WO2021248465A1 - 无纺布及其制备方法、锂电池隔膜及锂电池隔膜基膜 - Google Patents
无纺布及其制备方法、锂电池隔膜及锂电池隔膜基膜 Download PDFInfo
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/10—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically
- D04H3/115—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically by applying or inserting filamentary binding elements
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H13/00—Other non-woven fabrics
- D04H13/001—Making non-woven fabrics from staple fibres, filaments or yarns, bonded to at least one web-like material, e.g. woven, knitted non-woven fabric, paper, leather, during consolidation
- D04H13/007—Making non-woven fabrics from staple fibres, filaments or yarns, bonded to at least one web-like material, e.g. woven, knitted non-woven fabric, paper, leather, during consolidation strengthened or consolidated by welding together the various components
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- 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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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/42—Acrylic resins
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- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- H01M50/426—Fluorocarbon polymers
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/454—Separators, membranes or diaphragms characterised by the material having a layered structure comprising a non-fibrous layer and a fibrous layer superimposed on one another
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/494—Tensile strength
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/007—Addition polymers
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/009—Condensation or reaction polymers
- D04H3/011—Polyesters
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- 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 field of materials, in particular, to a non-woven fabric and a preparation method thereof, a lithium battery diaphragm, and a lithium battery diaphragm base film.
- the mainstream lithium-ion battery separators on the market are porous polyolefin membranes based on polyethylene (PE) and polypropylene (PP).
- separators of different specifications are used according to the application, such as single-layer, double-layer and three-layer wet methods. Or dry diaphragm.
- Porous polyolefin separators have been used in large-scale industrialization due to their high cost performance, but their poor thermal stability has become a bottleneck restricting the further improvement of battery energy density.
- the polyolefin lithium battery separator has a large thermal shrinkage at a high temperature of >140°C. When the separator thermally shrinks severely, the positive and negative poles of the battery are easily contacted and short-circuited, causing the thermal runaway of the battery and spontaneous combustion and spontaneous explosion.
- Non-woven separators have great application potential in high-energy lithium battery systems due to their excellent heat resistance.
- the non-woven fabric diaphragm has high porosity and high thermal stability, and can reach a heat-resistant temperature above 150°C.
- the three-dimensional pore structure of the non-woven fabric can ensure a high electrolyte retention rate and effectively prevent short circuits caused by the puncture of the diaphragm. There was a problem.
- Non-woven fabrics have a natural large pore size and high porosity. In order to prevent dendrites from growing through the pore size, their thickness must be increased. Therefore, it is difficult to meet both the pore size and thickness requirements of lithium ion battery separators. Under the existing technology, It cannot be used directly as a lithium-ion battery separator, and is generally only suitable for use as a base film of a lithium-ion battery composite separator.
- the coating layer on the non-woven fabric needs to have excellent consistency, which in turn requires the uniformity of the non-woven fabric and the smoothness of the coating surface, and the non-woven fabric coating surface
- the adhesiveness also needs to be excellent to ensure that the coating layer and the non-woven fabric are firmly bonded to each other, and the coating layer and the non-woven fabric do not delaminate or peel off.
- the purpose of the embodiments of the present application is to provide a non-woven fabric and a preparation method thereof, a lithium battery separator film, and a lithium battery separator base film, which are intended to improve the bonding performance of the non-woven fabric and other materials such as coatings.
- the first aspect of the present application provides a non-woven fabric.
- the raw material of the non-woven fabric includes backbone fibers and bonding fibers.
- the bonding fiber includes a first bonding fiber and a second bonding fiber.
- the melting point or softening point of the first bonding fiber is 120-220°C; the melting point or softening point of the second bonding fiber is 100-170°C, and the melting point or softening point of the second bonding fiber is higher than that of the first bonding fiber.
- the melting point or softening point is lower than 15°C.
- the melting point or softening point of the backbone fiber is higher than the melting point or softening point of the first binder fiber by more than 20°C.
- the second bonding fiber has a relatively low melting point or softening point, 105 to 170°C, and is first melted during the thermal calendering process to form a discontinuous fine uneven structure on the surface of the non-woven fabric.
- the melting point or softening point of the backbone fiber is higher than that of the first bonding fiber and the second bonding fiber, and it can have high dimensional stability during the hot pressing process.
- the first bonding fiber is partially melted, and the second bonding fiber is completely Melting, bonding each fiber to each other, and forming a three-dimensional network structure of non-woven fabric after cooling.
- the melting point or softening point of the second bonding fiber is lower than the melting point or softening point of the first bonding fiber by more than 15°C.
- the degree of melting at each temperature during the formation of the non-woven fabric forms a fine uneven structure on the surface.
- the concave-convex structure can make the coating layer and the non-woven fabric have an anchoring effect for realizing strong bonding.
- the coating slurry is embedded in the fine cavities on the surface of the non-woven fabric, and the coating cannot move after curing, resulting in extremely strong bonding strength.
- the melting point or softening point of the second bonding fiber is 20-100° C. lower than the melting point or softening point of the first bonding fiber.
- the fiber lengths of the first bonding fiber and the second bonding fiber are both 1 to 6 mm, and the fiber diameters of the first bonding fiber and the second bonding fiber are both smaller than or Equal to 10 ⁇ m.
- the fiber length of the backbone fiber is 1 ⁇ 6mm; the fiber diameter of the backbone fiber is less than or equal to 4 ⁇ m;
- the fiber diameter of the first bonding fiber and the second bonding fiber are both 2.5-9 ⁇ m; the fiber diameter of the backbone fiber is 1-3.5 ⁇ m.
- the backbone fiber accounts for 60-80% of the total mass of the non-woven fabric backbone fiber and bonding fiber.
- the backbone fibers account for 65 to 75% of the total mass of the non-woven fabric backbone fibers and bonding fibers.
- the second bonding fiber accounts for 10-40% of the total mass of the bonding fiber.
- the second bonding fiber accounts for 20-30% of the total mass of the bonding fiber.
- the density of the non-woven fabric is 0.50-0.9 g/cm 3
- the average pore diameter is not more than 4.5 ⁇ m
- the ratio of the maximum pore diameter to the average pore diameter is 1-10.
- the material of the backbone fiber includes polyester fiber, polyolefin fiber, polyamide fiber, polyimide fiber, polytetrafluoroethylene fiber, polyphenylene sulfide fiber, polyether ether At least one of ketone fiber, polyacrylonitrile fiber, polycarbonate fiber and aramid fiber.
- the material of the first bonding fiber includes at least one of undrawn polyester fiber, polyvinylidene fluoride fiber, polyamide fiber, copolyamide fiber, and polyolefin fiber.
- the material of the second bonding fiber includes at least one of polyolefin fiber, copolyester fiber, and copolyamide fiber.
- the second aspect of the present application provides a method for preparing a non-woven fabric.
- the heat-pressing treatment temperature is higher than the melting point or softening point temperature of the second binding fiber by more than 10°C, and the heat-pressing treatment temperature is not higher than the The melting point or softening point temperature of the backbone fiber; optionally, the hot pressing speed of the hot pressing treatment is 1-100 m/min.
- a third aspect of the present application provides a lithium battery separator base film, and the lithium ion separator base film includes the non-woven fabric provided in the above-mentioned first aspect.
- a fourth aspect of the present application provides a lithium battery separator.
- the lithium battery separator includes a coating and the base film provided in the second aspect, and the coating is attached to the surface of the base film.
- the non-woven fabric Due to the uneven surface structure of the non-woven fabric provided by the present application, it can improve the meshing property of the non-woven fabric, increase the contact area between the coating slurry and the non-woven fabric, and make the surfaces of the two inlaid with each other to generate meshing force to achieve strong strength The effect of joining.
- the uniformity and excellent meshing properties of the non-woven fabric enable the coating layer and the non-woven fabric to be firmly combined with each other, and the coating layer and the non-woven fabric do not delaminate or peel off.
- Figure 1 is a surface electron micrograph of the non-woven fabric described in Example 1.
- FIG. 2 is a surface electron micrograph of the non-woven fabric described in Comparative Example 1.
- FIG. 2 is a surface electron micrograph of the non-woven fabric described in Comparative Example 1.
- FIG. 3 is a surface electron micrograph of the non-woven fabric described in Comparative Example 2.
- FIG. 4 is a surface electron micrograph of the non-woven fabric described in Comparative Example 3.
- FIG. 4 is a surface electron micrograph of the non-woven fabric described in Comparative Example 3.
- FIG. 5 is a surface electron micrograph of the non-woven fabric described in Comparative Example 4.
- FIG. 5 is a surface electron micrograph of the non-woven fabric described in Comparative Example 4.
- FIG. 6 is a surface electron micrograph of the non-woven fabric sample described in Comparative Example 5.
- the method of composite coating on the non-woven fabric support layer is usually to first prepare the coating slurry, and then apply the slurry to the surface of the non-woven fabric by micro-gravure roll coating, spray coating, dip coating, etc., and then dry to coat the surface. The layer is cured.
- the binding force between the coating and the non-woven fabric is the result of the interaction between the interfaces of different materials.
- the influencing factors are complex and may be affected by the interfacial tension, surface free energy, and functional groups between the coating and the non-woven fabric. Group properties, inter-interface reactions, etc.
- the main source of the binding force between the coating and the non-woven fabric is the molecular force of the system, namely van der Waals attraction and hydrogen bonding force.
- the coating and the base film are combined by chemical bonds, but the formation of chemical bonds is not common. To form chemical bonds, certain conditions must be met. It is impossible to form chemical bonds at all contact points between the adhesive and the substrate.
- the bonding force between the coating layer and the non-woven fabric is mainly caused by the coating slurry penetrating into the pores or uneven structure on the surface of the non-woven fabric. The essence of this connection force is friction.
- the coating slurry cannot well infiltrate the surface of the non-woven fabric, and the air bubbles remain in the pores so that the coating slurry is elevated at the pores of the non-woven fabric, reducing the coating slurry
- the actual contact area between the material and the non-woven fabric will cause serious problems such as the weakening of the bonding force of the coating and the non-woven fabric, and the significant decrease in the performance of the non-woven fabric coating diaphragm.
- the non-woven fabric, lithium battery separator, and lithium battery separator base film of the embodiments of the present application will be specifically described below.
- the raw materials of the non-woven fabric include backbone fibers and bonding fibers; the bonding fibers include a first bonding fiber and a second bonding fiber; the melting point or softening point of the first bonding fiber is 120-220°C
- the melting point or softening point of the second bonding fiber is 100 ⁇ 170°C; and the melting point or softening point of the second bonding fiber is 15°C or more lower than the melting point or softening point of the first bonding fiber; the melting point or softening of the backbone fiber The point is higher than the melting point or softening point of the first binder fiber by more than 20°C.
- the material of the backbone fiber includes polyester fiber, polyolefin fiber, polyamide fiber, polyimide fiber, polytetrafluoroethylene fiber, polyphenylene sulfide fiber, polyether At least one of ether ketone fiber, polyacrylonitrile fiber, polycarbonate fiber and aramid fiber.
- the polyester fiber may be selected from polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyisophthalic resin, and the like.
- the polyolefin fiber can be selected from polyethylene, polypropylene, polyvinyl chloride, polystyrene, ES (Ethylene-Propylene Side By Side) fiber, etc.
- the polyamide fiber can be, for example, PA66.
- the material of the first bonding fiber includes at least one of undrawn polyester fiber, polyvinylidene fluoride fiber, polyamide fiber, copolyamide fiber, and polyolefin fiber.
- the undrawn polyester fiber may be selected from polyethylene terephthalate, polybutylene terephthalate, and the like.
- Polyolefin fibers can be selected from polyethylene, polypropylene, polyvinyl chloride, polystyrene, ES fibers, and the like.
- the material of the second bonding fiber includes at least one of polyolefin fiber, copolyester fiber, and copolyamide fiber.
- polyolefin fibers can be selected from polyethylene, polypropylene, polyvinyl chloride, polystyrene, ES fibers, and the like.
- Copolyester fibers can be selected from CoPET, CoPBT (copolymerized polybutylene terephthalate) and the like.
- Copolyamide fibers can be selected from PA6/6, PA6/66, PA6/66/12, PA6/66/69, PA6/66/610, PA6/66/612, PA6/66/1010, PA6/612/12, PA6/610/12, PA6/66/69/12, PA6/66/11/12, etc.
- first bonding fiber, the second bonding fiber, and the backbone fiber can also be selected from other materials.
- the melting point or softening point of the first bonding fiber may be 120°C, 125°C, 130°C, 140°C, 145°C, 155°C, 167°C, 183°C, 190°C, 200°C, 210°C or 220°C and so on.
- the melting point or softening point of the second bonding fiber may be 100°C, 105°C, 108°C, 120°C, 126°C, 138°C, 147°C, 156°C, 162°C, 170°C, or the like.
- the melting point or softening point of the backbone fiber is higher than the melting point or softening point of the first binder fiber by 20°C, 21°C, 23°C, 25°C, 26°C, 28°C, 30°C, 40°C, 50°C, 60°C, 100 °C, 150°C, 200°C, 280°C and so on.
- the second bonding fiber has a relatively low melting point or softening point, 105 to 170°C, and is first melted during the thermal calendering process to form a discontinuous fine uneven structure on the surface of the non-woven fabric.
- the melting point or softening point of the backbone fiber is higher than that of the first bonding fiber and the second bonding fiber, and can have high dimensional stability during the hot pressing process.
- the first bonding fiber and the second bonding fiber are partially or completely Melting, bonding each fiber to each other, and forming a three-dimensional network structure of non-woven fabric after cooling. If the melting point or softening point of the first and second bonding fibers is too low, it will cause excessive melting and serious sticking during the hot pressing process; the melting point or softening point of the first and second bonding fibers is too high It cannot be melted in time during hot pressing, and it is difficult to obtain the desired fine uneven structure on the surface of the non-woven fabric.
- the concave-convex structure can make the coating layer and the non-woven fabric have an anchoring effect for realizing strong bonding.
- the coating slurry is embedded in the fine cavities on the surface of the non-woven fabric, and the coating cannot move after curing, resulting in extremely strong bonding strength.
- the melting point or softening point of the second bonding fiber is lower than the melting point or softening point of the first bonding fiber by more than 15°C.
- the melting point or softening point of the second bonding fiber is set according to the melting point or softening point of the first bonding fiber, so as to select the material.
- the melting point or softening point of the second binding fiber is 15°C, 18°C, 20°C, 25°C, 45°C, 40°C, 28°C, 30°C, 50°C lower than the melting point or softening point of the first binding fiber Or 70°C, 90°C or 115°C and so on.
- the melting point or softening point of the second bonding fiber is lower than the melting point or softening point of the first bonding fiber by more than 15°C.
- the degree of melting at each temperature during the formation of the non-woven fabric forms a fine uneven structure on the surface.
- the backbone fiber accounts for 60-80% of the total mass of the backbone fiber and the bonding fiber; in other words, the backbone fiber accounts for 60-80% of the total mass of all fibers, for example, the backbone fiber accounts for all the fibers. 60%, 62%, 67%, 69%, 72%, 74%, 76% or 80% of the total mass, etc.
- the content of the backbone fiber as the main body of the structure is low, it will affect the mechanical strength of the non-woven fabric.
- the main function of the backbone fiber is to provide support strength. If the content of the backbone fiber is high, the backbone fiber will not be fully bonded and solidified by the bonding fiber. Affect the volume density of the non-woven fabric, and the mechanical strength is also difficult to guarantee.
- the second bonding fiber accounts for 10-40% of the total mass of the bonding fiber; as mentioned above, the melting point of the second bonding fiber is lower, and the content of the second bonding fiber is less, which will affect the non-woven fabric The formation of fine concave-convex structure on the surface; a high content of the second bonding fiber will cause the polymer to melt on the surface of the non-woven fabric, causing serious pore blockage and failing to obtain the desired pore structure.
- the fiber lengths of the first bonding fiber and the second bonding fiber are both 1 to 6 mm, and the fiber diameters of the first bonding fiber and the second bonding fiber are both Less than or equal to 10 ⁇ m.
- the fiber length of the backbone fiber is 1 to 6 mm; the fiber diameter of the backbone fiber is less than or equal to 4 ⁇ m.
- the fiber length of the first bonding fiber and the second bonding fiber may be 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, or the like.
- the fiber diameter of the first bonding fiber and the second bonding fiber can be 0.5 ⁇ m, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4.5 ⁇ m, 6 ⁇ m, 6.2 ⁇ m, 7.2 ⁇ m, 7.6 ⁇ m, 8.0 ⁇ m, 9.2 ⁇ m, or 10 ⁇ m, etc. .
- the fiber length of the backbone fiber can be 1mm, 2.5mm, 3mm, 3.6mm, 4.2mm, 5.1mm or 6mm and so on.
- the fiber diameter of the backbone fiber may be 0.2 ⁇ m, 0.6 ⁇ m, 1.2 ⁇ m, 1.8 ⁇ m, 2.5 ⁇ m, 3 ⁇ m, 3.2 ⁇ m, 3.6 ⁇ m, 4 ⁇ m, or the like.
- the fiber length of the backbone fiber and the bonding fiber is 1 to 6 mm.
- the fiber length of the backbone fiber and the bonding fiber is less than 1mm, and there may be a problem of too low strength of the non-woven fabric; the fiber length of the backbone fiber and the bonding fiber is greater than 6mm, and the excessively long fibers are easy to agglomerate and entangle, causing serious non-woven fabrics. Defects in appearance and performance.
- the diameter of the backbone fiber is less than or equal to 4 ⁇ m, the diameter of the bonding fiber is less than or equal to 10 ⁇ m, and the thickness of the obtained non-woven fabric is moderate. If the diameter of the backbone fiber is greater than 4 ⁇ m and the diameter of the bonding fiber is greater than 10 ⁇ m, the resulting non-woven fabric has a larger thickness.
- the non-woven fabric is used for lithium battery separators, and the battery can be filled with less active materials, reducing the battery capacity.
- the diameter of the backbone fiber is greater than 4 ⁇ m and the diameter of the bonding fiber is greater than 10 ⁇ m, which increases the possibility of large holes in the non-woven fabric.
- the coating slurry easily penetrates from the upper layer to the lower layer through the through holes, thereby increasing the number of needles in the coating layer. Possibility of defects such as holes.
- the length and diameter of the backbone fiber and the bonding fiber are within the above range, so that the pore size of the final non-woven fabric can be in an appropriate range; the concave-convex structure on the inner wall of the hole can improve the meshing of the non-woven fabric and the coating.
- Controlling the length and diameter of the backbone fiber and the bonding fiber to control the pore size which can avoid the formation of coating pinholes due to excessive pore structure, and the coating penetrates the back of the non-woven fabric, and even causes electrochemical safety problems; it can avoid excessive pore size.
- the small size makes it difficult for the coating to penetrate into the hole and engage with the uneven structure, resulting in low peel strength.
- the average pore diameter of the obtained non-woven fabric is not greater than 4.5 ⁇ m, and the ratio of the maximum pore diameter to the average pore diameter is 1-10. It is beneficial to prevent the coating slurry from penetrating from the coating surface to the back surface, causing the coating slurry to adhere to the surface of the guide roller and cause foreign matter contamination.
- the density of the non-woven fabric is 0.50 to 0.9 g/m 3 . It can prevent the coating slurry from penetrating from the coated surface to the back side, and reduce the probability of non-woven fabric blocking holes, can ensure sufficient porosity so as not to affect the ion transmission efficiency, and ensure the electrical performance of the non-woven fabric separator.
- the non-woven fabric of the present application can be obtained by preparing fiber base paper from various raw materials, and then subjecting the formed fiber base paper to hot calendering treatment.
- the surface of the non-woven fabric provided by the embodiments of the application has a fine uneven structure, so that when the surface of the non-woven fabric is coated, the uneven structure of the non-woven fabric can improve the adhesiveness of the non-woven fabric and improve the coating slurry
- the wetting ability of the surface of the non-woven fabric increases the contact area between the coating slurry and the non-woven fabric, so that the surfaces of the two are inlaid with each other to generate meshing force and achieve the effect of strong bonding.
- the non-woven fabric provided in the embodiments of the present application can be used to prepare the base film of the lithium battery separator. It should be noted that in other embodiments of the present application, the non-woven fabric can be used in other scenarios, and it is particularly suitable for For the application of coating or slurry for strong bonding, the embodiments of the present application do not limit the application of the non-woven fabric.
- the present application also provides a method for preparing the above-mentioned non-woven fabric.
- the heat-pressing treatment temperature is higher than the melting point or softening point temperature of the second bonding fiber by more than 10°C, for example 10-200°C higher, and the heat-pressing treatment temperature is higher than the aforementioned
- the backbone fiber has a low melting point or softening point temperature.
- the second bonding fiber can be almost completely melted, and the first bonding fiber is partially melted; in the process of hot pressing, the second bonding fiber is extruded to form a concave-convex structure, and accordingly, the first A bonding fiber bonds the backbone fiber.
- the hot pressing speed of the hot pressing treatment is 1-100 m/min. At this hot pressing speed, it is possible to prevent the second bonding fiber from clogging the formed pores.
- the application also provides a lithium battery separator base film, the lithium ion separator base film includes the non-woven fabric described in the claims.
- the present application also provides a lithium battery separator.
- the lithium battery separator includes a coating and the above-mentioned base film, and the coating is attached to the surface of the base film.
- the non-woven fabric provided in the embodiments of the present application can improve the adhesiveness of the non-woven fabric due to the uneven structure on the surface of the non-woven fabric, increase the contact area between the coating slurry and the non-woven fabric, and make the surfaces of both Mutual inlays generate meshing force to achieve the effect of strong joining.
- the uniformity and excellent adhesiveness of the non-woven fabric enable the coating layer and the non-woven fabric to be firmly combined with each other, and the coating layer and the non-woven fabric do not delaminate or peel off.
- Examples 1 to 6 respectively provide a non-woven fabric, and the specific fiber ratio is shown in Table 1;
- the raw materials of each embodiment were used to make fiber base paper with an areal density of 12g/m 2 using an inclined wire machine, and then the base paper was subjected to hot calendering treatment.
- the hot press used a steel roller/soft roller combination.
- the hot pressing temperature of each example See Table 1.
- the non-woven fabric was obtained by hot pressing.
- the obtained non-woven fabric was cut into A4 size samples, and alumina ceramic particles were coated on one of its outer surfaces through a mesh roll.
- the solid content of the coating slurry was 35% alumina/10% PVDF by weight. After coating, drying and drying are performed, and finally the non-woven fabric coating sample of this embodiment is obtained.
- Comparative Example 1 to Comparative Example 5 respectively provide a non-woven fabric, and the specific fiber ratio is shown in Table 2.
- each comparative example was used to make fiber base paper with an areal density of 12g/m 2 using an inclined wire paper machine, and then the base paper was subjected to hot calendering treatment.
- the hot press used a steel roller/soft roller combination.
- the hot pressing temperature of each comparative example See Table 2, to obtain a non-woven fabric.
- the obtained non-woven fabric was cut into A4 size samples, and alumina ceramic particles were coated on one of its outer surfaces through a mesh roll.
- the solid content of the coating slurry was 35% alumina/10% PVDF by weight. After coating, drying and drying are performed, and finally the non-woven fabric coating sample of this embodiment is obtained.
- the "area density" of the non-woven fabric is measured.
- the "thickness" of the non-woven fabric is measured; the "density” of the non-woven fabric is obtained by dividing the "area density” of the non-woven fabric and the "thickness” of the non-woven fabric.
- the "pore size" of the non-woven fabric is measured.
- Figure 1 is a surface electron micrograph of the non-woven fabric described in Example 1.
- FIG. 2 is a surface electron micrograph of the non-woven fabric described in Comparative Example 1.
- FIG. 3 is a surface electron micrograph of the non-woven fabric described in Comparative Example 2.
- FIG. 4 is a surface electron micrograph of the non-woven fabric described in Comparative Example 3.
- FIG. 5 is a surface electron micrograph of the non-woven fabric described in Comparative Example 4.
- Comparative Example 1 show that when the melting point or softening point of the main fiber used is close to the same as that of the first bonding fiber, that is, the difference between the melting point or softening point of the main fiber and the melting point or softening point of the first bonding fiber is less than 20 °C; As shown in Figure 2, excessive polymer melts on the surface of the non-woven fabric, causing serious pore blockage, making it difficult to obtain the desired pore structure, and the fine uneven structure on the surface of the non-woven fabric cannot be formed.
- Comparative Example 2 show that when the difference between the melting point or softening point of the first bonding fiber and the melting point or softening point of the second bonding fiber is less than 15°C, the first bonding fiber and the softening point The second bonding fiber melts almost simultaneously. As shown in Figure 3, the fine uneven structure on the surface of the non-woven fabric cannot be formed.
- the test results of Comparative Example 3 show that when the melting point or softening point of the first bonding fiber used is higher than 220°C and the difference between the melting point or softening point of the second bonding fiber is greater than 15°C, the first bonding fiber is The bonding fibers cannot be melted in time, the fibers cannot be fully bonded and solidified, and the structure of the non-woven fabric is loose. As shown in Figure 4, the fine uneven structure on the surface of the non-woven fabric cannot be formed.
- Comparative Example 4 show that when the melting point or softening point of the second bonding fiber used is lower than 100°C, the difference between the melting point or softening point of the first bonding fiber and the melting point or softening point of the second bonding fiber is greater than 15 At °C, as shown in Figure 5, the second bonding fiber is excessively melted during the hot pressing process, and the sticking roll is severe, which affects the surface smoothness of the non-woven fabric, and the fine uneven structure on the surface of the non-woven fabric cannot be formed.
- FIG. 6 is a surface electron micrograph of the non-woven fabric sample described in Comparative Example 5.
- FIG. 6 the non-woven fabric of Comparative Example 5 has no uneven structure formed in the holes, resulting in low peel strength.
- the non-woven fabrics of Examples 1-7 of this application have good properties, especially the peel strength of the coating layer is significantly higher than the peel strength of the samples of Comparative Examples 1-5, indicating that the bonding strength of the coating layer to the support layer has been significantly improved. Enhanced.
- the non-woven fabric provided by the embodiments of the present disclosure has good adhesiveness, and can increase the contact area between the coating slurry and the non-woven fabric, so that the surfaces of the two are inlaid with each other to generate meshing force, and achieve a strong The effect of joining.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Cell Separators (AREA)
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Abstract
Description
Claims (10)
- 一种无纺布,其特征在于,所述无纺布的原料包括主干纤维和粘结纤维;所述粘结纤维包括第一粘结纤维和第二粘结纤维;所述第一粘结纤维的熔点或软化点为120~220℃;所述第二粘结纤维的熔点或软化点为100~170℃,且所述第二粘结纤维的熔点或软化点比所述第一粘结纤维的熔点或软化点低15℃以上;所述主干纤维的熔点或软化点比所述第一粘结纤维的熔点或软化点高20℃以上。
- 根据权利要求1所述的无纺布,其特征在于,所述第二粘结纤维的熔点或软化点比所述第一粘结纤维的熔点或软化点低20~100℃。
- 根据权利要求1所述的无纺布,其特征在于,所述第一粘结纤维和所述第二粘结纤维的纤维长度均为1~6mm,且所述第一粘结纤维和所述第二粘结纤维的纤维直径均小于或等于10μm;所述主干纤维的纤维长度为1~6mm;所述主干纤维的纤维直径小于或等于4μm。
- 根据权利要求1所述的无纺布,其特征在于,所述主干纤维占所述主干纤维和所述粘结纤维总质量的60~80%;可选地,所述主干纤维占所述主干纤维和所述粘结纤维总质量的65~75%。
- 根据权利要求1所述的无纺布,其特征在于,所述第二粘结纤维占所述粘结纤维的总质量的10~40%;可选地,所述第二粘结纤维占所述粘结纤维总质量的20~30%。
- 根据权利要求1-5任一项所述的无纺布,其特征在于,所述无纺布的密度为0.50~0.9g/cm 3,平均孔径小于或等于4.5μm,最大孔径与平均孔径之比为1~10。
- 根据权利要求1-5任一项所述的无纺布,其特征在于,所述主干纤维的材料包括聚酯纤维,聚烯烃纤维,聚酰胺纤维,聚酰亚胺纤维,聚四氟乙烯纤维,聚苯硫醚纤维,聚醚醚酮纤维,聚丙烯腈纤维,聚碳酸酯纤维以及芳纶纤维中的至少一种;可选地,所述第一粘结纤维的材料包括未拉伸聚酯纤维,聚偏氟乙烯纤维,聚酰胺纤维,共聚酰胺纤维以及聚烯烃纤维中的至少一种;所述第二粘结纤维的材料包括聚烯烃纤维,共聚聚酯纤维以及共聚酰胺纤维中的至少一种。
- 如权利要求1-7任一项所述无纺布的制备方法,其特征在于,热压处理温度比所述第二粘结纤维的熔点或软化点温度高10℃以上,且所述热压处理温度不高于所述主干纤维的熔点或软化点温度;可选地,热压处理的热压速度为1~100m/min。
- 一种锂电池隔膜基膜,其特征在于,所述锂电池隔膜基膜包括权利要求1-7任一项所述的无纺布。
- 一种锂电池隔膜,其特征在于,所述锂电池隔膜包括涂层和权利要求9所述的基膜,所述涂层附着于所述基膜的表面。
Priority Applications (6)
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KR1020227039947A KR20230002768A (ko) | 2020-06-12 | 2020-06-12 | 부직포 및 그 제조 방법, 리튬 배터리 분리막 및 리튬 배터리 분리막 기저막 |
JP2022573619A JP2023528395A (ja) | 2020-06-12 | 2020-06-12 | 不織布、その作製方法、リチウム電池用セパレータおよびリチウム電池用セパレータベースフィルム |
EP20940422.7A EP4145613A4 (en) | 2020-06-12 | 2020-06-12 | NONWOVEN FABRIC AND PREPARATION METHOD THEREFOR, LITHIUM BATTERY DIAPHRAGM AND LITHIUM BATTERY DIAPHRAGM BASE MEMBRANE |
PCT/CN2020/095860 WO2021248465A1 (zh) | 2020-06-12 | 2020-06-12 | 无纺布及其制备方法、锂电池隔膜及锂电池隔膜基膜 |
CN202080001117.5A CN114080723B (zh) | 2020-06-12 | 2020-06-12 | 无纺布及其制备方法、锂电池隔膜及锂电池隔膜基膜 |
US17/928,412 US20230216142A1 (en) | 2020-06-12 | 2020-06-12 | Non-woven fabric and preparation method therefor, lithium battery diaphragm, and lithium battery diaphragm base membrane |
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PCT/CN2020/095860 WO2021248465A1 (zh) | 2020-06-12 | 2020-06-12 | 无纺布及其制备方法、锂电池隔膜及锂电池隔膜基膜 |
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EP (1) | EP4145613A4 (zh) |
JP (1) | JP2023528395A (zh) |
KR (1) | KR20230002768A (zh) |
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WO (1) | WO2021248465A1 (zh) |
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JPH11354093A (ja) * | 1998-06-04 | 1999-12-24 | Miki Tokushu Seishi Kk | 二次電池用セパレータ |
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- 2020-06-12 KR KR1020227039947A patent/KR20230002768A/ko unknown
- 2020-06-12 CN CN202080001117.5A patent/CN114080723B/zh active Active
- 2020-06-12 WO PCT/CN2020/095860 patent/WO2021248465A1/zh unknown
- 2020-06-12 US US17/928,412 patent/US20230216142A1/en active Pending
- 2020-06-12 EP EP20940422.7A patent/EP4145613A4/en active Pending
- 2020-06-12 JP JP2022573619A patent/JP2023528395A/ja active Pending
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KR20230002768A (ko) | 2023-01-05 |
EP4145613A4 (en) | 2023-10-25 |
CN114080723A (zh) | 2022-02-22 |
EP4145613A1 (en) | 2023-03-08 |
CN114080723B (zh) | 2022-10-14 |
US20230216142A1 (en) | 2023-07-06 |
JP2023528395A (ja) | 2023-07-04 |
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