WO2019218888A1 - 一种电池、电池隔膜及其制备方法 - Google Patents
一种电池、电池隔膜及其制备方法 Download PDFInfo
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- WO2019218888A1 WO2019218888A1 PCT/CN2019/085704 CN2019085704W WO2019218888A1 WO 2019218888 A1 WO2019218888 A1 WO 2019218888A1 CN 2019085704 W CN2019085704 W CN 2019085704W WO 2019218888 A1 WO2019218888 A1 WO 2019218888A1
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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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- 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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- 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
- H01M50/411—Organic material
- H01M50/429—Natural polymers
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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
- H01M50/431—Inorganic 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
- H01M50/431—Inorganic material
- H01M50/434—Ceramics
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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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- 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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M50/449—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M50/463—Separators, membranes or diaphragms characterised by their shape
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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
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M50/60—Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
- H01M50/609—Arrangements or processes for filling with liquid, e.g. electrolytes
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present disclosure relates to the field of batteries, and in particular to a battery, a battery separator, and a method of fabricating the same.
- a lithium ion battery is a secondary battery that is currently widely used.
- Lithium-ion batteries mainly rely on lithium ions to move between the positive and negative electrodes to work.
- Li + is intercalated and deintercalated between the two electrodes.
- the electrolyte is inserted into the negative electrode, the negative electrode is in a lithium-rich state, and the more lithium ions are embedded in the negative electrode, the higher the charging capacity); when discharged, the lithium ions embedded in the negative carbon layer are released. And returning to the positive electrode through electrolyte movement, the more lithium ions return to the positive electrode, the higher the discharge capacity.
- Lithium-ion batteries have the advantages of high operating voltage, large specific energy, long cycle life, low self-discharge, no pollution, no memory effect, etc., so they are widely used in mobile phones, portable devices, automobiles, aviation, scientific research, Modern electronics such as entertainment and military, and gradually replace traditional batteries.
- Lithium-ion batteries are mainly composed of four materials, including positive electrode materials, negative electrode materials, separators, and electrolytes. As one of its important components, the diaphragm plays a very important role in its performance.
- a battery separator is a layer of separator material between the positive and negative electrodes of a battery, usually referred to as a battery separator. The main function of the battery separator is to isolate the positive and negative electrodes and prevent electrons in the battery from passing freely, while allowing ions in the electrolyte to pass freely between the positive and negative electrodes.
- the ion conductivity of the battery separator is directly related to the overall performance of the battery.
- the function of isolating the positive and negative poles can limit the increase of current in the case of overcharging or temperature increase, prevent the battery short circuit from causing explosion, and have microporous self-closing protection function to protect the battery user and equipment.
- the role. Polyolefin materials are widely used as microporous separators because of their low cost, good mechanical strength and chemical stability, good overall performance, and low cost. However, due to its lack of thermal stability, its further application in batteries has been limited.
- the present disclosure provides a battery separator.
- the battery separator has a composite structure composed of a first member and a second member.
- the diaphragm includes:
- the first component is fabricated from a modified material that is provided to improve the thermal stability of the battery separator, the first component being a stack of nanowires distributed in layers;
- the second component is fabricated from a substrate material that is provided as a body of the battery separator, the first component being supported by the second component and supported by the second component.
- the thickness of the first element is on the order of microns and/or sub-micron.
- the first element has a thickness of 0.01 to 1 ⁇ m.
- the nanowires have an aspect ratio greater than 50.
- the nanowires have a diameter of from 1 to 100 nm and a length of from 0.1 to 100 ⁇ m.
- the modifying material comprises one of carbon nanotubes, nanosilver wires, boron carbide nanowires, nanocellulose, copper hydroxide nanowires, silicon oxide nanowires, hydroxyapatite nanowireskind or more.
- the substrate material is an organic polymeric material.
- the organic polymeric material includes a polyolefin.
- the polyolefin comprises polyethylene
- the first element has a porous structure.
- the present disclosure also provides a method of making the above battery separator.
- a method of preparing a battery separator is used to fabricate a battery separator having the following structure.
- the battery separator includes a first member and a second member, wherein the first member is supported in a layered manner on the second member, and the first member is composed of nanowires;
- Preparation methods include:
- the dispersion is transferred to the surface of the second member, and the dispersant in the dispersion on the surface of the second member is removed to load the nanowires in a layered manner on the surface of the second member.
- the dispersing agent includes one or more of water, ethanol, acetone, N-methylpyrrolidone, and the dispersion further contains an adhesive.
- the adhesive includes one or more of polyvinyl alcohol, polyacrylonitrile, polyacrylic acid, styrene butadiene rubber, carboxymethyl cellulose, polyvinylidene fluoride, polyvinyl pyrrolidone, and polyimide.
- polyvinyl alcohol polyacrylonitrile
- polyacrylic acid polyacrylic acid
- styrene butadiene rubber carboxymethyl cellulose
- polyvinylidene fluoride polyvinyl pyrrolidone
- polyimide polyimide
- an adjuvant is also included in the dispersion.
- the nanowires in the dispersion have a mass concentration of 0.01 to 50% and the adhesive has a mass concentration of 0.01 to 49%.
- the dispersion is transferred to the surface of the two components by coating.
- the manner of coating includes spin coating or knife coating or dip coating.
- the dispersion is transferred to the surface of the second component by dip coating, and the dip coating method includes:
- the second member is immersed in the dispersion at a first given speed and detached from the dispersion at a second given speed under tension by stretching.
- the second element is tensioned by a tensioning system consisting of a plurality of rollers, the tensioning system having at least one dip coating roller for immersing the second element in the dispersion, dip coating Part or all of the roller is immersed in the dispersion.
- the dip coating roller has a hollow cavity
- the dip coating roller has a vent passage that communicates with the hollow cavity and extends to the surface, and the second component contacts the dip coating roller in a face-to-face manner
- the surface, the cavity has a given degree of vacuum.
- the degree of vacuum is from 0.01 to 0.1 MPa.
- the present disclosure also provides a battery having the battery separator as described above.
- the battery separator provided by the present disclosure has a composite structure which is an innovation of the existing battery separator and improves its thermal stability by using a modified material. Further, the use of the modified material in the form of a nanowire can avoid the problem of an increase in the thickness and weight of the separator due to the introduction of the modified material, thereby achieving the effects of thermal stability, thickness and weight increase of the battery separator.
- FIG. 1 is a schematic structural view of a first battery separator according to an embodiment of the present disclosure
- FIG. 2 is a schematic structural view of a second battery separator according to an embodiment of the present disclosure
- FIG. 3 is a schematic structural view of a film forming apparatus for fabricating a second battery separator according to an embodiment of the present disclosure
- Figure 4 is a schematic view showing the structure of the first viewing angle of the dip coating roller in the film forming apparatus of Figure 3;
- Figure 5 is a schematic view showing the structure of a second viewing angle of the dip coating roller in the film forming apparatus of Figure 3;
- Fig. 6 is a cross-sectional view showing the cross-sectional structure of the dip coating roller in the film forming apparatus of Fig. 3 taken along the axial direction.
- Icons 100 - first element; 200 - second element; 300 - porous structure; 401 - storage slot; 402 - tensioning system; 403 - dip coating roller; 4031 - hollow cavity; 4032 - venting channel; Two components.
- the orientation or positional relationship of the indications is based on the orientation or positional relationship shown in the drawings, or the orientation or positional relationship that is conventionally placed when the disclosed product is used, for the convenience of describing the present disclosure and simplifying the description, rather than indicating or implying
- the device or component referred to must have a particular orientation, is constructed and operated in a particular orientation, and thus is not to be construed as limiting the disclosure.
- the terms “first”, “second”, “third”, and the like are used merely to distinguish a description, and are not to be construed as indicating or implying a relative importance.
- the first feature "on” or “under” the second feature may include direct contact of the first and second features, and may also include first and second features, unless otherwise specifically defined and defined. It is not in direct contact but through additional features between them.
- the first feature “above”, “above” and “above” the second feature includes the first feature directly above and above the second feature, or merely indicating that the first feature level is higher than the second feature.
- the first feature “below”, “below” and “below” the second feature includes the first feature directly below and below the second feature, or merely the first feature level being less than the second feature.
- battery separators particularly polyolefin separators for lithium ion batteries (including primary batteries and secondary batteries)
- battery separators particularly polyolefin separators for lithium ion batteries (including primary batteries and secondary batteries)
- defects of poor thermal stability in order to modify them to improve thermal stability.
- sexuality often requires improvements based on existing membranes.
- coating an inorganic material such as alumina on the surface of an existing (battery) membrane is a simple and efficient means of improving the thermal stability of the separator.
- a material capable of improving the thermal stability of the separator is used in the form of a nanowire, and is loaded on the original separator. material.
- a nanowire is used as a coating (as achieved by coating). The size and density of the one-dimensional nanowires are much smaller than those of the inorganic materials, and the thickness can be controlled to be smaller.
- one-dimensional nanowires have the potential to create new properties or improve existing properties due to their unique structural and interfacial effects.
- the battery separator is a multilayer composite bond.
- the battery separator has a composite structure composed of the first member 100 and the second member 200. Further, the above battery separator structure may be modified as needed.
- the battery separator has a composite structure composed of the first element 100 and the second element 200, and at the same time, the first element also has a plurality of holes.
- the porous structure 300 is shown in Figure 1, this embodiment provides that the battery separator is a multilayer composite bond.
- the battery separator has a composite structure composed of the first member 100 and the second member 200. Further, the above battery separator structure may be modified as needed. For example, in FIG. 2, the battery separator has a composite structure composed of the first element 100 and the second element 200, and at the same time, the first element also has a plurality of holes.
- the porous structure 300 is a multilayer composite bond.
- FIGS. 1 and 2 merely show the structure of the battery separator in a schematic manner, but the absolute thickness of the first member, the absolute thickness of the second member, and the relative thickness between the two.
- the size ratio relationship is not based on the size and scale in the figure.
- the thickness of the first element in the battery separator is significantly less than the thickness of the second element.
- the thickness of the first element is on the order of submicron or micron, and the thickness of the second element can be on the order of millimeters or centimeters.
- the thickness of the first component may be 0.01 to 1 micrometer ( ⁇ m), or the thickness of the first component is 0.03 ⁇ m, 0.05 ⁇ m, 0.08 ⁇ m, 0.1 ⁇ m, 0.4 ⁇ m, 0.6 ⁇ m. Any one of a range value determined between 0.8 ⁇ m and 1 ⁇ m or any range of values between any two point values.
- the thickness of the first component may be specified and verified according to specific product parameter requirements and test effects, and is not specifically limited in the embodiment of the present disclosure.
- the first element is composed of nanowires, and therefore, based on the difference in performance of the first element and the nanowire, and the difficulty of the preparation method thereof, combined with the performance consideration of the battery separator, the nanowire
- the specifications may have the following alternative definitions, for example, the nanowires have an aspect ratio greater than 50, such as an aspect ratio of 146, 138, 127, and the like. Further, the adjustment of the aspect ratio thereof is achieved by controlling the proper length and diameter of the nanowires, for example, the nanowires have a diameter of 1 to 100 nm and a length of 0.1 to 100 ⁇ m. In some specific alternative examples, the nanowires have a diameter of 100 nm and a length of 5 [mu]m.
- the material selection of the battery separator can be various, and it can be selected according to the actual situation.
- the first element is made of a modified material provided to improve the thermal stability of the separator, and the first element is a stack of nanowires distributed in layers.
- the first element is in the form of a film (film layer) having a thickness of the submicron or micron order as described above.
- the aforementioned first element is a stack of nanowires, and the stack of nanowires may exist in various ways.
- the first element is a single layer stack structure having a nanowire diameter, wherein the nanowires are arranged in an array. In the longitudinal direction, the nanowires in the same column are arranged end to end; in the lateral direction, the columns are arranged side by side. Or, in some examples, the nanowires are stacked in a crisscross pattern. Or, in other examples, the nanowires are staggered and staggered.
- the manner of stacking the nanowires may be defined by the manner in which the battery separator is prepared, and is not specifically limited in the embodiment of the present disclosure. Further, the deposit composed of the nanowires may also be two layers, three layers, or even more layers, and each layer may be made of the same or different stacked forms.
- the first element produced by the deposit formed by the nanowire in an appropriate manner has the characteristics of high porosity, uniform pore size, light weight, and high strength. Therefore, under the premise of solving the thermal stability of the polyolefin separator, the nanowire coating has the characteristics of thin thickness and light weight, and is in line with the development direction of light weight and high energy of the battery.
- the aforementioned first element having a hole may be formed by stacking nanowires on the second element.
- the holes can be made by a non-human active layer in the process of fabricating the battery separator, and the holes can also be considered to be purposefully controlled (distribution density, distribution mode, pore size) and formed.
- the effect of the movement of the ions is determined by the manner in which the holes are formed, such as the aperture, the void ratio, etc., in order to adjust the application of the battery separator having the first element and the second element to the battery.
- modifying materials such as one of carbon nanotubes, nano silver wires, boron carbide nanowires, nanocellulose, copper hydroxide nanowires, silicon oxide nanowires, and hydroxyapatite nanowires. kind or more.
- the second element is fabricated from a base material that is provided as a body of the diaphragm, and the first element is loaded on the second element and supported by the second element.
- the aforementioned body as a diaphragm may be the diaphragm itself in the prior art battery separator technology.
- a separator that separates electrons and allows ions to pass therethrough it is provided and used as a body, and exerts its corresponding action on electrons and ions.
- the modifying material for the first component has a plurality of options, and accordingly, the substrate material for the second component can be selected in a variety of ways, and can be appropriately selected depending on the specific properties and process requirements.
- the second member is selected to be a polyolefin such as polyethylene, polypropylene or the like.
- a battery is also provided in the embodiment of the present disclosure, which may be a primary battery or a secondary battery, such as a rechargeable lithium ion battery.
- the battery has a casing in which the battery separator is disposed, and a positive electrode and a negative electrode separated by a battery separator. A positive electrode region is formed between the positive electrode and the battery separator, and a negative electrode region is formed between the negative electrode and the battery separator. The same electrolyte is injected into the positive electrode region and the negative electrode region.
- a method of fabricating the battery separator is also provided accordingly.
- Preparation methods include:
- Step S101 providing a dispersion in which nanowires are dispersed in a dispersant.
- the nanowires are preferably sufficiently dispersed in the dispersant, and in order to maintain the structure of the nanowires, the dispersant is generally a poor solvent for the nanowires, ie, the dispersant does not significantly dissolve the nanowires, thereby destroying the nanostructures.
- the nanowires are also preferably uniformly dispersed in the dispersant rather than being sequestered in the dispersant.
- the dispersion may optionally be present in the form of a suspension, suspension, emulsion, and used.
- the dispersant is selected to be water and the nanowires are selected as carbon nanotubes. It can be uniformly dispersed in water by a vibration method such as ultrasonic treatment or high-speed stirring. Generally, the dispersion is easily prepared on site and used in the field to avoid the problem of uneven distribution of the nanowires in the dispersant. However, in some cases where the requirements are relatively not too high or dispersions which are well dispersed and stable, the dispersion may be pre-formulated or purchased. Further, the concentration of the nanowires in the dispersion may be from 0.01 to 50% by weight, for example, from 0.1 to 43% by weight, from 3 to 36% by weight, from 14 to 29% by weight, and the like.
- the material selection of the nanowire can be referred to the foregoing, and will not be described herein.
- the dispersing agent may be selected from one or more of water, ethanol, acetone, and N-methylpyrrolidone.
- the adhesive may be selected from polyvinyl alcohol, polyacrylonitrile, polyacrylic acid, One or more of styrene-butadiene rubber, carboxymethyl cellulose, polyvinylidene fluoride, polyvinylpyrrolidone, and polyimide.
- the mass concentration of the adhesive may be 0.01 to 49%, 5 to 37%, 11 to 27%, 16 to 20%, or the like.
- an auxiliary agent may be added to the dispersant as a wetting action, including glycerin, sodium butylbenzenesulfonate, propylene glycol, and polyoxyethylene sulfide.
- Step S102 transferring the dispersion to the surface of the second element, removing the dispersing agent in the dispersion liquid on the surface of the second element to load the nanowires in a layered manner on the surface of the second element.
- the method of transferring the dispersion may be coating, such as spin coating or knife coating or dip coating. Removal of the dispersant in the dispersion can be achieved by evaporation, for example, heating a second component loaded with a dispersion to evaporate a dispersant such as water. The heating can be by irradiation heating.
- the evaporation speed of the dispersion should be appropriately controlled to avoid the degree of bonding of the formed first member to the second member due to the unreasonable evaporation mode.
- the dispersion is transferred to the surface of the second member by dip coating.
- dip coating methods include:
- the second member is immersed in the dispersion at a first given speed and detached from the dispersion at a second given speed under tension by stretching.
- the second element passes through the dispersion, and the nanowires or optionally added adhesive in the dispersion are combined in the second element by chemical action and adsorption, capillary action, and the like.
- the dispersant in the dispersion is then removed from the surface of the second component in a suitable manner while leaving the nanowires on the surface of the second component.
- the dispersion is transferred to the second member through a film forming device.
- the general structure of the film forming apparatus can be referred to as follows, see Fig. 3.
- the film forming apparatus has a liquid storage tank 401 which is used to store the dispersion.
- the film forming apparatus also has a tensioning system 402.
- the tensioning system includes a plurality of rollers.
- the tensioning system comprises three rollers, one of which is distributed between the other two rollers, and the center point of the projection of the three rollers on the plane can form a triangle.
- the second element in the battery diaphragm is tensioned by a tensioning system having at least one dip coating roller 403 for immersing the second member 200 in the dispersion (i.e., the roller located in the middle portion), dip coating Part or all of the shaft is immersed in the dispersion (in one example, the immersion depth is 1/4 of its radius to full immersion).
- the immersion depth of the dip-coated roller can be achieved by a moving mechanism (not shown) which enables the immersion roller to be moved in a suitable manner, such as vertically, relative to the dispersion.
- the tensioning system can properly release the second member to adjust the immersion depth of the dip coating roller without moving the two rollers outside the dip roller.
- the three rollers that make up the tensioning system are movable, making it easier to control the immersion depth adjustment of the dip coating roller.
- the dip coating roller 403 has a hollow cavity 4031, and the dip coating roller has a vent channel 4032 that communicates with the hollow cavity and extends to the surface.
- the second component is in contact with the surface of the dip coating roller in a face-to-face manner, and has a given degree of vacuum in the hollow cavity, for example, a degree of vacuum of 0.01 to 0.1 MPa.
- a vacuum generator diagram for causing the dip coating roller to produce a desired degree of vacuum is not shown, and a commercially available vacuum pump or the like can be used.
- the dispersion is more easily adsorbed and bonded to the surface of the second member under the action of the negative pressure.
- the pore passage of the dip coating roller it is also possible to modulate the porosity, pore size, and pore distribution pattern of the first member to achieve the desired effect.
- the adjustment of the thickness of the first member can be achieved by adjusting the concentration of the nanowires in the dispersion, the depth of the dip coating roller immersed in the dispersion, and the degree of vacuum of the dip coating roller.
- concentration of the nanowires in the dispersion the concentration of the nanowires in the dispersion
- depth of the dip coating roller immersed in the dispersion the depth of the dip coating roller immersed in the dispersion
- degree of vacuum of the dip coating roller The inventors have found that the thicker the solution, the thicker the coating; the deeper the immersion, the thicker the coating; the higher the vacuum, the thicker the coating.
- the battery separator is a sheet structure having a multilayer film structure.
- the second element constitutes a base film
- the first element constitutes a surface film.
- the surface film may be one layer or multiple layers. When the surface film has a plurality of layers, it may be respectively distributed on two sides in the thickness direction of the base film, and the number of layers of the surface film distributed on each side may be different or the same, or may be distributed only in the two sides in the thickness direction. Any one of them.
- Table 1 lists examples of a plurality of battery separators, including the materials of manufacture, process methods, and properties.
- the battery was fabricated using the battery separator prepared in the above Examples 1-4, and the electrical properties were examined. The test results are shown in Table 2 below.
- Table 2 shows the battery performance of the battery separator.
- the batteries of Examples 1-4 and Comparative Examples 1-6 have the same main structure including a positive electrode, a negative electrode, an electrolyte, and a separator.
- the separator of the battery of Examples 1-4 was produced by the method proposed in the examples of the present disclosure and loaded with a nanowire coating; the separator of the battery of Comparative Examples 1-4 was a commercially available product. It is loaded with a millimeter-scale coating of particulate matter.
- the separator of the battery of Comparative Example 5-6 was a commercially available product and was not loaded with a substance for forming a coating.
- the polyethylene film or the polypropylene film can be produced, for example, by a wet non-woven process.
- the battery separator provided by the present disclosure has a composite structure which is an innovation of the existing battery separator and improves its thermal stability by using a modified material. Further, the use of the modified material in the form of a nanowire can avoid the problem of an increase in the thickness and weight of the separator due to the introduction of the modified material, thereby achieving the effects of thermal stability, thickness and weight increase of the battery separator.
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Abstract
Description
Claims (19)
- 一种电池隔膜,其特征在于,所述电池隔膜具有第一元件和第二元件构成的复合结构,所述电池隔膜包括:所述第一元件由被提供来改善所述电池隔膜的热稳定性的改性材料制作而成,所述第一元件是以层状分布的纳米线的堆积体;所述第二元件由被提供来作为所述电池隔膜的本体的基底材料制作而成,所述第一元件负载在所述第二元件、并且受到所述第二元件的支撑。
- 根据权利要求1所述的电池隔膜,其特征在于,所述第一元件的厚度为微米和/或亚微米级以下。
- 根据权利要求1所述的电池隔膜,其特征在于,所述第一元件的厚度为0.01~1μm。
- 根据权利要求1所述的电池隔膜,其特征在于,所述纳米线的长径比大于50。
- 根据权利要求4所述的电池隔膜,其特征在于,所述纳米线的直径为1~100nm,长度为0.1~100μm。
- 根据权利要求1所述的电池隔膜,其特征在于,所述改性材料包括碳纳米管、纳米银线、碳化硼纳米线、纳米纤维素、氢氧化铜纳米线、一氧化硅纳米线、羟基磷灰石纳米线中的一种或多种。
- 根据权利要求1所述的电池隔膜,其特征在于,所述基底材料为有机高分子材料,优选地,所述有机高分子材料包括聚烯烃,更优选地,所述聚烯烃包括聚乙烯。
- 根据权利要求1所述的电池隔膜,其特征在于,第一元件具有多孔结构。
- 一种电池隔膜的制备方法,其特征在于,所述电池隔膜包括第一元件和第二元件,其中,所述第一元件以层状方式负载在所述第二元件,且 所述第一元件由纳米线构成;所述制备方法包括:提供在分散剂中分散有所述纳米线的分散液;将所述分散液转移至所述第二元件表面,去除在所述第二元件表面的所述分散液中的所述分散剂以使所述纳米线以层状的方式负载在所述第二元件表面。
- 根据权利要求9所述的电池隔膜的制备方法,其特征在于,所述分散剂包括水、乙醇、丙酮、N-甲基吡咯烷酮中的一种或多种。
- 根据权利要求10所述的电池隔膜的制备方法,其特征在于,所述分散液中还包含有胶粘剂,优选地,所述胶粘剂包括聚乙烯醇、聚丙烯腈、聚丙烯酸、丁苯橡胶、羧甲基纤维素、聚偏氟乙烯、聚乙烯吡咯烷酮、聚酰亚胺中的一种或多种,更优选地,所述分散液中还包括助剂。
- 根据权利要求10所述的电池隔膜的制备方法,其特征在于,分散液中的纳米线的质量浓度为0.01~50%,所述胶粘剂的质量浓度为0.01~49%。
- 根据权利要求9所述的电池隔膜的制备方法,其特征在于,所分散液是通过涂覆的方式被转移至所述二元件表面的,优选地,所述涂覆的方式包括旋涂或刮涂或浸涂。
- 根据权利要求9所述的电池隔膜的制备方法,其特征在于,所分散液是通过浸涂的方式被转移至所述第二元件表面,所述浸涂的方法包括:使所述第二元件通过拉伸而张紧的条件下,以第一给定速度浸入所述分散液并以第二给定速度从所述分散液中脱离;优选地,所述第二元件是由多个滚轴组成的张紧系统而被张紧的,所述张紧系统中至少具有一个使所述第二元件浸入所述分散液的浸涂滚轴,所述浸涂滚轴的部分或全部浸入所述分散液;更优选地,所述浸涂滚轴具有中空腔,且所述浸涂滚轴具有与所述中 空腔连通且延伸至表面的气孔通道,所述第二元件以面面贴合的方式接触于所述浸涂滚轴表面,所述中空腔内具有给定的真空度,进一步优选地,所述真空度为0.01~0.1MPa。
- 一种电池,其特征在于,所述电池具有如权利要求1至8中任意一项所述的电池隔膜。
- 根据权利要求15所述的电池,其特征在于,所述电池是锂离子电池。
- 根据权利要求16所述的电池,其特征在于,所述锂离子电池是可充电的锂离子电池。
- 根据权利要求15所述的电池,其特征在于,所述电池包括壳体,所述壳体内设置有所述电池隔膜,以及由所述电池隔膜分隔开的正极和负极;所述正极和所述电池隔膜之间形成正极区,所述负极和所述电池隔膜之间形成负极区。
- 根据权利要求18所述的电池,其特征在于,所述正极区和所述负极区内注入有相同的电解液。
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JP2020566870A JP2021514111A (ja) | 2018-05-16 | 2019-05-06 | 電池、電池用セパレータ及びその製造方法 |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111682157A (zh) * | 2020-06-19 | 2020-09-18 | 珠海冠宇电池股份有限公司 | 电池及其制备方法以及用电设备 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108630871B (zh) * | 2018-05-16 | 2021-05-28 | 深圳市星源材质科技股份有限公司 | 一种电池、电池隔膜及其制备方法 |
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CN113140872B (zh) * | 2021-04-14 | 2022-10-14 | 湖南农业大学 | 双面不对称锂电池复合涂层隔膜、生产工艺及锂电池 |
CN113540697B (zh) * | 2021-06-28 | 2022-09-09 | 合肥国轩高科动力能源有限公司 | 一种复合隔膜及其制备方法 |
KR102617166B1 (ko) * | 2021-12-21 | 2023-12-21 | 주식회사 엘지에너지솔루션 | 전기화학소자용 분리막 및 이를 포함하는 전기화학소자 |
WO2023183239A1 (en) * | 2022-03-24 | 2023-09-28 | Celgard, Llc | Coated separator with ceramic micro-wires |
CN115799610B (zh) * | 2023-02-06 | 2023-05-02 | 星源材质(南通)新材料科技有限公司 | 复合膜及其制备方法、包裹锂盐接枝碳纳米管的pvdf微孔膜与固态电池 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102769116A (zh) * | 2012-08-09 | 2012-11-07 | 常州大学 | 一种具有多孔复合涂层的锂离子电池隔膜及其制备方法 |
CN104157812A (zh) * | 2014-04-23 | 2014-11-19 | 华南理工大学 | 锂离子电池隔膜及其制备方法及锂离子电池 |
CN105140451A (zh) * | 2015-07-06 | 2015-12-09 | 佛山荷韵特种材料有限公司 | 一种锂离子电池隔膜及其制备方法 |
CN105529425A (zh) * | 2014-11-19 | 2016-04-27 | 比亚迪股份有限公司 | 一种陶瓷隔膜及其制备方法和应用 |
CN107565081A (zh) * | 2017-07-11 | 2018-01-09 | 中国科学院上海硅酸盐研究所 | 一种羟基磷灰石超长纳米线基耐高温电池隔膜及其应用 |
CN107785522A (zh) * | 2016-08-29 | 2018-03-09 | 比亚迪股份有限公司 | 一种锂离子电池隔膜和锂离子电池及其制备方法 |
CN108630871A (zh) * | 2018-05-16 | 2018-10-09 | 深圳市星源材质科技股份有限公司 | 一种电池、电池隔膜及其制备方法 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9486821B2 (en) * | 2012-09-28 | 2016-11-08 | Nissan Motor Co., Ltd. | Coating apparatus for applying coating material onto sheet member |
WO2014091856A1 (ja) * | 2012-12-12 | 2014-06-19 | 日本電気株式会社 | セパレータ、電極素子、蓄電デバイスおよび前記セパレータの製造方法 |
CN103236512A (zh) * | 2013-04-19 | 2013-08-07 | 厦门大学 | 一种陶瓷隔膜及其在锂离子电池中的应用 |
US10476114B2 (en) * | 2013-05-03 | 2019-11-12 | The Board Of Trustees Of The Leland Stanford Junior University | Rechargeable battery safety by multifunctional separators and electrodes |
JP6445273B2 (ja) * | 2013-08-14 | 2018-12-26 | 三菱製紙株式会社 | リチウムイオン電池用セパレータ用塗液及びリチウムイオン電池用セパレータ |
WO2015171607A1 (en) * | 2014-05-05 | 2015-11-12 | Board Of Regents, The University Of Texas System | Bifunctional separators for lithium-sulfur batteries |
JP6428536B2 (ja) * | 2014-08-29 | 2018-11-28 | 日産自動車株式会社 | 塗膜を形成したシート材の製造装置、および塗膜を形成したシート材の製造方法 |
JP6152184B2 (ja) * | 2015-03-13 | 2017-06-21 | 住友化学株式会社 | セパレータ捲回体、電池の製造方法、及びセパレータ捲回体の製造方法 |
KR20160133275A (ko) * | 2015-05-12 | 2016-11-22 | 주식회사 엘지화학 | 셀룰로오스 나노섬유 코팅된 전기화학소자용 세퍼레이터 및 그의 제조방법 |
CN105185940B (zh) * | 2015-10-23 | 2018-10-09 | 旭成(福建)科技股份有限公司 | 聚烯烃/纳米晶体纤维素复合隔膜的制备方法及其应用 |
CN105374971A (zh) * | 2015-11-30 | 2016-03-02 | 江苏华东锂电技术研究院有限公司 | 一种锂离子电池隔膜及其制备方法 |
CN106299222B (zh) * | 2016-09-05 | 2019-05-07 | 东莞新能源科技有限公司 | 一种隔膜及其二次电池 |
CN106684298B (zh) * | 2017-01-22 | 2020-03-31 | 湖南立方新能源科技有限责任公司 | 一种锂离子电池的应用方法 |
CN107342386A (zh) * | 2017-07-03 | 2017-11-10 | 河北金力新能源科技股份有限公司 | 一种耐高温低电阻率锂离子电池隔膜的制备方法 |
-
2018
- 2018-05-16 CN CN201810471842.3A patent/CN108630871B/zh active Active
-
2019
- 2019-05-06 EP EP19802545.4A patent/EP3796418A4/en active Pending
- 2019-05-06 KR KR1020207024767A patent/KR102475114B1/ko active IP Right Grant
- 2019-05-06 WO PCT/CN2019/085704 patent/WO2019218888A1/zh unknown
- 2019-05-06 US US16/975,206 patent/US20200411829A1/en active Pending
- 2019-05-06 JP JP2020566870A patent/JP2021514111A/ja active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102769116A (zh) * | 2012-08-09 | 2012-11-07 | 常州大学 | 一种具有多孔复合涂层的锂离子电池隔膜及其制备方法 |
CN104157812A (zh) * | 2014-04-23 | 2014-11-19 | 华南理工大学 | 锂离子电池隔膜及其制备方法及锂离子电池 |
CN105529425A (zh) * | 2014-11-19 | 2016-04-27 | 比亚迪股份有限公司 | 一种陶瓷隔膜及其制备方法和应用 |
CN105140451A (zh) * | 2015-07-06 | 2015-12-09 | 佛山荷韵特种材料有限公司 | 一种锂离子电池隔膜及其制备方法 |
CN107785522A (zh) * | 2016-08-29 | 2018-03-09 | 比亚迪股份有限公司 | 一种锂离子电池隔膜和锂离子电池及其制备方法 |
CN107565081A (zh) * | 2017-07-11 | 2018-01-09 | 中国科学院上海硅酸盐研究所 | 一种羟基磷灰石超长纳米线基耐高温电池隔膜及其应用 |
CN108630871A (zh) * | 2018-05-16 | 2018-10-09 | 深圳市星源材质科技股份有限公司 | 一种电池、电池隔膜及其制备方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3796418A4 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111682157A (zh) * | 2020-06-19 | 2020-09-18 | 珠海冠宇电池股份有限公司 | 电池及其制备方法以及用电设备 |
US11450932B2 (en) | 2020-06-19 | 2022-09-20 | Zhuhai Cosmx Battery Co., Ltd. | Battery, preparation method thereof and electric device |
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