WO2024021018A1 - 干法电极用底涂胶及其制备方法、复合集流体、电池极片、二次电池、电池模块、电池包和用电装置 - Google Patents
干法电极用底涂胶及其制备方法、复合集流体、电池极片、二次电池、电池模块、电池包和用电装置 Download PDFInfo
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- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical class [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical class [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J135/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J135/06—Copolymers with vinyl aromatic monomers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/668—Composites of electroconductive material and synthetic resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/33—Applications of adhesives in processes or use of adhesives in the form of films or foils for batteries or fuel cells
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2423/00—Presence of polyolefin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2451/00—Presence of graft polymer
-
- 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
Definitions
- This application relates to the technical field of lithium batteries, and in particular to a primer glue for dry electrodes and a composite current collector including the primer glue for dry electrodes, battery pole pieces, secondary batteries, battery modules, battery packs and electricity consumption. device.
- lithium-ion batteries are widely used in energy storage power systems such as hydraulic, thermal, wind and solar power stations, as well as power tools, electric bicycles, electric motorcycles, electric vehicles, Military equipment, aerospace and other fields. Due to the great development of lithium-ion batteries, higher requirements have been put forward for their energy density, cycle performance and safety performance.
- This application was made in view of the above problems, and its purpose is to provide a primer for dry electrodes that improves the adhesion between the dry electrode film layer and the current collector, and at the same time reduces the volume resistivity of the battery pole piece. , and provide a method for preparing the above-mentioned primer glue for dry electrodes, as well as a composite current collector, battery pole piece, secondary battery, battery module, battery pack and electrical device including the primer glue for dry electrodes.
- the first aspect of the present application provides a primer glue for dry electrodes
- the primer glue includes the following components in parts by mass:
- the modified polyolefin resin is a copolymer obtained by polymerizing maleic anhydride, polyolefin and petroleum resin.
- the primer glue for dry electrodes of the present application can effectively improve the adhesion between the dry electrode film layer and the current collector, and in particular, can effectively improve the drying process under long-term immersion in electrolyte. It improves the adhesion between the electrode film layer and the current collector, and also reduces the volume resistivity of the battery pole piece.
- the primer for dry electrodes includes the following components in parts by mass:
- the adhesion between the dry electrode film layer and the current collector can be further improved, while the volume resistance of the battery pole pieces can be further reduced. Rate.
- the weight average molecular weight of the modified polyolefin resin is 1 million to 1.5 million. By regulating the weight average molecular weight of the modified polyolefin resin, the adhesion between the dry electrode film layer and the current collector can be further improved.
- the polyolefin is selected from one or more of the following: polyethylene, polypropylene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-ethylene-butylene -Styrene block copolymer, styrene-isoprene-styrene block copolymer and amorphous polyalpha olefin resin, optionally, the polyolefin is selected from one or more of the following: poly Ethylene, polypropylene, ethylene-vinyl acetate copolymer and styrene-ethylene-butylene-styrene block copolymer.
- polyolefin By selecting polyolefin, the adhesion between the dry electrode film layer and the current collector can be further improved.
- the conductive material is a carbon material selected from one or more of the following: carbon black, graphene, carbon nanotubes, graphite, and mesophase carbon microspheres.
- the mass ratio of the modified polyolefin resin to the conductive material is 0.8-1.7:1, optionally 1-1.4:1.
- the maleic anhydride, polyolefin and petroleum resin in the modified polyolefin resin satisfy the following formula:
- a1 is the mass percentage of maleic anhydride in the modified polyolefin resin
- a2 is the mass percentage of polyolefin in the modified polyolefin resin
- a3 is the mass percentage of petroleum resin in the modified polyolefin resin.
- the primer for dry electrodes further includes 0.1-1 parts by mass, optionally 0.2-0.5 parts by mass of additives, and the additives include antioxidants and anti-aging agents.
- the selection and regulation of the additives can improve the thermal stability and production time storage properties of the primer.
- the primer for dry electrodes further includes 1-10 parts by mass of paraffin wax.
- the paraffin wax can improve the adhesion of the primer glue.
- the second aspect of the present application provides a method for preparing primer glue for dry electrodes of the first aspect, including
- the preparation of the modified polyolefin resin includes copolymerizing maleic anhydride, polyolefin and petroleum resin at 150-180°C to obtain the modified polyolefin resin.
- the primer for dry electrodes of the present application can be produced.
- a third aspect of the present application provides a composite current collector.
- the composite current collector includes an undercoating layer.
- the undercoating layer is disposed on at least one surface of the current collector.
- the undercoating layer is on the current collector.
- the thickness on one surface is 1-10 ⁇ m, optionally 5-8 ⁇ m, and the primer layer is coated with the dry electrode primer according to the first aspect of the present application.
- the fourth aspect of the application provides a battery pole piece, which includes the composite current collector of the third aspect of the application; and a dry electrode film layer, the dry film layer is disposed in the composite current collector. on top of the primer layer.
- a fifth aspect of the present application provides a secondary battery, which includes the battery pole piece of the fourth aspect of the present application.
- a sixth aspect of the present application provides a battery module including the secondary battery of the fifth aspect of the present application.
- a seventh aspect of the present application provides a battery pack, which includes the battery module of the sixth aspect of the present application.
- An eighth aspect of the present application provides an electrical device, which includes at least one selected from the group consisting of the secondary battery of the fifth aspect of the present application, the battery module of the sixth aspect of the present application, or the battery pack of the seventh aspect of the present application. A sort of.
- the battery modules, battery packs and electrical devices of the present application include the secondary battery provided by the present application, and therefore have at least the same advantages as the secondary battery.
- FIG. 1 is a schematic diagram of a secondary battery according to an embodiment of the present application.
- FIG. 2 is an exploded view of the secondary battery according to the embodiment of the present application shown in FIG. 1 .
- FIG. 3 is a schematic diagram of a battery module according to an embodiment of the present application.
- Figure 4 is a schematic diagram of a battery pack according to an embodiment of the present application.
- FIG. 5 is an exploded view of the battery pack according to an embodiment of the present application shown in FIG. 4 .
- FIG. 6 is a schematic diagram of a power consumption device using a secondary battery as a power source according to an embodiment of the present application.
- the primer glue for dry electrodes of the present application and the composite current collector, battery pole piece, secondary battery, battery module, battery pack and electrical device including the primer will be specifically disclosed in detail with appropriate reference to the drawings. implementation. However, unnecessary detailed explanations may be omitted. For example, detailed descriptions of well-known matters may be omitted, or descriptions of substantially the same structure may be repeated. This is to prevent the following description from becoming unnecessarily lengthy and to facilitate understanding by those skilled in the art. In addition, the drawings and the following description are provided for those skilled in the art to fully understand the present application, and are not intended to limit the subject matter described in the claims.
- Ranges disclosed herein are defined in terms of lower and upper limits. A given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive of the endpoints, and may be arbitrarily combined, that is, any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, understand that ranges of 60-110 and 80-120 are also expected. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-5.
- the numerical range “a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
- the numerical range “0-5" means that all real numbers between "0-5" have been listed in this article, and "0-5" is just an abbreviation of these numerical combinations.
- a certain parameter is an integer ⁇ 2
- the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially.
- step (c) means that step (c) may be added to the method in any order.
- the method may include steps (a), (b) and (c). , may also include steps (a), (c) and (b), may also include steps (c), (a) and (b), etc.
- condition "A or B” is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists) ; Or both A and B are true (or exist).
- the preparation of electrode sheets by dry technology is a new lithium battery preparation process.
- the dry electrode processing technology has the following advantages: 1) It can streamline the two processes of homogenization and electrode sheet baking, reduce the area occupied by the electrode workshop and reduce the equipment cost. Direct investment reduces equipment and factory construction investment costs. 2) Since there is no need for NMP solvents, it saves raw material costs and is conducive to environmental safety, reducing environmental management and control operating costs. 3) Dry electrode sheets can produce thick electrodes, which are flexible and safe. It has high performance and is expected to be used in the development of pre-lithium and solid-state battery technologies.
- Patent CN106654177A proposes mixing and shearing an easily fiberized binder with an active material and a conductive agent at high speed, rolling it through a roller press multiple times, and then compounding it with a current collector with a conductive adhesive layer to prepare a dry electrode sheet.
- This process does not use a large amount of organic solvents, which is beneficial to extending the capacity and cycle life of the battery.
- the conductive adhesive layer coated on the surface of the current collector is 98-99.5% of the conductive agent and 0.5-2% of the total mass of the conductive adhesive.
- the conductive adhesive layer contains a large amount of conductive agent, the adhesive force between the dry film layer and the current collector is poor.
- the internal resistance of the battery cell will also cause the electrode film to peel off and powder to shake during the use of the battery, seriously affecting the service life and safety performance of the battery.
- the first aspect of this application provides a primer for dry electrodes.
- the primer includes the following components in parts by mass:
- the modified polyolefin resin is a copolymer obtained by polymerizing maleic anhydride, polyolefin and petroleum resin.
- the primer for dry electrodes of the present application can improve the adhesion between the dry electrode film layer and the current collector, and at the same time reduce the internal stress of the entire battery pole piece. block.
- the modified polyolefin resin is a copolymer of maleic anhydride, polyolefin and petroleum resin, which is further improved by introducing maleic anhydride with polar functionality into the polyolefin.
- the polarity of the molecular chain segments can improve the adhesion between the dry electrode film layer and the current collector, especially the adhesion between the dry electrode film layer and the current collector under long-term immersion in electrolyte.
- the uniformly dispersed conductive material is conducive to electron transmission, which can effectively avoid the deterioration of battery performance caused by electrode film peeling, dust shaking, etc. during battery use.
- the primer for dry electrodes includes the following components in parts by mass:
- the adhesion between the dry electrode film layer and the current collector can be further improved, while the volume resistance of the battery pole pieces can be further reduced. Rate. If the content of modified polyolefin resin is too much, the conductive material will be too dispersed in the primer system, which is not conducive to the transmission of electrons in the pole piece; and if the content of modified polyolefin is too small, the pole piece film layer will be The reduced bonding force between current collectors can easily cause the electrode film layer to fall off during battery use, affecting the service life and safety performance of the battery.
- the modified polyolefin resin has a weight average molecular weight of 1 million to 1.5 million. By regulating the weight average molecular weight of the modified polyolefin resin, the adhesion between the dry electrode film layer and the current collector can be further improved.
- the polyolefin is selected from one or more of the following: polyethylene, polypropylene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-ethylene-butylene -Styrene block copolymer, styrene-isoprene-styrene block copolymer and amorphous polyalpha olefin resin, optionally, the polyolefin is selected from one or more of the following: poly Ethylene, polypropylene, ethylene-vinyl acetate copolymer and styrene-ethylene-butylene-styrene block copolymer.
- polyolefin By selecting polyolefin, the adhesion between the dry electrode film layer and the current collector can be further improved.
- the conductive material is a carbon material selected from one or more of the following: carbon black, graphene, carbon nanotubes, graphite, and mesophase carbon microspheres.
- carbon black carbon black
- graphene carbon nanotubes
- graphite graphite
- mesophase carbon microspheres the volume resistivity of the battery pole pieces.
- the shape of the conductive material may be granular, fibrous, sheet, etc.
- the Dv50 of the conductive material is 20 nm, and the D50 is the particle size corresponding to when the cumulative volume distribution percentage of the sample reaches 50%.
- the mass ratio of the modified polyolefin resin to the conductive material is 0.8-1.7:1, optionally 1-1.4:1, for example, it can be 1:1, 1.1:1, 1.2: 1, 1.3:1 or 1.4:1, but not limited to the listed pip values.
- the weight ratio of the modified polyolefin resin to the conductive material meets the above range, the adhesion between the dry electrode film layer and the current collector can be further improved, while the volume resistivity of the battery pole piece can be further reduced.
- the conductive material will be too dispersed in the primer system, which is not conducive to the transmission of electrons in the pole piece; and if the content of modified polyolefin is too small, the pole piece film layer will be The reduced bonding force between current collectors can easily cause the electrode film layer to fall off during battery use, affecting the service life and safety performance of the battery.
- the maleic anhydride, polyolefin and petroleum resin in the modified polyolefin resin satisfy the following formula:
- a1 is the mass percentage of maleic anhydride in the modified polyolefin resin
- a2 is the mass percentage of polyolefin in the modified polyolefin resin
- a3 is the mass percentage of petroleum resin in the modified polyolefin resin.
- Modified polyolefin resin further increases the polarity of the molecular chain segments by introducing maleic anhydride with polar functionality into the polyolefin, thereby improving the adhesion between the dry electrode film layer and the current collector.
- the adhesive force between the dry electrode film layer and the current collector can be further improved.
- the primer for dry electrodes also includes 0.1-1 parts by mass, optionally 0.2-0.5 parts by mass of additives, such as 0.2, 0.3, 0.4 or 0.5 parts by mass, etc., but not
- additives include antioxidants and anti-aging agents, limited to the values listed, as long as values within the above ranges are equally applicable.
- the selection and regulation of the additives can improve the thermal stability and long-term storage properties of the primer and prevent the primer from carbonizing or aging at high temperatures and affecting its performance.
- the primer for dry electrodes also includes 1-10 parts by mass of paraffin wax, for example, it can be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 parts by mass, etc. , but not limited to the listed point values, as long as the values are within the above range, the same applies.
- the paraffin wax can improve the adhesiveness of the primer and is beneficial to improving the adhesive force between the dry electrode film layer and the current collector.
- the second aspect of the present application provides a method for preparing primer glue for dry electrodes of the first aspect, including
- the preparation of modified polyolefin resin includes copolymerizing maleic anhydride, polyolefin and petroleum resin at 150-180°C, such as 150°C, 160°C, 170°C or 180°C, etc., but It is not limited to the listed point values, as long as the values are within the above range, the same applies, and the modified polyolefin resin is obtained.
- a third aspect of the present application provides a composite current collector.
- the composite current collector includes an undercoating layer.
- the undercoating layer is disposed on at least one surface of the current collector.
- the undercoating layer is disposed on the current collector.
- the thickness on one surface of the fluid is 1-10 ⁇ m, optionally 5-8 ⁇ m, for example, the thickness can be 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m or 10 ⁇ m, etc., but is not limited to the listed point values, as long as it is within the above range The numerical value of is also applicable.
- the primer layer is coated with the dry electrode primer according to the first aspect of the present application.
- the current collector may be a metal foil, such as aluminum foil or copper foil.
- the current collector may also be a current collector that includes a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer, which can be made by adding a metal material (aluminum, aluminum alloy, copper, copper alloy nickel, nickel alloy , titanium, titanium alloys, silver and silver alloys, etc.) are formed on polymer material substrates (such as polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate ( PBT), polystyrene (PS), polyethylene (PE), etc.).
- PP polypropylene
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- PS polystyrene
- PE polyethylene
- the fourth aspect of the application provides a battery pole piece, which includes the composite current collector of the third aspect of the application; and a dry electrode film layer, the dry film layer is disposed in the composite current collector. on top of the primer layer.
- the battery pole piece is made by laminating the composite current collector of the third aspect of the present application and the dry electrode film layer through a hot pressing process, wherein the temperature of the hot pressing process is 120-180 °C, for example, can be 120°C, 130°C, 140°C, 150°C, 160°C, 170°C or 180°C, etc., but is not limited to the listed point values, and any value within the above range is also applicable.
- the dry electrode film layer is prepared by methods known to those skilled in the art, such as the dry electrode film layer disclosed in patent CN106654177A.
- a fifth aspect of the present application provides a secondary battery, which includes the battery pole piece of the fourth aspect of the present application.
- a sixth aspect of the present application provides a battery module including the secondary battery of the fifth aspect of the present application.
- a seventh aspect of the present application provides a battery pack, which includes the battery module of the sixth aspect of the present application.
- An eighth aspect of the present application provides an electrical device, which includes at least one selected from the group consisting of the secondary battery of the fifth aspect of the present application, the battery module of the sixth aspect of the present application, or the battery pack of the seventh aspect of the present application. A sort of.
- a secondary battery is provided.
- a secondary battery typically includes a positive electrode plate, a negative electrode plate, an electrolyte and a separator.
- active ions are inserted and detached back and forth between the positive and negative electrodes.
- the electrolyte plays a role in conducting ions between the positive and negative electrodes.
- the isolation film is placed between the positive electrode piece and the negative electrode piece. It mainly prevents the positive and negative electrodes from short-circuiting and allows ions to pass through.
- the positive electrode sheet includes the positive electrode composite current collector of the present application and a positive electrode film layer disposed on at least one surface of the positive electrode composite current collector.
- the positive electrode composite current collector includes a primer layer, which is disposed on at least one surface of the current collector.
- the thickness of the primer layer on one surface of the current collector is 1-10 ⁇ m, optional. is 5-8 ⁇ m, for example, the thickness can be 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m or 10 ⁇ m, etc., but is not limited to the listed point values. As long as the value is within the above range, the same applies.
- the base coating layer adopts this application
- the dry electrode is coated with primer glue.
- the current collector may be a metal foil, such as an aluminum foil, or may be a current collector including a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer, which can be made by adding the metal material (Aluminum, aluminum alloy, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) are formed on polymer material substrates (such as polypropylene (PP), polyethylene terephthalate (PET), polyparaethylene It is formed on a base material such as butylene phthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
- PP polypropylene
- PET polyethylene terephthalate
- PBT polystyrene
- PE polyethylene
- a metal foil such as aluminum foil has two surfaces opposite in its own thickness direction, which can be provided with a primer layer on any one or both of them, and a positive electrode film layer is provided on two opposite sides of the metal foil. On one of the surfaces that has a primer on it.
- the cathode active material may be a cathode active material known in the art for batteries.
- the cathode active material may include at least one of the following materials: an olivine-structured lithium-containing phosphate, a lithium transition metal oxide, and their respective modified compounds.
- the present application is not limited to these materials, and other traditional materials that can be used as positive electrode active materials of batteries can also be used. Only one type of these positive electrode active materials may be used alone, or two or more types may be used in combination.
- lithium transition metal oxides may include, but are not limited to, lithium cobalt oxides (such as LiCoO 2 ), lithium nickel oxides (such as LiNiO 2 ), lithium manganese oxides (such as LiMnO 2 , LiMn 2 O 4 ), lithium Nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (such as LiNi 1/3 Co 1/3 Mn 1/3 O 2 (also referred to as NCM 333 ), LiNi 0.5 Co 0.2 Mn 0.3 O 2 (can also be abbreviated to NCM 523 ), LiNi 0.5 Co 0.25 Mn 0.25 O 2 (can also be abbreviated to NCM 211 ), LiNi 0.6 Co 0.2 Mn 0.2 O 2 (can also be abbreviated to NCM 622 ), LiNi At least one of 0.8 Co 0.1 Mn 0.1 O 2 (also referred to as NCM 811 ), lithium nickel cobalt aluminum oxide (such as Li Li
- the olivine structure contains Examples of lithium phosphates may include, but are not limited to, lithium iron phosphate (such as LiFePO 4 (also referred to as LFP)), composites of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO 4 ), lithium manganese phosphate and carbon. At least one of composite materials, lithium iron manganese phosphate, and composite materials of lithium iron manganese phosphate and carbon.
- lithium iron phosphate such as LiFePO 4 (also referred to as LFP)
- composites of lithium iron phosphate and carbon such as LiMnPO 4
- LiMnPO 4 lithium manganese phosphate and carbon.
- At least one of composite materials, lithium iron manganese phosphate, and composite materials of lithium iron manganese phosphate and carbon At least one of composite materials, lithium iron manganese phosphate, and composite materials of lithium iron manganese phosphate and carbon.
- the positive electrode membrane layer further includes a fiberizable binder.
- the binder may include fiberizable polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber, polypropylene, polyethylene, and ethylene vinyl acetate (EVA). At least one.
- the positive electrode film layer optionally further includes a conductive agent.
- the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
- the mass ratio of the cathode active material, conductive agent and fiberizable binder in the cathode film layer is 70-90:5-10:3-10.
- the dry cathode film layer can be prepared by mixing the above-mentioned components for preparing the cathode film layer, such as cathode active material, conductive agent, fiberizable binder and any other components. Perform fiberization treatment to obtain a highly fiberized mixed material, and then roll the mixed material to obtain a continuous self-supporting dry positive electrode membrane layer.
- components for preparing the cathode film layer such as cathode active material, conductive agent, fiberizable binder and any other components.
- the positive electrode sheet can be obtained by laminating the positive electrode composite current collector and the dry positive electrode film layer through a hot pressing process, where the temperature of the hot pressing process is 120-180°C.
- the negative electrode sheet includes the negative electrode composite current collector of the present application and a negative electrode film layer disposed on at least one surface of the negative electrode composite current collector.
- the negative electrode composite current collector includes a primer layer, which is disposed on at least one surface of the current collector.
- the thickness of the primer layer on one surface of the current collector is 1-10 ⁇ m, optional. is 5-8 ⁇ m, for example, the thickness can be 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m or 10 ⁇ m, etc., but is not limited to the listed point values. As long as the value is within the above range, the same applies.
- the base coating layer adopts this application
- the dry electrode is coated with primer glue.
- the current collector may be a metal foil, such as a copper foil, or may be a current collector including a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer, which can be made by adding metal Materials (copper, copper alloy, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) are formed on polymer material substrates (such as polypropylene (PP), polyethylene terephthalate (PET), poly It is formed on base materials such as butylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
- PP polypropylene
- PET polyethylene terephthalate
- base materials such as butylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.
- a metal foil such as copper foil has two surfaces opposite in its own thickness direction, which can be provided with a primer layer on either or both of them, and the positive electrode film layer is provided on the opposite side of the metal foil. On the surface with primer glue on one of the two surfaces.
- the negative active material may be a negative active material known in the art for batteries.
- the negative active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, and the like.
- the silicon-based material may be selected from at least one of elemental silicon, silicon oxide compounds, silicon carbon composites, silicon nitrogen composites and silicon alloys.
- the tin-based material may be selected from at least one of elemental tin, tin oxide compounds and tin alloys.
- the present application is not limited to these materials, and other traditional materials that can be used as battery negative electrode active materials can also be used.
- the negative electrode active material may have an average particle diameter (D 50 ) of 12 ⁇ m to 22 ⁇ m, where the D 50 is the particle diameter corresponding to when the cumulative volume distribution percentage of the sample reaches 50%.
- the positive electrode film layer also includes a fiberizable binder.
- the binder may include fiberizable polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber, polypropylene, polyethylene, and ethylene vinyl acetate (EVA). At least one.
- the negative electrode film layer optionally further includes a conductive agent.
- the conductive agent may be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
- the negative electrode film layer optionally includes other auxiliaries, such as thickeners (such as sodium carboxymethylcellulose (CMC-Na)) and the like.
- thickeners such as sodium carboxymethylcellulose (CMC-Na)
- the mass ratio of the negative active material, conductive agent and fiberizable binder in the negative electrode film layer is 70-90:5-10:3-10.
- the dry negative electrode film layer can be prepared by: using the above-mentioned components for preparing the negative electrode film layer, such as negative active material, conductive agent, fiberizable binder and any other components. Fibrization treatment is performed to obtain a highly fibrous mixed material, and then the mixed material is rolled to obtain a continuous self-supporting dry negative electrode film layer.
- a negative electrode sheet can be obtained by laminating the negative electrode composite current collector and the dry negative electrode film layer through a hot pressing process, where the temperature of the hot pressing process is 120-180°C.
- the electrolyte plays a role in conducting ions between the positive and negative electrodes.
- the type of electrolyte in this application can be selected according to needs.
- the electrolyte can be liquid, gel, or completely solid.
- the electrolyte is an electrolyte solution.
- the electrolyte solution includes electrolyte salts and solvents.
- the electrolyte salt may be selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bisfluorosulfonimide, lithium bistrifluoromethanesulfonimide, trifluoromethane At least one of lithium sulfonate, lithium difluorophosphate, lithium difluoroborate, lithium dioxaloborate, lithium difluorodioxalate phosphate and lithium tetrafluoroxalate phosphate.
- the solvent may be selected from the group consisting of ethylene carbonate, propylene carbonate, methylethyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, Butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate At least one of ester, 1,4-butyrolactone, sulfolane, dimethyl sulfone, methyl ethyl sulfone and diethyl sulfone.
- the electrolyte optionally further includes additives.
- additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives that can improve certain properties of the battery, such as additives that improve battery overcharge performance, additives that improve battery high-temperature or low-temperature performance, etc.
- the secondary battery further includes a separator film.
- a separator film There is no particular restriction on the type of isolation membrane in this application. Any well-known porous structure isolation membrane with good chemical stability and mechanical stability can be used.
- the material of the isolation membrane can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
- the isolation film can be a single-layer film or a multi-layer composite film, with no special restrictions. When the isolation film is a multi-layer composite film, the materials of each layer can be the same or different, and there is no particular limitation.
- the positive electrode piece, the negative electrode piece and the separator film can be made into an electrode assembly through a winding process or a lamination process.
- the secondary battery may include an outer packaging.
- the outer packaging can be used to package the above-mentioned electrode assembly and electrolyte.
- the outer packaging of the secondary battery may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc.
- the outer packaging of the secondary battery may also be a soft bag, such as a bag-type soft bag.
- the soft bag may be made of plastic. Examples of plastic include polypropylene, polybutylene terephthalate, polybutylene succinate, and the like.
- FIG. 1 shows a square-structured secondary battery 5 as an example.
- the outer package may include a housing 51 and a cover 53 .
- the housing 51 may include a bottom plate and side plates connected to the bottom plate, and the bottom plate and the side plates enclose a receiving cavity.
- the housing 51 has an opening communicating with the accommodation cavity, and the cover plate 53 can cover the opening to close the accommodation cavity.
- the positive electrode piece, the negative electrode piece and the isolation film can be formed into the electrode assembly 52 through a winding process or a lamination process.
- the electrode assembly 52 is packaged in the containing cavity.
- the electrolyte soaks into the electrode assembly 52 .
- the number of electrode assemblies 52 contained in the secondary battery 5 can be one or more, and those skilled in the art can select according to specific actual needs.
- secondary batteries can be assembled into battery modules, and the number of secondary batteries contained in the battery module can be one or more. Those skilled in the art can select the specific number according to the application and capacity of the battery module.
- FIG. 3 is a battery module 4 as an example.
- a plurality of secondary batteries 5 may be arranged in sequence along the length direction of the battery module 4 .
- the plurality of secondary batteries 5 can be fixed by fasteners.
- the battery module 4 may further include a housing having a receiving space in which a plurality of secondary batteries 5 are received.
- the above-mentioned battery modules can also be assembled into a battery pack.
- the number of battery modules contained in the battery pack can be one or more. Those skilled in the art can select the specific number according to the application and capacity of the battery pack.
- the battery pack 1 may include a battery box and a plurality of battery modules 4 disposed in the battery box.
- the battery box includes an upper box 2 and a lower box 3 .
- the upper box 2 can be covered with the lower box 3 and form a closed space for accommodating the battery module 4 .
- Multiple battery modules 4 can be arranged in the battery box in any manner.
- the present application also provides an electrical device, which includes at least one of the secondary battery, battery module, or battery pack provided by the present application.
- the secondary battery, battery module, or battery pack may be used as a power source for the electrical device, or may be used as an energy storage unit for the electrical device.
- the electric device may include mobile devices (such as mobile phones, laptops, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, and electric golf carts). , electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but are not limited to these.
- a secondary battery, a battery module or a battery pack can be selected according to its usage requirements.
- FIG. 6 is an electrical device as an example.
- the electric device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, etc.
- a battery pack or battery module can be used.
- the device may be a mobile phone, a tablet, a laptop, etc.
- the device is usually required to be thin and light, and a secondary battery can be used as a power source.
- Carbon black (purchased from Guangdong Kaijin New Energy Technology Co., Ltd.)
- Antioxidant (thanox1726, purchased from Tianjin Li'anlong New Materials Co., Ltd.)
- Anti-aging agent (Tinuvin326, purchased from BASF)
- Paraffin (58#, purchased from China Petrochemical Corporation)
- Petroleum resin (C5/C9, purchased from Shandong Tianzhao Chemical Group Co., Ltd.)
- Polyethylene (PE, CAS: 9002-88-4, its molecular weight is 800,000-1.2 million, purchased from China Petrochemical Corporation)
- Polypropylene (PP, CAS: 9003-07-0, its molecular weight is 1.2-1.5 million, purchased from China Petrochemical Corporation)
- Ethylene-vinyl acetate copolymer (EVA, CAS: 24937-78-8, its molecular weight is 800,000-1.2 million, the vinyl acetate content ranges from 5% to 50%, purchased from Mitsui Chemicals, Japan)
- Styrene-butadiene copolymer (SBS, CAS: 9003-55-8, its molecular weight is 500,000-800,000, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.)
- Styrene-ethylene-butylene-styrene block copolymer (SEBS, G1654X, its molecular weight is 500,000-800,000, purchased from Caton, USA)
- Styrene-isoprene-styrene block copolymer (SIS, D1163, its molecular weight is 500,000-800,000, purchased from Caton, USA)
- Amorphous polyalpha olefin resin (APAO, VESTOPLAST 508, its molecular weight is 500,000-800,000, purchased from Degussa)
- the dispensing temperature is 180°C
- the coating thickness of the primer glue is 5 ⁇ m.
- the dispensing temperature is 180°C
- the coating thickness of the primer glue is 5 ⁇ m.
- Dry method positive electrode film layer Weigh the positive electrode active material LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NCM523), conductive agent carbon black, and fiberizable binder polytetrafluoroethylene at a certain mass ratio of 92:4:4. Add NCM523 and carbon black into the mixing barrel of the internal mixer (10L, Guangdong Lina Industrial Co., Ltd.), stir and mix at 100rpm/min for 10 minutes, then add the fiberizable binder polytetrafluoroethylene, first stir at 200rpm/min Stir and mix for 10 minutes until the materials are evenly mixed, and then stir and mix at 400 rpm/min for 30 minutes to perform the fiberization process.
- NCM523 and carbon black into the mixing barrel of the internal mixer (10L, Guangdong Lina Industrial Co., Ltd.), stir and mix at 100rpm/min for 10 minutes, then add the fiberizable binder polytetrafluoroethylene, first stir at 200rpm/min Stir and mix for 10 minutes until the materials
- the mixed materials are put into a roller press (model MSK-H2300-E-CBTR, instrument manufacturer Shenzhen Kejing Zhida Technology Co., Ltd.) and hot-rolled at 180°C to form a self-supporting film to obtain a dry positive electrode. film layer.
- a roller press model MSK-H2300-E-CBTR, instrument manufacturer Shenzhen Kejing Zhida Technology Co., Ltd.
- the prepared dry positive electrode film layer is laminated together with the positive electrode composite current collector in 2 above, and put into a roller press (model MSK-H2300-E-CBTR, instrument manufacturer Shenzhen Kejing Zhida Technology Co., Ltd.)
- the positive electrode piece is obtained by hot rolling at 160°C.
- Dry negative electrode film layer Weigh the negative active material graphite, conductive agent carbon black, and fiberizable binder polyvinylidene fluoride according to a certain mass ratio of 92:4:4, and add the graphite and carbon black to the internal mixer ( 10L, Guangdong Lina Industrial Co., Ltd.) mixing barrel, stir and mix at 100rpm/min for 10min, then add the fiberizable binder polyvinylidene fluoride, stir and mix at 200rpm/min for 10min first, so that the materials are evenly mixed, and then Stir and mix at 400 rpm/min for 30 minutes to perform the fiberization process.
- the internal mixer 10L, Guangdong Lina Industrial Co., Ltd.
- the mixed materials are put into a roller press (model MSK-H2300-E-CBTR, instrument manufacturer Shenzhen Kejing Zhida Technology Co., Ltd.) and hot-rolled at 180°C to form a self-supporting film to obtain a dry negative electrode. film layer.
- a roller press model MSK-H2300-E-CBTR, instrument manufacturer Shenzhen Kejing Zhida Technology Co., Ltd.
- the prepared dry negative electrode film layer is laminated together with the negative electrode composite current collector in 2 above, and put into a roller press (model MSK-H2300-E-CBTR, instrument manufacturer Shenzhen Kejing Zhida Technology Co., Ltd.)
- the positive electrode piece is obtained by hot rolling at 160°C.
- the preparation of the primer glue, the preparation of the composite current collector and the preparation of the battery pole pieces are generally as described in Example 1.
- the difference is that the mass fraction of the modified polyolefin resin in the preparation of the primer glue is different. See Table 1 for details.
- the preparation of the primer glue, the preparation of the composite current collector and the preparation of the battery pole pieces are generally as described in Example 1.
- the difference is that the mass fraction of the conductive material in the preparation of the primer glue is different. See Table 1 for details.
- Example 1 The preparation of the primer glue, the preparation of the composite current collector and the preparation of the battery pole pieces are generally referred to Example 1.
- the difference is that the mass ratio of each component in the modified polyolefin resin in the preparation of the primer glue is different. For details, see the table 1.
- the preparation of the primer glue, the preparation of the composite current collector and the preparation of the battery pole pieces are generally referred to Example 1.
- the difference is that in the preparation of the primer glue, the polypropylene is weighed according to a mass ratio of 20:3:10:10. , maleic anhydride, styrene-isoprene-styrene block copolymer, and petroleum resin to prepare modified polyolefin resin, see Table 1 for details.
- the preparation of the primer glue, the preparation of the composite current collector and the preparation of the battery pole pieces are generally referred to Example 1.
- the mass ratio is 10:10:3:10:10.
- Amorphous polyalpha olefin resin, ethylene-vinyl acetate copolymer, maleic anhydride, styrene-ethylene-butylene-styrene block copolymer, and petroleum resin are used to prepare modified polyolefin resin. See Table 1 for details.
- the preparation of the primer glue, the preparation of the composite current collector and the preparation of the battery pole pieces are generally referred to Example 1.
- the difference is that in the preparation of the primer glue, the polyethylene is weighed according to a mass ratio of 20:3:10:10. , maleic anhydride, styrene-ethylene-butylene-styrene block copolymer, and petroleum resin to prepare modified polyolefin resin, see Table 1 for details.
- the preparation of the primer glue, the preparation of the composite current collector and the preparation of the battery pole pieces are generally referred to Example 1.
- the difference is that in the preparation of the primer glue, the polypropylene is weighed according to a mass ratio of 20:3:10:10. , maleic anhydride, styrene-butadiene copolymer, and petroleum resin to prepare modified polyolefin resin, see Table 1 for details.
- the preparation of the primer glue, the preparation of the composite current collector and the preparation of the battery pole pieces are generally as described in Example 1. The difference is that in the preparation of the composite current collector, the coating thickness of the primer glue is 8 ⁇ m. See Table 1 for details.
- the preparation of the primer glue, the preparation of the composite current collector, and the preparation of the battery pole pieces are generally as described in Example 1. The difference is that in the preparation of the composite current collector, the coating thickness of the primer glue is 10 ⁇ m. See Table 1 for details.
- the preparation of the dry cathode film layer is generally referred to Example 1.
- the prepared dry positive electrode film layer and carbon-coated aluminum foil (purchased from Suzhou Qiandingli Technology Co., Ltd., the carbon layer contains hot melt adhesive and carbon materials, the coating thickness is 3 ⁇ m) are laminated together and placed in a roller press. Hot rolling is performed at 160°C to obtain the positive electrode piece.
- the preparation of the dry negative electrode film layer is generally referred to Example 1.
- the prepared dry-process negative electrode film layer and carbon-coated copper foil purchased from Shanghai Zhaoyuan Industrial Co., Ltd., the carbon layer contains hot melt adhesive and carbon materials, the coating thickness is 3 ⁇ m) are bonded together and placed in a roller press. Hot rolling is performed at 160°C to obtain a negative electrode piece.
- the preparation process of the electrolyte for soaking is as follows: Mix ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) in a volume ratio of 1:1:1, and then uniformly dissolve LiPF 6 in the above solution. An electrolyte was obtained from the solution, in which the concentration of LiPF 6 was 1 mol/L.
- the primer glue for dry electrodes of the present application can greatly improve the adhesion between the dry electrode film layer and the current collector. This advantage can be achieved when immersed in electrolyte. This is especially obvious in the environment. This can improve the interface contact between the active material and the current collector, thereby effectively avoiding the phenomenon of electrode film peeling off and dust shaking during battery use.
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Abstract
本申请提供了一种干法电极用底涂胶,所述底涂胶包括按质量份计的下列组分:30-70份改性聚烯烃树脂和10-60份导电材料,其中所述改性聚烯烃树脂为马来酸酐、聚烯烃和石油树脂聚合而成的共聚物。本申请的干法电极用底涂胶能够有效改善干法电极膜层与集流体之间的粘接力,同时还能够降低电池极片的体积电阻率。本申请还提供上述干法电极用底涂胶的制备方法以及包含该干法电极用底涂胶的复合集流体、电池极片、二次电池、电池模块、电池包和用电装置。
Description
本申请涉及锂电池技术领域,尤其涉及一种干法电极用底涂胶及包括该干法电极用底涂胶的复合集流体、电池极片、二次电池、电池模块、电池包和用电装置。
近年来,随着锂离子电池的应用范围越来越广泛,锂离子电池广泛应用于水力、火力、风力和太阳能电站等储能电源系统,以及电动工具、电动自行车、电动摩托车、电动汽车、军事装备、航空航天等多个领域。由于锂离子电池取得了极大的发展,因此对其能量密度、循环性能和安全性能等也提出了更高的要求。
锂离子电池的电池极片大数采用湿法涂布方式,该工艺是将活性物质、导电剂和粘结剂溶解混合在有机溶剂中,再通过挤压涂布或转移涂布的方式涂覆于集流体表面并进行烘烤;但这种方式存在长时间烘烤和溶剂回收的问题,大大增加生产成本和工艺的复杂性。干法技术制备电池极片是一种新型制备工艺,该工艺不使用大量的有机溶剂,有利于延长电池的容量和循环寿命。然而,在干法电极极片的制备过程中,因集流体例如铝箔表面较为光滑,很难保确保干法电极膜层与集流体之间能够紧密贴合。此外,在电池的使用过程中,若干法电极膜层与集流体之间粘接力不足,容易导致膜层脱落、抖粉等现象,严重影响电池的使用寿命和安全性能。因此,需要采取一定策略来优化干法电极膜层与集流体之间的粘接力,从而改善二次电池的使用寿命和安全性能。
发明内容
本申请是鉴于上述课题而进行的,其目的在于,提供一种干法电极用底涂胶,改善干法电极膜层与集流体之间的粘接力,同时降低电池极片的体积电阻率,并提供上述干法电极用底涂胶的制备方法以及包含该 干法电极用底涂胶的复合集流体、电池极片、二次电池、电池模块、电池包和用电装置。
为了达到上述目的,本申请的第一方面提供了一种干法电极用底涂胶,所述底涂胶包括按质量份计的下列组分:
30-70份 改性聚烯烃树脂,和
10-60份 导电材料,
其中,所述改性聚烯烃树脂为马来酸酐、聚烯烃和石油树脂聚合而成的共聚物。
由此,相对于现有技术,本申请的干法电极用底涂胶能够有效改善干法电极膜层与集流体之间的粘接力,特别是能够有效改善在电解液长期浸泡下的干法电极膜层与集流体之间的粘接力,同时还能够降低电池极片的体积电阻率。
在任意实施方式中,所述干法电极用底涂胶包括按质量份计的下列组分:
40-60份 改性聚烯烃树脂,和
20-50份 导电材料。
通过调控所述干法电极用底涂胶中改性聚烯烃树脂和导电材料的含量,能够进一步改善干法电极膜层与集流体之间的粘接力,同时进一步降低电池极片的体积电阻率。
在任意实施方式中,所述改性聚烯烃树脂的重均分子量为100万-150万。通过调控改性聚烯烃树脂的重均分子量,能够进一步改善干法电极膜层与集流体之间的粘接力。
在任意实施方式中,所述聚烯烃选自以下中的一种或多种:聚乙烯、聚丙烯、乙烯-醋酸乙烯共聚物、苯乙烯-丁二烯共聚物、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物、苯乙烯-异戊二烯-苯乙烯嵌段共聚物和无定型聚α烯烃树脂,可选地,所述聚烯烃选自以下中的一种或多种:聚乙烯、聚丙烯、乙烯-醋酸乙烯共聚物和苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物。通过选择聚烯烃,能够进一步改善干法电极膜层与集流体之间的粘接力。
在任意实施方式中,所述导电材料为碳材料,所述碳材料选自以下中的一种或多种:炭黑、石墨烯、碳纳米管、石墨和中间相碳微球。 通过选择导电材料,能够进一步降低电池极片的体积电阻率。
在任意实施方式中,所述改性聚烯烃树脂与所述导电材料的质量比为0.8-1.7:1,可选为1-1.4:1。通过调控改性聚烯烃树脂与导电材料的质量比能够进一步改善干法电极膜层与集流体之间的粘接力,并进一步改善电池极片的体积电阻率。
在任意实施方式中,所述改性聚烯烃树脂中的马来酸酐、聚烯烃和石油树脂聚满足下式:
其中a1为改性聚烯烃树脂中的马来酸酐的质量百分比,a2为改性聚烯烃树脂中的聚烯烃的质量百分比,且a3为改性聚烯烃树脂中的石油树脂的质量百分比。当所述底涂胶中的改性聚烯烃树脂中的组分满足上述关系式时,能够进一步改善干法电极膜层与集流体之间的粘接力。
在任意实施方式中,所述干法电极用底涂胶还包括0.1-1质量份、可选地0.2-0.5质量份的添加剂,所述添加剂包括抗氧化剂和抗老化剂。所述添加剂的选择和调控可以改善底涂胶的热稳定性和产时间储存性。
在任意实施方式中,所述干法电极用底涂胶还包括1-10质量份的石蜡。所述石蜡可以改善改善底涂胶的粘结性。
本申请的第二方面提供第一方面的干法电极用底涂胶的制备方法,包括
S1)制备改性聚烯烃树脂;和
S2)将改性聚烯烃树脂、导电材料、添加剂、石蜡混合。
在任意实施方式中,所述制备改性聚烯烃树脂包括将马来酸酐、聚烯烃和石油树脂在150-180℃下共聚,得到改性聚烯烃树脂。
由此,能够制得本申请的干法电极用底涂胶。
本申请的第三方面提供一种复合集流体,所述复合集流体包括底涂胶层,所述底涂胶层设置集流体的至少一个表面上,所述底涂胶层在所述集流体的一个表面上的厚度为1-10μm、可选为5-8μm,所述底涂胶层采用本申请第一方面的干法电极用底涂胶涂布而成。
本申请的第四方面提供一种电池极片,所述电池极片包括本申请第三方面的复合集流体;和干法电极膜层,所述干法膜层设置在所述复合集流体中的底涂胶层之上。
本申请的第五方面提供一种二次电池,所述二次电池包括本申请第四方面的电池极片。
本申请的第六方面提供一种电池模块,其包括本申请的第五方面的二次电池。
本申请的第七方面提供一种电池包,其包括本申请的第六方面的电池模块。
本申请的第八方面提供一种用电装置,其包括选自本申请的第五方面的二次电池、本申请的第六方面的电池模块或本申请的第七方面的电池包中的至少一种。
本申请的电池模块、电池包和用电装置包括本申请提供的二次电池,因此至少具有与所述二次电池相同的优势。
图1是本申请一实施方式的二次电池的示意图。
图2是图1所示的本申请一实施方式的二次电池的分解图。
图3是本申请一实施方式的电池模块的示意图。
图4是本申请一实施方式的电池包的示意图。
图5是图4所示的本申请一实施方式的电池包的分解图。
图6是本申请一实施方式的二次电池用作电源的用电装置的示意图。
附图标记说明:
1电池包;2上箱体;3下箱体;4电池模块;5二次电池;51壳体;52电极组件;53顶盖组件
以下,适当地参照附图详细说明具体公开了本申请的干法电极用底涂胶以及包含该底涂胶的复合集流体、电池极片、二次电池、电池模块、电池包和电学装置的实施方式。但是会有省略不必要的详细说明的情况。例如,有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长,便于本领域技术人员的理解。此外,附图及以下说明是为了本领域技术人员充分理解本申请而提供的,并不旨在限定权利要求书所记载的主题。
本申请所公开的“范围”以下限和上限的形式来限定,给定范围是通过选定一个下限和一个上限进行限定的,选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的,并且可以进行任意地组合,即任何下限可以与任何上限组合形成一个范围。例如,如果针对特定参数列出了60-120和80-110的范围,理解为60-110和80-120的范围也是预料到的。此外,如果列出的最小范围值1和2,和如果列出了最大范围值3,4和5,则下面的范围可全部预料到:1-3、1-4、1-5、2-3、2-4和2-5。在本申请中,除非有其他说明,数值范围“a-b”表示a到b之间的任意实数组合的缩略表示,其中a和b都是实数。例如数值范围“0-5”表示本文中已经全部列出了“0-5”之间的全部实数,“0-5”只是这些数值组合的缩略表示。另外,当表述某个参数为≥2的整数,则相当于公开了该参数为例如整数2、3、4、5、6、7、8、9、10、11、12等。
如果没有特别的说明,本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案。
如果没有特别的说明,本申请的所有技术特征以及可选技术特征可以相互组合形成新的技术方案。
如果没有特别的说明,本申请的所有步骤可以顺序进行,也可以随机进行,优选是顺序进行的。例如,所述方法包括步骤(a)和(b),表示所述方法可包括顺序进行的步骤(a)和(b),也可以包括顺序进行的步骤(b)和(a)。例如,所述提到所述方法还可包括步骤(c),表示步骤(c)可以任意顺序加入到所述方法,例如,所述方法可以包括步骤(a)、(b)和(c),也可包括步骤(a)、(c)和(b),也可以包括步骤(c)、(a)和(b)等。
如果没有特别的说明,本申请所提到的“包括”和“包含”表示开放式,也可以是封闭式。例如,所述“包括”和“包含”可以表示还可以包括或包含没有列出的其他组分,也可以仅包括或包含列出的组分。
如果没有特别的说明,在本申请中,术语“或”是包括性的。举例来说,短语“A或B”表示“A,B,或A和B两者”。更具体地,以下任一条件均满足条件“A或B”:A为真(或存在)并且B为假(或不存在);A为假(或不存在)而B为真(或存在);或A和B都为真(或存在)。
干法技术制备电极片是一种新型锂电池制备工艺,干法电极加工工艺 具有以下优势:1)可精简掉匀浆和极片烘烤两道工序,减少电极车间厂房占地面积以及降低设备直接投资,降低设备及厂建投资成本,2)由于无需NMP溶剂,节省原材料成本且有利于环境安全,降低了环境管控运营成本,3)干法极片可制作厚电极,柔韧性好,安全性高,有望用于预锂和固态电池技术开发领域。专利CN106654177A提出将易纤维化的粘结剂与活性材料、导电剂高速混合剪切,经过辊压机多次辊压,再与具有导电胶层的集流体进复合,制得干法电极片。该工艺不使用大量的有机溶剂,有利于延长电池的容量和循环寿命,然而,集流体表面上涂覆的导电胶层为占导电胶总质量百分比98-99.5%的导电剂和0.5-2%的树脂混合物,尽管导电胶层含有大量的导电剂,然而因干法膜层与集流体之间粘接力较差,一方面会影响活性材料与集流体间界面接触,阻碍电子传输,增大电芯内阻,另一方面也会导致在电池使用过程中出现电极膜层脱落、抖粉等现象,严重影响电池的使用寿命和安全性能。
针对上述问题,本申请第一方面提供了一种干法电极用底涂胶,所述底涂胶包括按质量份计的下列组分:
30-70份 改性聚烯烃树脂,和
10-60份 导电材料,
其中,所述改性聚烯烃树脂为马来酸酐、聚烯烃和石油树脂聚合而成的共聚物。
虽然机理尚不明确,但本申请人意外地发现:本申请的干法电极用底涂胶可以提高干法电极膜层与集流体之间的粘接力,同时可以降低电池极片整体的内阻。在本申请的底涂胶中,所述改性聚烯烃树脂为马来酸酐、聚烯烃和石油树脂聚合而成的共聚物,通过在聚烯烃上引入具有极性官能的马来酸酐而进一步提高分子链段的极性,改善干法电极膜层与集流体之间的粘接力,特别是能够有效改善在电解液长期浸泡下的干法电极膜层与集流体之间的粘接力,从而能够提高活性材料与集流体间界面接触,同时均匀分散的导电材料又有利于电子传输,从而能够有效避免在电池使用过程中出现电极膜层脱落、抖粉等而造成电池性能的恶化。
在一些实施方式中,所述干法电极用底涂胶包括按质量份计的下列组分:
40-60份 改性聚烯烃树脂,和
20-50份 导电材料。
通过调控所述干法电极用底涂胶中改性聚烯烃树脂和导电材料的含量,能够进一步改善干法电极膜层与集流体之间的粘接力,同时进一步降低电池极片的体积电阻率。若改性聚烯烃树脂的含量过多,会导致导电材料在底涂胶体系中过于分散,不利于极片中电子的传输;而若改性聚烯烃的含量过少,导致极片膜层与集流体之间的粘结力降低,容易造成在电池使用过程中出现极片膜层脱落的问题,影响电池的使用寿命和安全性能。
在一些实施方式中,所述改性聚烯烃树脂的重均分子量为100万-150万。通过调控改性聚烯烃树脂的重均分子量,能够进一步改善干法电极膜层与集流体之间的粘接力。
在一些实施方式中,所述聚烯烃选自以下中的一种或多种:聚乙烯、聚丙烯、乙烯-醋酸乙烯共聚物、苯乙烯-丁二烯共聚物、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物、苯乙烯-异戊二烯-苯乙烯嵌段共聚物和无定型聚α烯烃树脂,可选地,所述聚烯烃选自以下中的一种或多种:聚乙烯、聚丙烯、乙烯-醋酸乙烯共聚物和苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物。通过选择聚烯烃,能够进一步改善干法电极膜层与集流体之间的粘接力。
在一些实施方式中,所述导电材料为碳材料,所述碳材料选自以下中的一种或多种:炭黑、石墨烯、碳纳米管、石墨和中间相碳微球。通过选择导电材料,能够进一步降低电池极片的体积电阻率。在本申请中,所述导电材料的形状可以为颗粒状、纤维状、片状等。所述导电材料的Dv50为20nm,所述D
50为样品的体积累计分布百分数达到50%时对应的粒径。
在一些实施方式中,所述改性聚烯烃树脂与所述导电材料的质量比为0.8-1.7:1,可选为1-1.4:1,例如可以为1:1、1.1:1、1.2:1、1.3:1或1.4:1,但不限于所列点值。当所述改性聚烯烃树脂与导电材料的重量比满足上述范围时,能够进一步改善干法电极膜层与集流体之间的粘接力,同时进一步降低电池极片的体积电阻率。若改性聚烯烃树脂的含量过多,会导致导电材料在底涂胶体系中过于分散,不利于极片中电子的传输;而若改性聚烯烃的含量过少,导致极片膜层与集流体之间的粘结力降低,容易造成在电池使用过程中出现极片膜层脱落的问题,影响电池的使用寿命和安全性能。
在一些实施方式中,所述改性聚烯烃树脂中的马来酸酐、聚烯烃和石油树脂聚满足下式:
其中a1为改性聚烯烃树脂中的马来酸酐的质量百分比,a2为改性聚烯烃树脂中的聚烯烃的质量百分比,且a3为改性聚烯烃树脂中的石油树脂的质量百分比。改性聚烯烃树脂是通过在聚烯烃上引入具有极性官能的马来酸酐而进一步提高分子链段的极性,改善干法电极膜层与集流体之间的粘接力。当所述底涂胶中的改性聚烯烃树脂中的组分马来酸酐、聚烯烃、石油树脂满足上述关系式时,能够进一步改善干法电极膜层与集流体之间的粘接力。
在一些实施方式中,所述干法电极用底涂胶还包括0.1-1质量份、可选地0.2-0.5质量份的添加剂,例如可以是0.2、0.3、0.4或0.5质量份等,但不限于所列点值,只要是在上述范围内的数值同样适用,所述添加剂包括抗氧化剂和抗老化剂。所述添加剂的选择和调控可以改善底涂胶的热稳定性和长期储存性,防止底涂胶在高温下发生碳化或老化而影响其性能。
在一些实施方式中,所述干法电极用底涂胶还包括1-10质量份的石蜡,例如可以是1、2、3、4、5、6、7、8、9或10质量份等,但不限于所列点值,只要是在上述范围内的数值同样适用。所述石蜡可以提高底涂胶粘结性,有利于改善改善干法电极膜层与集流体之间的粘接力。
本申请的第二方面提供第一方面的干法电极用底涂胶的制备方法,包括
S1)制备改性聚烯烃树脂;和
S2)将改性聚烯烃树脂、导电材料、添加剂、石蜡混合。
在一些实施方式中,所述制备改性聚烯烃树脂包括将马来酸酐、聚烯烃和石油树脂在150-180℃下共聚,例如可以是150℃、160℃、170℃或180℃等,但不限于所列点值,只要是在上述范围内的数值同样适用,得到改性聚烯烃树脂。
在针对干法电极用底涂胶的描述部分对于改性聚烯烃树脂、导电材料、添加剂、石蜡的说明和限定同样适用于底涂胶的制备方法。
本申请的第三方面提供一种复合集流体,所述复合集流体包括底涂胶层,所述底涂胶层设置在集流体的至少一个表面上,所述底涂胶层在所述 集流体的一个表面上的厚度为1-10μm、可选为5-8μm,例如厚度可以为5μm、6μm、7μm、8μm、9μm或10μm等,但不限于所列点值,只要是在上述范围内的数值同样适用,所述底涂胶层采用本申请第一方面的干法电极用底涂胶涂布而成。
在本申请中,所述集流体可以为金属箔片,例如铝箔、铜箔。所述集流体还可以为包括高分子材料基层和形成于高分子材料基层至少一个表面上的金属层的集流体,其可通过将金属材料(铝、铝合金、铜、铜合金镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
本申请的第四方面提供一种电池极片,所述电池极片包括本申请第三方面的复合集流体;和干法电极膜层,所述干法膜层设置在所述复合集流体中的底涂胶层之上。
在一些实施方式中,所述电池极片是通过热压工艺贴合将本申请第三方面的复合集流体与干法电极膜层制得的,其中所述热压工艺的温度为120-180℃,例如可以是120℃、130℃、140℃、150℃、160℃、170℃或180℃等,但不限于所列点值,只要是在上述范围内的数值同样适用。
在本申请中,所述干法电极膜层的制备是通过本领域技术人员已知的方法制得的,例如专利CN106654177A中公开的干法电极膜层。
本申请的第五方面提供一种二次电池,所述二次电池包括本申请第四方面的电池极片。
本申请的第六方面提供一种电池模块,其包括本申请的第五方面的二次电池。
本申请的第七方面提供一种电池包,其包括本申请的第六方面的电池模块。
本申请的第八方面提供一种用电装置,其包括选自本申请的第五方面的二次电池、本申请的第六方面的电池模块或本申请的第七方面的电池包中的至少一种。
另外,以下适当参照附图对本申请的二次电池、电池模块、电池包和用电装置进行说明。
本申请的一个实施方式中,提供一种二次电池。
通常情况下,二次电池包括正极极片、负极极片、电解质和隔离膜。在电池充放电过程中,活性离子在正极极片和负极极片之间往返嵌入和脱出。电解质在正极极片和负极极片之间起到传导离子的作用。隔离膜设置在正极极片和负极极片之间,主要起到防止正负极短路的作用,同时可以使离子通过。
[正极极片]
正极极片包括本申请的正极复合集流体以及设置在正极复合集流体至少一个表面的正极膜层。所述正极复合集流体包括底涂胶层,所述底涂胶层设置在集流体的至少一个表面上,所述底涂胶层在集流体的一个表面上的厚度为1-10μm、可选为5-8μm,例如厚度可以为5μm、6μm、7μm、8μm、9μm或10μm等,但不限于所列点值,只要是在上述范围内的数值同样适用,所述底涂胶层采用本申请的干法电极用底涂胶涂布而成。
在本申请中,所述集流体可以为金属箔片,例如铝箔,还可以为包括高分子材料基层和形成于高分子材料基层至少一个表面上的金属层的集流体,其可通过将金属材料(铝、铝合金、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
作为示例,金属箔片例如铝箔具有在其自身厚度方向相对的两个表面,其可以在其中任意一者或两者上均设置有底涂胶层,正极膜层设置在金属箔片相对的两个表面中具有底涂胶的表面上。
在一些实施方式中,正极活性材料可采用本领域公知的用于电池的正极活性材料。作为示例,正极活性材料可包括以下材料中的至少一种:橄榄石结构的含锂磷酸盐、锂过渡金属氧化物及其各自的改性化合物。但本申请并不限定于这些材料,还可以使用其他可被用作电池正极活性材料的传统材料。这些正极活性材料可以仅单独使用一种,也可以将两种以上组合使用。其中,锂过渡金属氧化物的示例可包括但不限于锂钴氧化物(如LiCoO
2)、锂镍氧化物(如LiNiO
2)、锂锰氧化物(如LiMnO
2、LiMn
2O
4)、锂镍钴氧化物、锂锰钴氧化物、锂镍锰氧化物、锂镍钴锰氧化物(如LiNi
1/3Co
1/3Mn
1/3O
2(也可以简称为NCM
333)、LiNi
0.5Co
0.2Mn
0.3O
2(也 可以简称为NCM
523)、LiNi
0.5Co
0.25Mn
0.25O
2(也可以简称为NCM
211)、LiNi
0.6Co
0.2Mn
0.2O
2(也可以简称为NCM
622)、LiNi
0.8Co
0.1Mn
0.1O
2(也可以简称为NCM
811)、锂镍钴铝氧化物(如LiNi
0.85Co
0.15Al
0.05O
2)及其改性化合物等中的至少一种。橄榄石结构的含锂磷酸盐的示例可包括但不限于磷酸铁锂(如LiFePO
4(也可以简称为LFP))、磷酸铁锂与碳的复合材料、磷酸锰锂(如LiMnPO
4)、磷酸锰锂与碳的复合材料、磷酸锰铁锂、磷酸锰铁锂与碳的复合材料中的至少一种。
在一些实施方式中,正极膜层还包括可纤维化粘结剂。作为示例,所述粘结剂可以包括可纤维化聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、丁苯橡胶、聚丙烯、聚乙烯和乙烯-醋酸乙烯共聚物(EVA)中的至少一种。
在一些实施方式中,正极膜层还可选地包括导电剂。作为示例,所述导电剂可以包括超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施方式中,正极膜层中的正极活性物质、导电剂和可纤维化粘结剂的质量比为70-90:5-10:3-10。
在一些实施方式中,可以通过以下方式制备干法正极膜层:将上述用于制备正极膜层的组分,例如正极活性材料、导电剂、可纤维化粘结剂和任意其他的组分混合进行纤维化处理,得到高纤维化的混合物料,再将该混合物料经辊压后,得到连续化的自支撑干法正极膜层。
在一些实施方式中,可以通过热压工艺贴合将正极复合集流体与干法正极膜层来获得正极极片,其中所述热压工艺的温度为120-180℃。
[负极极片]
负极极片包括本申请的负极复合集流体以及设置在负极复合集流体至少一个表面的负极膜层。所述负极复合集流体包括底涂胶层,所述底涂胶层设置在集流体的至少一个表面上,所述底涂胶层在集流体的一个表面上的厚度为1-10μm、可选为5-8μm,例如厚度可以为5μm、6μm、7μm、8μm、9μm或10μm等,但不限于所列点值,只要是在上述范围内的数值同样适用,所述底涂胶层采用本申请的干法电极用底涂胶涂布而成。
在本申请中,所述集流体可以为金属箔片,例如铜箔,还可以为包括高分子材料基层和形成于高分子材料基层至少一个表面上的金属层的集 流体,其可通过将金属材料(铜、铜合金、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
作为示例,金属箔片例如铜箔具有在其自身厚度方向相对的两个表面,其可以在其中任意一者或两者上均设置有底涂胶层,正极膜层设置在金属箔片相对的两个表面中具有底涂胶的表面上。
在一些实施方式中,负极活性材料可采用本领域公知的用于电池的负极活性材料。作为示例,负极活性材料可包括以下材料中的至少一种:人造石墨、天然石墨、软炭、硬炭、硅基材料、锡基材料和钛酸锂等。所述硅基材料可选自单质硅、硅氧化合物、硅碳复合物、硅氮复合物以及硅合金中的至少一种。所述锡基材料可选自单质锡、锡氧化合物以及锡合金中的至少一种。但本申请并不限定于这些材料,还可以使用其他可被用作电池负极活性材料的传统材料。这些负极活性材料可以仅单独使用一种,也可以将两种以上组合使用。所述负极极活性材料可以具有具有12μm-22μm的平均粒径(D
50),所述D
50为样品的体积累计分布百分数达到50%时对应的粒径。
正极膜层还包括可纤维化粘结剂。作为示例,所述粘结剂可以包括可纤维化聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、丁苯橡胶、聚丙烯、聚乙烯和乙烯-醋酸乙烯共聚物(EVA)中的至少一种。
在一些实施方式中,负极膜层还可选地包括导电剂。导电剂可选自超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施方式中,负极膜层还可选地包括其他助剂,例如增稠剂(如羧甲基纤维素钠(CMC-Na))等。
在一些实施方式中,负极膜层中的负极活性物质、导电剂和可纤维化粘结剂的质量比为70-90:5-10:3-10。
在一些实施方式中,可以通过以下方式制备干法负极膜层:将上述用于制备负极膜层的组分,例如负极活性材料、导电剂、可纤维化粘结剂和任意其他的组分进行纤维化处理,得到高纤维化的混合物料,再将该混合物料经辊压后,得到连续化的自支撑干法负极膜层。
在一些实施方式中,可以通过热压工艺贴合将负极复合集流体与干法负极膜层来获得负极极片,其中所述热压工艺的温度为120-180℃。
[电解质]
电解质在正极极片和负极极片之间起到传导离子的作用。本申请对电解质的种类没有具体的限制,可根据需求进行选择。例如,电解质可以是液态的、凝胶态的或全固态的。
在一些实施方式中,所述电解质采用电解液。所述电解液包括电解质盐和溶剂。
在一些实施方式中,电解质盐可选自六氟磷酸锂、四氟硼酸锂、高氯酸锂、六氟砷酸锂、双氟磺酰亚胺锂、双三氟甲磺酰亚胺锂、三氟甲磺酸锂、二氟磷酸锂、二氟草酸硼酸锂、二草酸硼酸锂、二氟二草酸磷酸锂及四氟草酸磷酸锂中的至少一种。
在一些实施方式中,溶剂可选自碳酸亚乙酯、碳酸亚丙酯、碳酸甲乙酯、碳酸二乙酯、碳酸二甲酯、碳酸二丙酯、碳酸甲丙酯、碳酸乙丙酯、碳酸亚丁酯、氟代碳酸亚乙酯、甲酸甲酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯、丁酸乙酯、1,4-丁内酯、环丁砜、二甲砜、甲乙砜及二乙砜中的至少一种。
在一些实施方式中,所述电解液还可选地包括添加剂。例如添加剂可以包括负极成膜添加剂、正极成膜添加剂,还可以包括能够改善电池某些性能的添加剂,例如改善电池过充性能的添加剂、改善电池高温或低温性能的添加剂等。
[隔离膜]
在一些实施方式中,二次电池中还包括隔离膜。本申请对隔离膜的种类没有特别的限制,可以选用任意公知的具有良好的化学稳定性和机械稳定性的多孔结构隔离膜。
在一些实施方式中,隔离膜的材质可选自玻璃纤维、无纺布、聚乙烯、聚丙烯及聚偏二氟乙烯中的至少一种。隔离膜可以是单层薄膜,也可以是多层复合薄膜,没有特别限制。在隔离膜为多层复合薄膜时,各层的材料可以相同或不同,没有特别限制。
在一些实施方式中,正极极片、负极极片和隔离膜可通过卷绕工艺或叠片工艺制成电极组件。
在一些实施方式中,二次电池可包括外包装。该外包装可用于封装上述电极组件及电解质。
在一些实施方式中,二次电池的外包装可以是硬壳,例如硬塑料壳、铝壳、钢壳等。二次电池的外包装也可以是软包,例如袋式软包。软包的材质可以是塑料,作为塑料,可列举出聚丙烯、聚对苯二甲酸丁二醇酯以及聚丁二酸丁二醇酯等。
本申请对二次电池的形状没有特别的限制,其可以是圆柱形、方形或其他任意的形状。例如,图1是作为一个示例的方形结构的二次电池5。
在一些实施方式中,参照图2,外包装可包括壳体51和盖板53。其中,壳体51可包括底板和连接于底板上的侧板,底板和侧板围合形成容纳腔。壳体51具有与容纳腔连通的开口,盖板53能够盖设于所述开口,以封闭所述容纳腔。正极极片、负极极片和隔离膜可经卷绕工艺或叠片工艺形成电极组件52。电极组件52封装于所述容纳腔内。电解液浸润于电极组件52中。二次电池5所含电极组件52的数量可以为一个或多个,本领域技术人员可根据具体实际需求进行选择。
在一些实施方式中,二次电池可以组装成电池模块,电池模块所含二次电池的数量可以为一个或多个,具体数量本领域技术人员可根据电池模块的应用和容量进行选择。
图3是作为一个示例的电池模块4。参照图3,在电池模块4中,多个二次电池5可以是沿电池模块4的长度方向依次排列设置。当然,也可以按照其他任意的方式进行排布。进一步可以通过紧固件将该多个二次电池5进行固定。
可选地,电池模块4还可以包括具有容纳空间的外壳,多个二次电池5容纳于该容纳空间。
在一些实施方式中,上述电池模块还可以组装成电池包,电池包所含电池模块的数量可以为一个或多个,具体数量本领域技术人员可根据电池包的应用和容量进行选择。
图4和图5是作为一个示例的电池包1。参照图4和图5,在电池包1中可以包括电池箱和设置于电池箱中的多个电池模块4。电池箱包括上箱体2和下箱体3,上箱体2能够盖设于下箱体3,并形成用于容纳电池模块4的封闭空间。多个电池模块4可以按照任意的方式排布于电池箱中。
另外,本申请还提供一种用电装置,所述用电装置包括本申请提供的二次电池、电池模块、或电池包中的至少一种。所述二次电池、电池模块、或电池包可以用作所述用电装置的电源,也可以用作所述用电装置的能量存储单元。所述用电装置可以包括移动设备(例如手机、笔记本电脑等)、电动车辆(例如纯电动车、混合动力电动车、插电式混合动力电动车、电动自行车、电动踏板车、电动高尔夫球车、电动卡车等)、电气列车、船舶及卫星、储能系统等,但不限于此。
作为所述用电装置,可以根据其使用需求来选择二次电池、电池模块或电池包。
图6是作为一个示例的用电装置。该用电装置为纯电动车、混合动力电动车、或插电式混合动力电动车等。为了满足该用电装置对二次电池的高功率和高能量密度的需求,可以采用电池包或电池模块。
作为另一个示例的装置可以是手机、平板电脑、笔记本电脑等。该装置通常要求轻薄化,可以采用二次电池作为电源。
实施例
以下,说明本申请的实施例。下面描述的实施例是示例性的,仅用于解释本申请,而不能理解为对本申请的限制。实施例中未注明具体技术或条件的,按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者,均为可以通过市购获得的常规产品。
I.原材料
石墨烯(购自于广东凯金新能源科技股份有限公司)
碳黑(购自于广东凯金新能源科技股份有限公司)
抗氧化剂(thanox1726,购自于天津利安隆新材料股份有限公司)
抗老化剂(Tinuvin326,购自于BASF)
石蜡(58#,购自于中国石油化工股份有限公司)
石油树脂(C5/C9,购自于山东天曌化工集团有限公司)
马来酸酐(C
4H
2O
3,CAS:108-31-6,购自于淄博齐翔腾达化工股份 有限公司)
聚乙烯(PE,CAS:9002-88-4,其分子量为80-120万,购自于中国石油化工股份有限公司)
聚丙烯(PP,CAS:9003-07-0,其分子量为120-150万,购自于中国石油化工股份有限公司)
乙烯-醋酸乙烯共聚物(EVA,CAS:24937-78-8,其分子量为80-120万,醋酸乙烯含量范围在5%~50%,购自于日本三井化学)
苯乙烯-丁二烯共聚物(SBS,CAS:9003-55-8,其分子量为50-80万,购自于上海阿拉丁生化科技股份有限公司)
苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物(SEBS,G1654X,其分子量为50-80万,购自于美国科腾)
苯乙烯-异戊二烯-苯乙烯嵌段共聚物(SIS,D1163,其分子量为50-80万,购自于美国科腾)
无定型聚α烯烃树脂(APAO,VESTOPLAST 508,其分子量为50-80万,购自于德固赛)
实施例1
1.底涂胶的制备
按照质量比为20:3:10:10称取聚丙烯、马来酸酐、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物、石油树脂加入反应釜,将反应釜温度升至160℃,抽真空搅拌120min,得到改性聚烯烃树脂。按照质量份数称取50份上述改性聚烯烃树脂,随后加入5份石蜡、0.2份抗氧化剂、0.2份抗老化剂、50份导电剂石墨烯,先以1200rpm/min搅拌60min,随后以800rpm/min搅拌30min,使得各组分混合均匀,最后灌装出料,得到底涂胶。
2.复合集流体的制备
(1)正极复合集流体
将上述制得的底涂胶装入热熔点胶机(ET-420D,易视智瞳科技有限公司),点胶温度为180℃,将底涂胶涂覆在铝箔(铝箔的厚度为13μm)上,底涂胶的涂覆厚度为5μm,冷却固化后,将得到的正极复合集流体 收卷备用。
(2)负极复合集流体
将上述制得的底涂胶装入热熔点胶机(ET-420D,易视智瞳科技有限公司),点胶温度为180℃,将底涂胶涂覆在铜箔(铜箔的厚度为6μm)上,底涂胶的涂覆厚度为5μm,冷却固化后,将得到的负极复合集流体收卷备用。
3.电池极片的制备
(1)正极极片
干法正极膜层:按一定的质量比为92:4:4称取正极活性物质LiNi
0.5Co
0.2Mn
0.3O
2(NCM523)、导电剂炭黑、可纤维化粘结剂聚四氟乙烯,将NCM523和炭黑加入密炼机(10L,广东利拿实业有限公司)混炼桶中,以100rpm/min搅拌混合10min,再加入可纤维化粘结剂聚四氟乙烯,先以200rpm/min搅拌混合10min,使得物料混合均匀,随后以400rpm/min搅拌混合30min,进行纤维化过程。将混合后的物料放入辊压机(型号MSK-H2300-E-CBTR,仪器厂商深圳市科晶智达科技有限公司)中,在180℃下进行热辊压成自支撑膜,得到干法正极膜层。
随后将制得的干法正极膜层与上述2中的正极复合集流体贴合在一起,放入辊压机(型号MSK-H2300-E-CBTR,仪器厂商深圳市科晶智达科技有限公司)中在160℃下进行热辊压,得到正极极片。
(2)负极极片
干法负极膜层:按一定的质量比为92:4:4称取负极活性材料石墨、导电剂炭黑、可纤维化粘结剂聚偏氟乙烯,将石墨和炭黑加入密炼机(10L,广东利拿实业有限公司)混炼桶中,以100rpm/min搅拌混合10min,再加入可纤维化粘结剂聚偏氟乙烯,先以200rpm/min搅拌混合10min,使得物料混合均匀,随后以400rpm/min搅拌混合30min,进行纤维化过程。将混合后的物料放入辊压机(型号MSK-H2300-E-CBTR,仪器厂商深圳市科晶智达科技有限公司)中,在180℃下进行热辊压成自支撑膜,得到干法负极膜层。
随后将制得的干法负极膜层与上述2中的负极复合集流体贴合在一起,放入辊压机(型号MSK-H2300-E-CBTR,仪器厂商深圳市科晶智达科技有限公司)中在160℃下进行热辊压,得到正极极片。
实施例2-5
底涂胶的制备、复合集流体的制备和电池极片的制备整体上参照实施例1,区别在于,底涂胶的制备中的改性聚烯烃树脂的质量份数不同,具体参见表1。
实施例6-10
底涂胶的制备、复合集流体的制备和电池极片的制备整体上参照实施例1,区别在于,底涂胶的制备中的导电材料的质量份数不同,具体参见表1。
实施例11-14
底涂胶的制备、复合集流体的制备和电池极片的制备整体上参照实施例1,区别在于,底涂胶制备中的改性聚烯烃树脂中各组分的质量比不同,具体参见表1。
实施例15
底涂胶的制备、复合集流体的制备和电池极片的制备整体上参照实施例1,区别在于,在底涂胶的制备中,按照质量比为20:3:10:10称取聚丙烯、马来酸酐、苯乙烯-异戊二烯-苯乙烯嵌段共聚物、石油树脂来制备改性聚烯烃树脂,具体参见表1。
实施例16
底涂胶的制备、复合集流体的制备和电池极片的制备整体上参照实施例1,区别在于,在底涂胶的制备中,按照质量比为10:10:3:10:10称取无定型聚α烯烃树脂、乙烯-醋酸乙烯共聚物、马来酸酐、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物、石油树脂来制备改性聚烯烃树脂,具体参见表1。
实施例17
底涂胶的制备、复合集流体的制备和电池极片的制备整体上参照实施例1,区别在于,在底涂胶的制备中,按照质量比为20:3:10:10称取聚乙烯、马来酸酐、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物、石油树脂来制备改性聚烯烃树脂,具体参见表1。
实施例18
底涂胶的制备、复合集流体的制备和电池极片的制备整体上参照实施例1,区别在于,在底涂胶的制备中,按照质量比为20:3:10:10称取聚丙烯、马来酸酐、苯乙烯-丁二烯共聚物、石油树脂来制备改性聚烯烃树脂,具体参见表1。
实施例19
底涂胶的制备、复合集流体的制备和电池极片的制备整体上参照实施例1,区别在于,复合集流体的制备中底涂胶的涂覆厚度为8μm,具体参见表1。
实施例20
底涂胶的制备、复合集流体的制备和电池极片的制备整体上参照实施例1,区别在于,复合集流体的制备中底涂胶的涂覆厚度为10μm,具体参见表1。
对比例1
(1)正极极片
干法正极膜层的制备整体上参照实施例1。将制得的干法正极膜层与涂炭铝箔(购自于苏州乾鼎利科技有限公司,碳层包含热熔胶与碳材料,涂层厚度3μm)贴合在一起,放入辊压机中在160℃下进行热辊压,得到正极极片。
(2)负极极片
干法负极膜层制备的制备整体上参照实施例1。将制得的干法负极膜层与涂炭铜箔(购自于上海昭远实业有限公司,碳层包含热熔胶与碳材料,涂层厚度3μm)贴合在一起,放入辊压机中在160℃下进行热辊压,得到负极极片。
二、相关参数测试与性能测试
(1)聚烯烃树脂的重均分子量的凝胶渗透色谱法测试
采用Waters 2695 Isocratic HPLC型凝胶色谱仪(示差折光检测器2141)。质量分数为3.0%的聚苯乙烯溶液试样做参比,选择匹配的色谱柱(油性:Styragel HT5 DMF7.8*300mm+Styragel HT4)。用纯化后的N-甲基吡咯烷酮(NMP)溶剂配置3.0%的改性聚烯烃树脂的胶液,配置好的溶液静置一天,备用。测试时,先用注射器吸取四氢呋喃,进行冲洗,重复几次。然后吸取5ml实验溶液,排除注射器中的空气,将针尖擦干。最后将试样溶液缓缓注入进样口。待示数稳定后获取数据,得到改性聚烯烃树脂重均分子量。
(2)体积电阻率测试
将样品左、中、右处裁剪3*3mm小圆片。打开元能科技极片电阻仪指示灯,将置于膜层电阻仪“探头”合适位置,点击“开始”按钮,待示数稳定,读取即可。每个小圆片测试两个位置,最后计算六次测量的平均值,即为该样品的体积电阻率。
结果参见表2。
(3)粘接力测试
将样品裁剪为20*100mm尺寸备用;试样用双面胶粘接需要测试的那一面,并用压辊压实,使之与试样完全贴合;试样的双面胶的另外一面粘贴于不锈钢表面,将试样一端反向弯曲,弯曲角度为180°;采用高铁拉力机测试,将不锈钢一端固定于拉力机下方夹具,试样弯曲末端固定于上方夹具,调整试样角度,保证上下端位于垂直位置,然后以50mm/min的速度拉伸试样,直到试样全部从基板剥离,记录过程中的位移和作用力, 一般认为受力平衡时的力为试样的粘结力。
分别测试电解液浸泡前和电解液浸泡不同时间后样品的粘接力,结果参见表2和表3。
浸泡用的电解液制备过程如下:将碳酸亚乙酯(EC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)体积比1:1:1混合,然后将LiPF
6均匀溶解在上述溶液中得到电解液,其中LiPF
6的浓度为1mol/L。
从以上结果中能够看出,与对比例1相比,本申请的干法电极用底涂胶能够大大提高干法电极膜层与集流体之间的粘接力,这一优势在电解液浸泡环境中尤为明显,这样能够提高活性材料与集流体间界面接触,从而能够有效避免在电池使用过程中出现电极膜层脱落、抖粉等现象。
需要说明的是,本申请不限定于上述实施方式。上述实施方式仅为示例,在本申请的技术方案范围内具有与技术思想实质相同的构成、发挥相同作用效果的实施方式均包含在本申请的技术范围内。此外,在不脱离本申请主旨的范围内,对实施方式施加本领域技术人员能够想到的各种变形、将实施方式中的一部分构成要素加以组合而构筑的其它方式也包含在本申请的范围内。
Claims (17)
- 一种干法电极用底涂胶,其特征在于,所述底涂胶包括按质量份计的下列组分:30-70份 改性聚烯烃树脂,和10-60份 导电材料,其中所述改性聚烯烃树脂为马来酸酐、聚烯烃和石油树脂聚合而成的共聚物。
- 根据权利要求1所述的干法电极用底涂胶,其特征在于,所述底涂胶包括按质量份计的下列组分:40-60份 改性聚烯烃树脂,和20-50份 导电材料。
- 根据权利要求1或2所述的干法电极用底涂胶,其特征在于,所述改性聚烯烃树脂的重均分子量为100万-150万。
- 根据权利要求1或2所述的干法电极用底涂胶,其特征在于,所述聚烯烃选自以下中的一种或多种:聚乙烯、聚丙烯、乙烯-醋酸乙烯共聚物、苯乙烯-丁二烯共聚物、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物、苯乙烯-异戊二烯-苯乙烯嵌段共聚物和无定型聚α烯烃树脂,可选地,所述聚烯烃选自以下中的一种或多种:聚乙烯、聚丙烯、乙烯-醋酸乙烯共聚物和苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物。
- 根据权利要求1或2所述的干法电极用底涂胶,其特征在于,所述导电材料为碳材料,所述碳材料选自以下中的一种或多种:炭黑、石墨烯、碳纳米管、石墨和中间相碳微球。
- 根据权利要求1或2所述的干法电极用底涂胶,其特征在于,所述改性聚烯烃树脂与所述导电材料的质量比为0.8-1.7:1,可选为1-1.4:1。
- 根据权利要求1或2所述的干法电极用底涂胶,其特征在于,所 述底涂胶还包括0.1-1质量份、可选地0.2-0.5质量份的添加剂,所述添加剂包括抗氧化剂和抗老化剂。
- 根据权利要求1或2所述的干法电极用底涂胶,其特征在于,所述底涂胶还包括1-10质量份的石蜡。
- 一种制备权利要求1-9中任一项所述的干法电极用底涂胶的方法,其特征在于,包括S1)制备改性聚烯烃树脂;和S2)将改性聚烯烃树脂、导电材料、添加剂、石蜡混合。
- 根据权利要求10所述的制备干法电极用底涂胶的方法,其特征在于,所述制备改性聚烯烃树脂包括将马来酸酐、聚烯烃和石油树脂在150-180℃下共聚,得到改性聚烯烃树脂。
- 一种复合集流体,其特征在于,所述复合集流体包括底涂胶层,所述底涂胶层设置在集流体的至少一个表面上,所述底涂胶层在集流体的一个表面上的厚度为1-10μm、可选为5-8μm,所述底涂胶层采用权利要求1-9中任一项所述的干法电极用底涂胶涂布而成。
- 一种电池极片,其特征在于,所述电池极片包括权利要求12所述的复合集流体;和干法电极膜层,所述干法膜层设置在所述复合集流体中的底涂胶层之上。
- 一种二次电池,其特征在于,包括权利要求13所述的电池极片。
- 一种电池模块,其特征在于,包括权利要求14所述的二次电池。
- 一种电池包,其特征在于,包括权利要求15所述的电池模块。
- 一种用电装置,其特征在于,包括选自权利要求14所述的二次电池、权利要求15所述的电池模块或权利要求16所述的电池包中的至少一种。
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EP22937665.2A EP4343881A1 (en) | 2022-07-29 | 2022-07-29 | Undercoat adhesive for dry-method electrode and preparation method therefor, composite current collector, battery electrode plate, secondary battery, battery module, battery pack and electric device |
PCT/CN2022/108953 WO2024021018A1 (zh) | 2022-07-29 | 2022-07-29 | 干法电极用底涂胶及其制备方法、复合集流体、电池极片、二次电池、电池模块、电池包和用电装置 |
US18/384,650 US20240076531A1 (en) | 2022-07-29 | 2023-10-27 | Primer adhesive for dry electrode and preparation method therefor, composite current collector, battery electrode plate, secondary battery, battery module, battery pack and power consuming device |
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