphragm rubberized layer, which comprises the following steps:
extruding the gluing slurry at intervals on the surface of the diaphragm substrate to complete the setting of the diaphragm gluing layer;
the distance of the gap is 80 mm; the single-point gluing amount of the extrusion is 1.5g/m2The extrusion speed was 80 mm/s.
The gluing sizing agent comprises the following components in percentage by mass: 80 wt% of polymer, 5 wt% of surfactant and the balance of gluing solvent.
The polymer is polymethyl methacrylate with the number average molecular weight of 30000; the surfactant is a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer with the number average molecular weight of 6000; the gluing solvent is water.
The gluing sizing agent also comprises 0.01 wt% of viscosity regulator, and the viscosity regulator is glycerol.
The gluing slurry is prepared by the following method: mixing a polymer, a surfactant, a viscosity regulator and a solvent according to the formula ratio to obtain a mixture, and carrying out ultrasonic treatment on the mixture for 5 hours to uniformly mix the mixture to obtain the gluing slurry.
Example 6
The embodiment provides a method for arranging a diaphragm rubberized layer, which comprises the following steps:
extruding the gluing slurry at intervals on the surface of the diaphragm substrate to complete the setting of the diaphragm gluing layer;
the distance of the gap is 60 mm; the single-point gluing amount of the extrusion is 0.8g/m2The extrusion speed was 50 mm/s.
The gluing sizing agent comprises the following components in percentage by mass: 50 wt% of polymer, 12 wt% of surfactant and the balance of gelatinizing solvent.
The polymer is carboxymethyl cellulose with the number average molecular weight of 10000; the surfactant is polyoxyethylene octyl phenol ether-10 with the number average molecular weight of 3000; the gluing solvent is ethanol.
The gluing sizing agent also comprises 5 wt% of a viscosity regulator, and the viscosity regulator is glycerol.
The gluing slurry is prepared by the following method: mixing a polymer, a surfactant, a viscosity regulator and a solvent according to the formula ratio to obtain a mixture, and carrying out ultrasonic treatment on the mixture for 4 hours to uniformly mix the mixture to obtain the gluing slurry.
Example 7
The embodiment provides a method for arranging a diaphragm rubberized layer, which comprises the following steps:
extruding the gluing slurry at intervals on the surface of the diaphragm substrate to complete the setting of the diaphragm gluing layer;
the distance of the gap is 60 mm; the single-point gluing amount of the extrusion is 0.8g/m2The extrusion speed was 50 mm/s.
The gluing sizing agent comprises the following components in percentage by mass: 50 wt% of polymer, 12 wt% of surfactant and the balance of gelatinizing solvent.
The polymer is polyoxyethylene with the number average molecular weight of 20000; the surfactant is polyoxyethylene cetyl ether with the number average molecular weight of 5000; the gluing solvent is diethyl ether.
The gluing sizing agent also comprises 5 wt% of a viscosity regulator, and the viscosity regulator is glycerol.
The gluing slurry is prepared by the following method: mixing a polymer, a surfactant, a viscosity regulator and a solvent according to the formula ratio to obtain a mixture, and carrying out ultrasonic treatment on the mixture for 4 hours to uniformly mix the mixture to obtain the gluing slurry.
Example 8
Compared with the method in the embodiment 1, the diaphragm substrate in the embodiment is provided with the ceramic coating, and the thickness of the ceramic coating is 20 μm.
The ceramic slurry used for the ceramic coating comprises the following components in percentage by mass: 55 wt% of ceramic material, 12 wt% of binder and the balance of coating solvent.
The ceramic material is boehmite with the average grain diameter of 5 mu m, the binding agent is carboxymethyl cellulose with the number average molecular weight of 10000, and the coating solvent is water.
Example 9
Compared with the method in the embodiment 1, the diaphragm substrate in the embodiment is provided with the ceramic coating, and the thickness of the ceramic coating is 20 μm.
The ceramic slurry used for the ceramic coating comprises the following components in percentage by mass: 50 wt% of ceramic material, 15 wt% of binder and the balance of coating solvent.
The ceramic material is boehmite with the average grain diameter of 1 mu m, the binder is polyvinylidene fluoride with the number average molecular weight of 30000, and the coating solvent is water.
Example 10
Compared with the method in the embodiment 1, the diaphragm substrate in the embodiment is provided with the ceramic coating, and the thickness of the ceramic coating is 20 μm.
The ceramic slurry used for the ceramic coating comprises the following components in percentage by mass: 60 wt% of ceramic material, 10 wt% of binder and the balance of coating solvent.
The ceramic material is boehmite with the average grain diameter of 10 mu m, the binder is polyimide with the number average molecular weight of 50000, and the coating solvent is water.
Example 11
Compared with the method in the embodiment 1, the diaphragm substrate in the embodiment is provided with the ceramic coating, and the thickness of the ceramic coating is 5 μm.
The ceramic slurry used for the ceramic coating comprises the following components in percentage by mass: 40 wt% of ceramic material, 20 wt% of binder and the balance of coating solvent.
The ceramic material is alumina with the average grain diameter of 3 mu m, the binder is styrene butadiene rubber with the number average molecular weight of 30000, and the coating solvent is acetone.
Example 12
This example provides a method for providing a rubber-coated layer of a separator, and compared to example 1, the separator substrate of this example is a separator substrate provided with a ceramic coating having a thickness of 40 μm.
The ceramic slurry used for the ceramic coating comprises the following components in percentage by mass: 70 wt% of ceramic material, 5 wt% of binder and the balance of coating solvent.
The ceramic material is titanium oxide with the average grain diameter of 8 mu m, the binder is polyethylene with the number average molecular weight of 30000, and the coating solvent is diethyl ether.
Comparative example 1
This comparative example provides a method of laying a membrane rubberized layer, similar to example 1, except that the spacing is 30mm, compared to example 1.
Comparative example 2
This comparative example provides a method of laying a membrane rubberized layer, similar to example 1, except that the spacing is 90mm, compared to example 1.
Comparative example 3
This comparative example provides a method for applying a glue layer to a membrane, compared with example 1, except that the glue amount at a single point is 0.08g/m2Otherwise, the same procedure as in example 1 was repeated.
Comparative example 4
This comparative example provides a method for applying a glue layer to a membrane, compared to example 1, except that the glue amount at a single point is 1.8g/m2Otherwise, the same procedure as in example 1 was repeated.
The separators provided with rubber coated layers provided in examples 1 to 12 and comparative examples 1 to 4 were tested for coating peel force and air permeability, the coating peel force test method: firstly, cutting a rubber-coated membrane sample strip with a specific width; then, a double-sided adhesive tape is adhered to the upper end of the steel plate, the coating surface of the membrane sample strip is adhered to the adhesive tape, the membrane is parallel to the edge of the steel plate, the lower end of the steel plate is fixed on a lower clamp, and the end, not adhered with the adhesive tape, of the sample strip to be measured is fixed in an upper clamp; then starting a tensile testing machine, and reading the average peeling force after the sample is peeled off at a specific tensile rate;
the method for testing the air permeability comprises the following steps: cutting a membrane sample strip with a glue coating layer in a specific size, placing a sample in a testing area of a Wang research type air permeability tester, starting a button to start testing, and reading a numerical value after the testing is finished; the results obtained are shown in table 1.
TABLE 1
In conclusion, the method provided by the invention can not only ensure the bonding strength between the diaphragm and the anode and/or the cathode, but also ensure the lithium ion permeability of the diaphragm; the invention adopts the extrusion printing method to set the glue coating layer, and can realize the rapid printing and coating operation by continuously and rapidly repeating the process of moving the spray head and extruding the slurry from the spray head; moreover, the shape of the gluing point can be changed by changing the shape of the spray head, so that the specific identification can be carried out on the battery; the diaphragm obtained by the method has good wettability, the resistance value of the battery obtained by using the diaphragm is reduced, and the cycle performance is obviously improved.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method of providing a membrane rubberized layer, said method comprising the steps of:
extruding the gluing slurry at intervals on the surface of the diaphragm substrate to complete the setting of the diaphragm gluing layer;
the distance of the interval is 40-80 mm; the single-point gluing amount of the extrusion is 0.1-1.5g/m2。
2. The method of claim 1, wherein the speed of extrusion is 20-80 mm/s.
3. The method according to claim 1 or 2, characterized in that the gumming paste comprises, in mass percent:
30-80 wt% of polymer
5-20 wt% of surfactant
The balance being the gluing solvent.
4. The method of claim 3, wherein the polymer comprises any one of or a combination of at least two of carboxymethyl cellulose, polymethyl methacrylate, polyimide, or polyethylene oxide;
preferably, the number average molecular weight of the polymer is 10000-.
5. The method of claim 3 or 4, wherein the surfactant comprises any one of polyoxyethylene cetyl ether, polyoxyethylene octylphenol ether-10, or a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, or a combination of at least two thereof;
preferably, the number average molecular weight of the surfactant is 3000-10000.
6. A method according to any one of claims 3 to 5, wherein the gumming solvent comprises any one of, or a combination of at least two of, water, acetone, ethanol, dichloromethane, methanol, diethyl ether or pentane.
7. The method according to any one of claims 3 to 6, wherein the gumming slurry further comprises 0.01 to 10 wt% of a viscosity modifier;
preferably, the viscosity modifier comprises ethylene glycol and/or glycerol.
8. A method according to any one of claims 3-7, characterized in that the gumming slurry is prepared by a method comprising:
mixing a polymer, a surfactant and a gluing solvent according to a formula ratio to obtain a mixture, and treating the mixture by ultrasonic waves to uniformly mix the mixture to obtain the gluing slurry;
preferably, the mixture also comprises a viscosity regulator;
preferably, the time of the ultrasonic treatment is 2-6 h.
9. The method according to any one of claims 1 to 8, wherein the separator substrate is a separator substrate provided with a ceramic coating;
preferably, the thickness of the ceramic coating is 5-40 μm;
preferably, the ceramic slurry for the ceramic coating comprises the following components in percentage by mass:
40-70 wt% of ceramic material
5-20 wt% of binder
The balance being coating solvent.
10. The method according to claim 9, wherein the ceramic material has an average particle size of 1-10 μm;
preferably, the ceramic material comprises any one of silica, alumina, boehmite, magnesia, titania or zinc oxide or a combination of at least two thereof;
preferably, the binder comprises any one of or a combination of at least two of carboxymethyl cellulose, polyvinylidene fluoride, styrene-butadiene rubber, polyimide or polyethylene;
preferably, the number average molecular weight of the binder is 10000-;
preferably, the coating solvent comprises any one of water, acetone, ethanol, dichloromethane, methanol, diethyl ether or pentane or a combination of at least two thereof.
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