WO2023155191A1 - 纳米浆料及其制备方法、电池隔膜及其制作方法和电池 - Google Patents

纳米浆料及其制备方法、电池隔膜及其制作方法和电池 Download PDF

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WO2023155191A1
WO2023155191A1 PCT/CN2022/077088 CN2022077088W WO2023155191A1 WO 2023155191 A1 WO2023155191 A1 WO 2023155191A1 CN 2022077088 W CN2022077088 W CN 2022077088W WO 2023155191 A1 WO2023155191 A1 WO 2023155191A1
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nano
hydrophilic polymer
slurry
ceramic material
range
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English (en)
French (fr)
Inventor
王艳杰
陈泽林
沈剑强
林陆菁
黄慧桢
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Shenzhen Senior Technology Material Co Ltd
Senior Material Europe AB
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Shenzhen Senior Technology Material Co Ltd
Senior Material Europe AB
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Priority to EP22926518.6A priority Critical patent/EP4485662A4/en
Priority to JP2024545002A priority patent/JP7819330B2/ja
Priority to CN202280092215.3A priority patent/CN119096405A/zh
Priority to KR1020247025980A priority patent/KR20240131423A/ko
Priority to PCT/CN2022/077088 priority patent/WO2023155191A1/zh
Publication of WO2023155191A1 publication Critical patent/WO2023155191A1/zh
Priority to US18/792,273 priority patent/US20240396170A1/en
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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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • 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
    • 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
    • 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
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • 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
    • H01M50/44—Fibrous material
    • 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
    • H01M50/443—Particulate material
    • 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
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • 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
    • 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
    • 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
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H01M50/461—Separators, membranes or diaphragms characterised by their combination with electrodes with adhesive layers between electrodes and separators
    • 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
    • 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

  • the invention relates to the field of batteries, in particular to a nano-slurry and a preparation method thereof, a battery diaphragm and a preparation method thereof, and a battery.
  • Lithium battery separator is one of the core components of lithium-ion batteries, and its performance has a very important impact on the overall performance of lithium batteries, and is one of the key technologies restricting the development of lithium batteries. With the continuous expansion of the application field of lithium batteries and the deepening influence of lithium battery products in people's lives, people's requirements for the performance of lithium batteries are also getting higher and higher. In order to meet the development requirements of lithium batteries, the separator, as an important part of lithium batteries, should not only have good chemical stability and low manufacturing cost, but also improve the safety performance of lithium-ion batteries is also an important trend in the development of lithium batteries.
  • the diaphragm of lithium battery can include a base film and a coating covering at least one surface of the base film.
  • the slurry of the coating can be prepared based on ceramic particles.
  • the surface energy of ceramic particles can easily cause ceramic particles to agglomerate. Problems lead to poor surface uniformity of the coating, which in turn affects the bonding of the pole pieces in the subsequent battery assembly.
  • the invention provides a nano-slurry and its preparation method, a battery diaphragm and its preparation method and a battery, so as to solve the problem that the surface energy of ceramic particles can lead to agglomeration.
  • a nano-slurry for surface coating of a diaphragm including: a dispersion medium, a ceramic material, a one-dimensional nano-material, a linear hydrophilic polymer and an adhesive, wherein the The mass ratio of the one-dimensional nanomaterial to the ceramic material is in the range of 0.01% to 20%, the content of water in the dispersion medium is more than 90 wt%, and the particle size of the ceramic material is in the range of 5-500nm within range.
  • the linear hydrophilic polymer is attached to the one-dimensional nanomaterial and connected to the ceramic material.
  • the mass ratio of the linear hydrophilic polymer to the water in the dispersion medium is in the range of 0.01% to 0.1%.
  • the molecular weight of the linear hydrophilic polymer is in the range of 1000 g/mol-10000 g/mol.
  • the linear hydrophilic polymer includes an amine-based hydrophilic polymer.
  • the linear hydrophilic polymer includes at least one of the following:
  • Polyacrylamide polyethyleneimine.
  • the diameter of the one-dimensional nanomaterial is in the range of 1-50 nanometers, and the length of the one-dimensional nanomaterial is in the range of 100-1000 nanometers.
  • the mass ratio of the adhesive to the ceramic material is in the range of 1% to 10%.
  • the adhesive includes at least one of the following:
  • a method for preparing nano-slurries is provided, which is used to prepare the nano-slurries involved in the first aspect and its alternatives, the preparation method comprising:
  • Adhesives are added to the specified solution to obtain nanoslurries.
  • the linear hydrophilic polymer after the linear hydrophilic polymer is added to the specified dispersion, it also includes:
  • a battery separator including a base film and a coating:
  • the coating is formed by applying nano slurry to at least one surface of the base film
  • the specified nano-slurry is the nano-slurry involved in the first aspect and its alternatives or the nano-slurry prepared by the preparation method of the second aspect.
  • a battery separator including: a base film and a coating, the coating contains ceramic materials, one-dimensional nanomaterials and linear hydrophilic polymers, wherein the one-dimensional nanomaterials
  • the mass ratio of the material to the ceramic material is in the range of 0.01% to 20%, the particle size of the ceramic material is in the range of 5-500nm, and the linear hydrophilic polymer wraps the one-dimensional nanomaterial And connect the ceramic material.
  • a battery including the battery separator mentioned in the third aspect or the fourth aspect.
  • a one-dimensional nano-material is introduced into the ceramic material to reduce the surface energy of the ceramic material, thereby reducing the surface roughness of the formed coating degree, at the same time,
  • a linear hydrophilic polymer is also used, so that the linear hydrophilic polymer acts as a bridge between the one-dimensional nanomaterial and the ceramic material, so that the two can be completely combined, and the ceramic material can be further fully reduced.
  • the tendency of the material to agglomerate further reduces the surface roughness of the resulting coating.
  • the introduction of the linear hydrophilic polymer can also help to avoid the sedimentation of the slurry and improve the stability of the slurry.
  • the quality selection of one-dimensional nanomaterials has a certain correlation with the final slurry state (such as viscosity), and then, the present invention creatively discovers and utilizes this finding, and integrates a
  • the mass ratio of the nano-dimensional material to the ceramic material is selected in the range of 0.01% to 20%, which effectively ensures that the slurry can be easily coated.
  • Fig. 1 is the schematic flow sheet of the preparation method of nano slurry in an embodiment of the present invention
  • FIG. 2 is a schematic flowchart of a method for manufacturing a battery separator in an embodiment of the present invention.
  • first and second are only used for description purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the quantity of indicated technical features. Thus, a feature defined as “first” and “second” may explicitly or implicitly include one or more of these features.
  • a plurality means a plurality, such as two, three, four, etc., unless otherwise specifically defined.
  • connection and other terms should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral body; it can be a mechanical connection , can also be electrically connected or can communicate with each other; it can be directly connected or indirectly connected through an intermediary, and it can be the internal communication of two components or the interaction relationship between two components.
  • connection and other terms should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral body; it can be a mechanical connection , can also be electrically connected or can communicate with each other; it can be directly connected or indirectly connected through an intermediary, and it can be the internal communication of two components or the interaction relationship between two components.
  • An embodiment of the present invention provides a nano-slurry for surface coating of a diaphragm, including: a dispersion medium, a ceramic material, a one-dimensional nano-material, a linear hydrophilic polymer, and an adhesive.
  • the dispersion medium therein can be any liquid that can be used for material dispersion, and the content of water in the dispersion medium is more than 90wt%, and can also include dispersion mediums such as ethanol, acetone, and N-methylpyrrolidone.
  • the water content can be 90wt%, 92wt%, 93wt%, 95wt%, 98wt%, 99wt%, 100wt%.
  • the water content in the dispersion medium when the water content in the dispersion medium is not 100wt%, it shows that in the dispersion medium, in addition to water, other solvents are also introduced, and then, due to the introduction of other solvents in the water, the surface of the mixed solvent can be greatly reduced.
  • the reduction of tension and surface tension is beneficial to further enhance the dispersion uniformity of ceramic materials, one-dimensional nanomaterials and linear hydrophilic polymers, so that linear hydrophilic polymers can be more fully connected with ceramic materials and one-dimensional nanomaterials , so better solve the problem of agglomeration of ceramic particles.
  • the ceramic material therein includes, for example, at least one of the following: alumina, silicon oxide, titanium oxide, magnesium hydroxide, boehmite, etc., wherein the particle size of the ceramic material (such as alumina) is within the range of 5-500nm , in this range, the surface energy of the ceramic material is very large, so it is very easy to agglomerate, resulting in unstable slurry.
  • the embodiment of the present invention introduces one-dimensional nanomaterials and linear Hydrophilic polymers both reduce this tendency to agglomerate.
  • the ceramic material used is usually larger than 600nm, the technical problem of agglomeration usually does not occur, and furthermore, the discovery and solution of the agglomeration problem are both improvements of the embodiments of the present invention one.
  • the one-dimensional nanomaterials may also be understood as nanowires, nanotubes or nanorods, for example, may include at least one of the following: nanocellulose, carbon nanotubes, aramid nanofibers, and polyimide nanofibers.
  • the present invention introduces one-dimensional nanomaterials into the ceramic material to reduce the surface energy of the material, thereby reducing the surface roughness of the formed coating
  • the mass ratio of the one-dimensional nanomaterial to the ceramic material is in the range of 0.01% to 20%.
  • the mass ratio can be 0.01%, 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11% , 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%.
  • the mass ratio of the one-dimensional nanomaterial to the ceramic material is in the range of 12%-20%.
  • one-dimensional nanomaterials account for 1%-20% of ceramic materials.
  • the quality selection of one-dimensional nanomaterials has a certain correlation with the final slurry state (such as viscosity) (its correlation will be described later in conjunction with Table 1), and then, the present invention
  • the mass ratio of the one-dimensional nanometer material to the ceramic material is selected in the range of 0.01% to 20%, which effectively ensures that the slurry can be easily coated.
  • the diameter of the one-dimensional nanomaterial is in the range of 1-50 nanometers, and the length of the one-dimensional nanomaterial is in the range of 100-1000 nanometers.
  • the linear hydrophilic polymer plays a bridging role between the one-dimensional nanomaterial and the ceramic material, thereby completely combining the two, further fully reducing the tendency of the ceramic material to agglomerate, and further reducing the surface roughness of the formed coating.
  • the introduction of the linear hydrophilic polymer can also help to avoid the sedimentation of the slurry and improve the stability of the slurry. The specific performance comparison will be described later in conjunction with Table 1.
  • the mass ratio of the linear hydrophilic polymer to the water in the dispersion medium is in the range of 0.01% to 0.1%, such as 0.01%, 0.02%, 0.03%, 0.04%, 0.05% , 0.06%, 0.07%, 0.08%, 0.09%, 0.1%.
  • the molecular weight of the linear hydrophilic polymer is in the range of 1000 g/mol-10000 g/mol, for example, it can be 1000 g/mol, 2000 g/mol, 3000 g/mol, 4000 g/mol, 5000 g/mol mole, 6000 g/mole, 7000 g/mole, 8000 g/mole, 9000 g/mole, 10000 g/mole.
  • the linear hydrophilic polymer includes an amine-based hydrophilic polymer, wherein the amine-based hydrophilic polymer includes at least one of the following, for example: polyacrylamide, polyethyleneimine. But not limited to the examples here.
  • the amine group (-NH-) Since there are defect sites on the surface of the material, dangling bonds are formed, and the amine group (-NH-) has a lone pair of electrons, which is easy to combine with the dangling bonds on the surface of the material, so it has a very good affinity for the material.
  • the amine-based hydrophilic polymer can be firmly adsorbed on the ceramic surface.
  • the other end of the amine-based hydrophilic polymer is a non-polar carbon-based molecular chain, which has poor compatibility with polar water, so ceramics with amine-based hydrophilic polymers will directly settle.
  • the carbon-containing molecular chains on the amine-based hydrophilic polymers are very easy to have affinity with the carbon-containing molecular chains on the one-dimensional nanomaterials, thereby forming a ceramic-amine-based polymer-a
  • the structure of one-dimensional nanomaterials, the hydrophilic functional groups on one-dimensional nanomaterials form a highly stable network structure in water, which greatly enhances the stability of the structure in water.
  • the amine-based hydrophilic polymer can function like a dispersant.
  • a linear hydrophilic polymer is attached to the one-dimensional nanomaterial.
  • the linear hydrophilic polymer is associated with the state of the dispersion (its correlation will be described in conjunction with Table 1 below), and then, the present invention has found and utilized this creatively. It is found that the mass ratio of the linear hydrophilic polymer to the water in the dispersion medium is selected to be in the range of 0.01% to 0.1%. On the one hand, it can avoid slurry settlement and ensure the stability of the slurry. To reduce the effect of agglomeration of ceramic materials.
  • Adhesive wherein can be any material that can play an adhesive role, such as can include at least one of the following: polyvinyl alcohol, lithium polyacrylate, sodium carboxymethyl cellulose, and styrene-butadiene rubber.
  • the mass ratio of the adhesive to the ceramic material may be in the range of 1% to 10%, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%. , 8%, 9%, 10%.
  • the embodiment of the present invention also provides a preparation method of the nano-slurry mentioned above, for preparing the nano-slurry mentioned above, please refer to Figure 1, the preparation method includes :
  • S12 Disperse the one-dimensional nanomaterial in the ceramic dispersion to obtain a specified dispersion
  • the ceramic material can be fully dispersed in the dispersion medium, and the content of water in the dispersion medium is more than 90 wt%.
  • the dispersion method can be, for example, by at least one of high-speed stirring, high-pressure homogenization, and sand-milling dispersion to uniformly disperse the ceramic material in the dispersion medium to form a ceramic dispersion.
  • the concentration of the ceramic material in the ceramic dispersion can be 0.01-50 wt%.
  • one-dimensional nanomaterials can be added to the ceramic dispersion, and then the one-dimensional nanomaterials can be redispersed by at least one of high-speed stirring, high-pressure homogenization, and sand mill dispersion, so that the ceramic material and a Dimensional nanomaterials can be fully mixed evenly.
  • the distribution method in step S11 may be the same as the distribution method in step S12, or may be different.
  • the added linear hydrophilic polymer can also be homogenized at a specified pressure (for example, 500-2000bar) and/or stirred at a specified speed (for example, 3k-50kr/min).
  • a specified pressure for example, 500-2000bar
  • a specified speed for example, 3k-50kr/min.
  • a given dispersion of linear hydrophilic polymers is dispersed and the linear hydrophilic polymers are attached to the one-dimensional nanomaterials.
  • the attachment can be based on the properties of the linear hydrophilic polymer itself, and the attachment can be completed during dispersion.
  • the particles of ceramic materials and one-dimensional nanomaterials in the dispersion exist as agglomerates, and it is difficult for general polymers to enter the middle of these agglomerates.
  • the linear hydrophilic polymer selected by the present invention has linear characteristics, and the resistance to entering the interior of the aggregate is small.
  • amide materials when choosing amide materials as linear hydrophilic polymers, amide has strong polar characteristics and has excellent compatibility in water, so , the linear hydrophilic polymer is easy to enter the interior of the aggregate with water, and under the polar interaction, it is tightly coated on the surface of the nanomaterial. With the external force (such as high pressure, high-speed stirring, etc.), and then Agglomerates are broken up and dispersed in water stably.
  • step S14 an adhesive can be added to the specified solution obtained after step S13, and in some examples, an auxiliary agent can also be added subsequently.
  • an adhesive can be added to the specified solution obtained after step S13, and in some examples, an auxiliary agent can also be added subsequently.
  • Example 1 and Comparative Example 5 From the comparison of Example 1 and Comparative Example 5, it can be seen that when nanocellulose is not added, the slurry is easy to settle, and the surface roughness of the coated membrane is as high as 1200nm. From the comparison of Example 1 and Comparative Example 4, it can be seen that when the content of nanocellulose is too high (25%), the viscosity of the slurry is too high, resulting in failure to coat. Based on this, in the embodiment of the present invention, the mass ratio of the one-dimensional nanomaterial to the ceramic material is configured to be 0.01%-20%.
  • the main reason for the above roughness problem is that when the size of the ceramic material is small (particle size 5-500nm), the surface energy of the ceramic material is very large, so it is very easy to agglomerate, resulting in unstable slurry and roughness on the surface of the coated diaphragm. sharply increased.
  • Example 6 of Example 1 Comparative Example 7 of Example 5, and Comparative Example 8 of Example 3
  • the water content in the dispersion medium is not 100wt%
  • the introduction of other solvents in the water it can be Effectively reduce the surface roughness of the diaphragm.
  • the introduction of other solvents can greatly reduce the surface tension of the mixed solvent (that is, the dispersion medium).
  • one-dimensional nanomaterials, ceramic materials and linear hydrophilic polymers are added, further Enhance the dispersion uniformity of ceramic materials, one-dimensional nanomaterials and linear hydrophilic polymers, so better solve the problem of agglomeration of ceramic particles and further reduce the surface roughness of the coating.
  • the base film used is a PE base film with a thickness of 11 ⁇ m, a pore diameter of 40 nm, and a porosity of 42%. Furthermore, the above examples and comparative examples reflect the The above-mentioned technical effects are reflected by using the same (or similar) base film for coating.
  • an embodiment of the present invention provides a battery separator, including a base film and a coating,
  • the coating is formed by applying nano slurry to at least one surface of the base film
  • the specified nano-slurry is the above-mentioned nano-slurry used for the surface coating of the diaphragm, or: the specified nano-slurry is the nano-slurry prepared by the above-mentioned nano-slurry preparation method.
  • an embodiment of the present invention also provides a battery separator, including: a base film and a coating, wherein the coating contains ceramic materials, one-dimensional nanomaterials and linear hydrophilic polymers, wherein the one-dimensional nanomaterials
  • the mass ratio of the ceramic material is in the range of 0.01% to 20%, the particle size of the ceramic material is in the range of 5-500nm, the linear hydrophilic polymer is attached to the one-dimensional nanomaterial and Connect the ceramic material.
  • the embodiment of the present invention also provides a method for manufacturing a battery separator, including:
  • the slurry can be coated on the base film by at least one of gravure coating, spray coating, dip coating, extrusion coating, etc., and then dried to obtain a battery separator composed of ceramic materials.
  • the coating can be one-sided or double-sided, and further, the coating can be formed on one or both sides.
  • An embodiment of the present invention also provides a battery, including the battery separator involved in the above optional solution.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

本发明提供了一种纳米浆料及其制备方法、电池隔膜及其制作方法和电池，其中的纳米浆料，包括：分散剂、陶瓷材料、一维纳米材料、线性亲水聚合物与胶黏剂，其中，所述一维纳米材料与所述陶瓷材料的质量比处于0.01％至20％的区间范围内，所述陶瓷材料的粒径处于5-500nm的区间范围内。

Description

纳米浆料及其制备方法、电池隔膜及其制作方法和电池 技术领域
本发明涉及电池领域，尤其涉及一种纳米浆料及其制备方法、电池隔膜及其制作方法和电池。
背景技术
锂电池隔膜是锂离子电池核心部件之一，其性能的好坏对锂电池的整体性能有着非常重要的影响，是制约锂电池发展的关键技术之一。随着锂电池应用领域的不断扩大和锂电产品在人们生活中的影响不断深化，人们对锂电池性能的要求也越来越高。为了满足锂电池的发展要求，隔膜作为锂电池的重要部件不仅应具有良好的化学稳定性、较低的制造成本，提高锂离子电池的安全性能也是目前锂电发展的重要趋势。
现有相关技术中，锂电池的隔膜可以包括基膜与覆于基膜至少一表面的涂层，涂层的浆料可基于陶瓷颗粒制备而成，然而，陶瓷颗粒表面能容易引发陶瓷颗粒团聚问题，致使涂层表面均匀性差，进而影响在后续的电池组装中的极片贴合。
发明内容
本发明提供一种纳米浆料及其制备方法、电池隔膜及其制作方法和电池，以解决陶瓷颗粒表面能导致团聚问题的问题。
根据本发明的第一方面，提供了一种用于隔膜表面涂层的纳米浆料，包括：分散介质、陶瓷材料、一维纳米材料、线性亲水聚合物与胶黏剂，其中，所述一维纳米材料与所述陶瓷材料的质量比处于0.01％至20％的区间范围内，所述分散介质中，水的含量为90wt％以上，所述陶瓷材料的粒径处于5-500nm的区间范围内。
可选的，所述线性亲水聚合物附着于所述一维纳米材料并连接所述陶瓷材料。
可选的，所述线性亲水聚合物与所述分散介质中水的质量比处于0.01％ 至0.1％的区间范围内。
可选的，所述线性亲水聚合物的分子量处于1000克/摩尔-10000克/摩尔的区间范围内。
可选的，所述线性亲水聚合物包括胺基亲水聚合物。
可选的，所述线性亲水聚合物包括以下至少之一：
聚丙烯酰胺、聚乙烯亚胺。
可选的，所述一维纳米材料的直径处于1-50纳米的区间范围内，所述一维纳米材料的长度处于100-1000纳米的区间范围内。
可选的，所述胶黏剂与所述陶瓷材料的质量比处于1％至10％的区间范围。
可选的，所述胶黏剂包括以下至少之一：
聚乙烯醇、聚丙烯酸锂、羧甲基纤维素钠，丁苯橡胶。
根据本发明的第二方面，提供了一种纳米浆料的制备方法，用于制备第一方面及其可选方案涉及的纳米浆料，所述制备方法，包括：
将陶瓷材料分散于分散介质中，得到陶瓷分散液；所述分散介质中，水的含量为90wt％以上；
将一维纳米材料分散于所述陶瓷分散液，得到指定分散液；
将线性亲水聚合物加入所述指定分散液，得到指定溶液；
将胶黏剂加入所述指定溶液，得到纳米浆料。
可选的，将线性亲水聚合物加入所述指定分散液之后，还包括：
通过指定压力的均质和/或指定速度的搅拌，对已加入所述线性亲水聚合物的指定分散液进行分散，并使所述线性亲水聚合物附着于所述一维纳米材料。
根据本发明的第三方面，提供了一种电池隔膜，包括基膜和涂层：
所述涂层是指定纳米浆料涂覆于所述基膜至少一表面而形成的；
所述指定纳米浆料为第一方面及其可选方案涉及的纳米浆料或者第二方面的制备方法制备而成的纳米浆料。
。
根据本发明的第四方面，提供了一种电池隔膜，包括：基膜与涂层，所述涂层中包含陶瓷材料、一维纳米材料与线性亲水聚合物，其中，所述一维纳米材料与所述陶瓷材料的质量比处于0.01％至20％的区间范围内，所述陶 瓷材料的粒径处于5-500nm的区间范围内，所述线性亲水聚合物包裹所述一维纳米材料并连接所述陶瓷材料。
根据本发明的第五方面，提供了一种电池，包括第三方面或第四方面涉及的电池隔膜。
本发明提供的纳米浆料及其制备方法、电池隔膜及其制作方法和电池中，在陶瓷材料中引入了一维纳米材料，降低陶瓷材料的表面能，进而可降低所形成涂层的表面粗糙度，同时，
为了能够进一步降低表面粗糙度，还采用了线性亲水聚合物，从而通过线性亲水聚合物起到一维纳米材料与陶瓷材料之间的桥接作用，进而使两者完全结合，进一步充分降低陶瓷材料团聚的倾向，进一步降低所形成涂层的表面粗糙度。并且，通过线性亲水聚合物的引入，还可有助于避免浆料的沉降，提高浆料的稳定性。
此外，基于对浆料状态的研究，可发现：一维纳米材料的质量选择与最终浆料状态(例如粘度)具有一定关联性，进而，本发明创造性地发现并利用了这一发现，将一维纳米材料与陶瓷材料的质量比选择为0.01％至20％的区间，有效保障了浆料能够便于涂覆。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。
图1是本发明一实施例中纳米浆料的制备方法的流程示意图；
图2是本发明一实施例中电池隔膜的制作方法的流程示意图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
在本发明说明书的描述中，需要理解的是，术语“上部”、“下部”、“上端”、“下端”、“下表面”、“上表面”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。
在本发明说明书的描述中，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。
在本发明的描述中，“多个”的含义是多个，例如两个，三个，四个等，除非另有明确具体的限定。
在本发明说明书的描述中，除非另有明确的规定和限定，术语“连接”等术语应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或成一体；可以是机械连接，也可以是电连接或可以互相通讯；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通或两个元件的相互作用关系。对于本领域的普通技术人员而言，可以根据具体情况理解上述术语在本发明中的具体含义。
下面以具体地实施例对本发明的技术方案进行详细说明。下面这几个具体的实施例可以相互结合，对于相同或相似的概念或过程可能在某些实施例不再赘述。
本发明实施例提供了一种用于隔膜表面涂层的纳米浆料，包括：分散介质、陶瓷材料、一维纳米材料、线性亲水聚合物与胶黏剂。
其中的分散介质，可以为任意可用于材料分散的液体，所述分散介质中，水的含量为90wt％以上，此外还可以包括乙醇、丙酮、N-甲基吡咯烷酮等分散介质。
即水的含量可以是90wt％、92wt％、93wt％、95wt％、98wt％、99wt％、100wt％。
部分方案中，分散介质中水含量不为100wt％的情况下，即表明：在分散介质中，除了水，还引入其他溶剂，进而，由于水中引入了其他溶剂，可以大幅度降低混合溶剂的表面张力，表面张力的降低有利于进一步增强陶瓷材 料、一维纳米材料及线性亲水聚合物的分散均匀性，进而使线性亲水聚合物能更充分地与陶瓷材料及一维纳米材料相连接接触，因此更好地解决陶瓷颗粒的团聚问题。
其中的陶瓷材料，例如包括以下至少之一：氧化铝、氧化硅、氧化钛、氢氧化镁、勃姆石等，其中，陶瓷材料(例如氧化铝)的粒径处于5-500nm的区间范围内，在该区间范围时，陶瓷材料的表面能很大，因此，非常易于团聚，导致浆料不稳定，本发明实施例恰是针对于该条件下发生的团聚而引入了一维纳米材料与线性亲水聚合物，既降低这种团聚的倾向。相较而言，现有相关技术中，因其采用的陶瓷材料通常大于600nm，所以，通常并不会产生团聚的技术问题，进而，发现与解决该团聚问题均是本发明实施例的改进之一。
其中的一维纳米材料，也可理解为是纳米线、纳米管或纳米棒，例如可以包括以下至少之一：纳米纤维素、碳纳米管、芳纶纳米纤维、聚酰亚胺纳米纤维。
可见，本发明在陶瓷材料中引入了一维纳米材料，降低材料的表面能，进而可降低所形成涂层的表面粗糙度
其中，所述一维纳米材料与所述陶瓷材料的质量比处于0.01％至20％的区间范围内。例如该质量比可以为0.01％、0.05％、0.1％、0.5％、1％、2％、3％、4％、5％、6％、7％、8％、9％、10％、11％、12％、13％、14％、15％、16％、17％、18％、19％、20％。随着所选材料的变化，并结合试验，可从中选择、变化相应的取值。一种举例中，所述一维纳米材料与所述陶瓷材料的质量比处于12％-20％的区间范围内。
进一步的，一维纳米材料占陶瓷材料的1％-20％。
基于对浆料状态的研究，可发现：一维纳米材料的质量选择与最终浆料状态(例如粘度)具有一定关联性(其关联性将在后文中结合表一进行说明)，进而，本发明创造性地发现并利用了这一发现，将一维纳米材料与陶瓷材料的质量比选择为0.01％至20％的区间，有效保障了浆料能够便于涂覆。
其中，所述一维纳米材料的直径处于1-50纳米的区间范围内，所述一维纳米材料的长度处于100-1000纳米的区间范围内。
其中，通过线性亲水聚合物起到一维纳米材料与陶瓷材料之间的桥接作 用，进而使两者完全结合，进一步充分降低陶瓷材料团聚的倾向，进一步降低所形成涂层的表面粗糙度。并且，通过线性亲水聚合物的引入，还可有助于避免浆料的沉降，提高浆料的稳定性。具体的性能对比将在后文中结合表一进行阐述。
进一步的举例中，所述线性亲水聚合物与所述分散介质中水的质量比处于0.01％至0.1％的区间范围内，例如可以为0.01％、0.02％、0.03％、0.04％、0.05％、0.06％、0.07％、0.08％、0.09％、0.1％。
所述线性亲水聚合物的分子量处于1000克/摩尔-10000克/摩尔的区间范围内，例如可以为1000克/摩尔、2000克/摩尔、3000克/摩尔、4000克/摩尔、5000克/摩尔、6000克/摩尔、7000克/摩尔、8000克/摩尔、9000克/摩尔、10000克/摩尔。
所述线性亲水聚合物包括胺基亲水聚合物，其中的胺基亲水聚合物例如包括以下至少之一：聚丙烯酰胺、聚乙烯亚胺。但也不限于此处的举例。
针对于对胺基亲水聚合物的使用，其作用原理如下：
由于材料表面具有缺陷位，进而形成悬空键，而胺基(-NH-)具有孤对电子，易于与材料表面的悬空键结合，因此，对材料具有非常好的亲和性。从而使得胺基亲水聚合物能牢牢吸附在陶瓷表面。胺基亲水聚合物的另一端是非极性的碳基分子链，与极性的水相容性差，因此带有胺基亲水聚合物的陶瓷会直接沉降。在引入含碳基的一维纳米材料后，胺基亲水聚合物上的含碳分子链非常易于与一维纳米材料上的含碳分子链亲和，进而形成陶瓷-胺基聚合物-一维纳米材料的结构，一维纳米材料上亲水的官能团，在水中形成稳定性极高的网络化结构，进而使得该结构在水中稳定性大大增强。进而，胺基亲水聚合物可起到类似分散剂的作用。其中一种实施方式中，线性亲水聚合物附着于所述一维纳米材料。
基于对浆料状态的研究，可发现：线性亲水聚合物与分散液的状态相关联(其关联性将在后文中结合表一进行说明)，进而，本发明创造性地发现并利用了这一发现，将线性亲水聚合物占分散介质中水的质量比选择为处于0.01％至0.1％的区间范围，一方面可避免浆料沉降，保障浆料的稳定性，另一方面还可有效起到降低陶瓷材料团聚的效果。
其中的胶黏剂可以为任意可起到胶黏作用的材料，例如可以包括以下 至少之一：聚乙烯醇、聚丙烯酸锂、羧甲基纤维素钠，丁苯橡胶。
进一步的，所述胶黏剂与所述陶瓷材料的质量比可处于1％至10％的区间范围，例如可以为1％、2％、3％、4％、5％、6％、7％、8％、9％、10％。
针对于此，若胶黏剂过多(例如胶黏剂与陶瓷材料的质量比大于10％)，则会堵塞孔道影响锂离子的传输率；反之，若胶黏剂过少(例如胶黏剂与陶瓷材料的质量比小于1％)，陶瓷材料和一维纳米材料则容易脱落。故而，选择1％至10％的区间范围时，可有效兼顾传输率与胶黏性能。为了得到以上所提及的纳米浆料，本发明实施例还提供了一种纳米浆料的制备方法，用于制备以上所提及的纳米浆料，请参考图1，所述制备方法，包括：
S11：将陶瓷材料分散于分散介质中，得到陶瓷分散液；
S12：将一维纳米材料分散于所述陶瓷分散液，得到指定分散液；
S13：将线性亲水聚合物加入所述指定分散液，以软化所述指定分散液，得到指定溶液；
S14：将胶黏剂加入所述指定溶液，得到纳米浆料。
步骤S11的具体举例中，可将陶瓷材料充分地分散在分散介质中，分散介质中，水的含量为90wt％以上。分散方式可例如：通过高速搅拌、高压均质、砂磨分散等至少之一方式，均匀地将陶瓷材料分散在分散介质中，形成陶瓷分散液。一种举例中，陶瓷材料在陶瓷分散液中的浓度可以为0.01～50wt％。
步骤S12的具体举例中，可在陶瓷分散液中加入一维纳米材料，随后以高速搅拌、高压均质、砂磨分散等至少之一方式对一维纳米材料进行再次分散，使陶瓷材料与一维纳米材料能充分混合均匀。步骤S11中分散的方式与步骤S12中分散的方式可以是一样的，也可以是有区别的。
步骤S13的具体举例中，加入线性亲水聚合物之后，还可通过指定压力(例如500-2000bar)的均质和/或指定速度(例如3k-50kr/min)的搅拌，对已加入所述线性亲水聚合物的指定分散液进行分散，并使线性亲水聚合物附着于所述一维纳米材料。
其中的附着，可基于线性亲水聚合物本身的性能，在分散时完成附着。
部分举例中，由于巨大的表面能，陶瓷材料和一维纳米材料在分散液中的颗粒以团聚体存在，一般的聚合物很难进入到这些团聚体中间，本发明选 择的线性亲水聚合物，具有线性的特点，进入团聚体内部的阻力小，另一方面，在选择酰胺材料作为线性亲水聚合物时，酰胺具有强极性的特性，且在水中有非常优异的相容性，这样，线性亲水聚合物就很容易随着水进入到团聚体内部，并在极性的相互作用下，紧紧包覆于纳米材料表面，随着外部强力(如高压，高速搅拌等)，进而将团聚体破坏，并稳定分散到水中。
步骤S14的具体举例中，可在步骤S13之后得到的指定溶液中加入胶黏剂，部分举例中，还可在随后加入助剂。为便于说明以上具体举例中各特征的作用，以下将结合试验得到的数据进行说明：
表一：
Figure PCTCN2022077088-appb-000001
Figure PCTCN2022077088-appb-000002
从对比例2和对比例3可以看出，当不加线性亲水聚合物时，浆料不能稳定存在，且涂覆后的隔膜表面粗糙度为1000nm以上，其粗糙度远远大于基膜的粗糙度(450nm)，但仍然小于完全不加线性亲水聚合物和一维纳米材料的(对比例1)。当线性亲水聚合物加入量大于0.15％时，其粗糙度达400nm,对比实施例1、实施例3-5可见，其中体现了线性亲水聚合物的加入与否与粗糙度的关联性，通过加入合适量的线性亲水聚合物，可有助于降低粗糙度。
从实施例1和对比例5对比，可以看出，当不加入纳米纤维素时，浆料 易于沉降，且涂覆隔膜的表面粗糙度高达1200nm。从实施例1和对比例4对比可以看出，当纳米纤维素的含量过高时(25％)，浆料粘度过大，导致不能进行涂覆。基于此，本发明实施例将一维纳米材料与陶瓷材料的质量比配置为了0.01％-20％。
当处于合适范围内，其它一维纳米材料和线性亲水聚合物也存在类似的功能，即降低表面粗糙度(实施例3，实施例4，实施例5)。
导致以上粗糙度问题的主要原因在于，当陶瓷材料尺度较小时(粒径5-500nm)，陶瓷材料的表面能很大，因此，非常易于团聚，导致浆料不稳定，涂覆隔膜表面的粗糙度急剧上升。为了降低表面能，可通过加入亲水性聚合物实现，通过亲水性聚合物与陶瓷材料表面结合，增强与水的亲和性，进而能够降低表面能，如对比例5、6所示，线性亲水聚合物与水的质量比配置为0.01-0.1％时，隔膜表面粗糙度相对对比例1较好，但因其未添加一维纳米材料故其稳定性依然差，且粗糙度依然很大。
通过实施例1对比实施例6，实施例5对比实施例7，实施例3对比实施例8，可以看出：分散介质中水含量不为100wt％的情况下，由于水中引入了其他溶剂，可有效降低隔膜表面粗糙度，之所以如此，是因为引入其他溶剂，大幅度降低混合溶剂(即分散介质)的表面张力，当一维纳米材料、陶瓷材料与线性亲水聚合物加入后，可进一步增强陶瓷材料、一维纳米材料及线性亲水聚合物的分散均匀性，因此更好地解决陶瓷颗粒的团聚问题，进一步降低涂层的表面粗糙度。
此外，以上实施例、对比例的实现过程中，所采用的基膜选用了PE基膜，厚度为11μm，孔径为40nm，孔隙率为42％，进而，以上实施例和对比例所体现出的上述技术效果是使用相同(或相似)基膜进行涂覆而体现出来的。
对应于前文提及的纳米浆料及其制备方法，本发明实施例提供了一种电池隔膜，包括基膜和涂层，
所述涂层是指定纳米浆料涂覆于所述基膜至少一表面而形成的；
所述指定纳米浆料为以上所涉及的用于隔膜表面涂层的纳米浆料，或者：所述指定纳米浆料为以上所涉及的纳米浆料的制备方法制备而成的纳米浆料。
此外，本发明实施例还提供了一种电池隔膜，包括：基膜与涂层，所述 涂层中包含陶瓷材料、一维纳米材料与线性亲水聚合物，其中，所述一维纳米材料与所述陶瓷材料的质量比处于0.01％至20％的区间范围内，所述陶瓷材料的粒径处于5-500nm的区间范围内，所述线性亲水聚合物附着所述一维纳米材料并连接所述陶瓷材料。
其中所涉及的任意技术名词、技术手段、技术效果、可选实施方式，均可参照前文中的相关描述理解。
基于以上的电池隔膜，请参考图2本发明实施例还提供了一种电池隔膜的制作方法，包括：
S21：将以上所涉及的纳米浆料涂覆于基膜，以在所述基膜上形成涂层；
S22：烘干具有所述涂层的所述基膜，得到电池隔膜。
步骤S21的具体举例中，可通过微凹辊涂，喷涂，浸涂，挤涂等至少之一方式，将浆料涂覆于基膜上，烘干即可得到陶瓷材料复合的电池隔膜。此外，其中的涂覆可以是单面的，也可以是双面的，进而，在单面或双面形成涂层。
本发明实施例还提供了一种电池，包括以上可选方案涉及的电池隔膜。
在本说明书的描述中，参考术语“一种实施方式”、“一种实施例”、“具体实施过程”、“一种举例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不一定指的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (13)

  1. 一种用于隔膜表面涂层的纳米浆料，其特征在于，包括：分散介质、陶瓷材料、一维纳米材料、线性亲水聚合物与胶黏剂，其中，所述一维纳米材料与所述陶瓷材料的质量比处于0.01％至20％的区间范围内，所述分散介质中，水的含量为90wt％以上，所述陶瓷材料的粒径处于5-500nm的区间范围内。
  2. 根据权利要求1所述的纳米浆料，其特征在于，所述线性亲水聚合物附着于所述一维纳米材料并连接所述陶瓷材料。
  3. 根据权利要求1所述的纳米浆料，其特征在于，所述线性亲水聚合物与所述分散介质中水的质量比处于0.01％至0.1％的区间范围内，所述线性亲水聚合物的分子量处于1000克/摩尔-10000克/摩尔的区间范围内。
  4. 根据权利要求1所述的纳米浆料，其特征在于，所述线性亲水聚合物包括胺基亲水聚合物。
  5. 根据权利要求4所述的纳米浆料，其特征在于，所述胺基亲水聚合物包括以下至少之一：
    聚丙烯酰胺、聚乙烯亚胺。
  6. 根据权利要求1所述的纳米浆料，其特征在于，所述一维纳米材料的直径处于1-50纳米的区间范围内，所述一维纳米材料的长度处于100-1000纳米的区间范围内。
  7. 根据权利要求1至6任一项所述的纳米浆料，其特征在于，所述胶黏剂与所述陶瓷材料的质量比处于1％至10％的区间范围。
  8. 根据权利要求1至6任一项所述的纳米浆料，其特征在于，所述胶黏剂包括以下至少之一：
    聚乙烯醇、聚丙烯酸锂、羧甲基纤维素钠，丁苯橡胶。
  9. 一种纳米浆料的制备方法，其特征在于，用于制备权利要求1至8任意之一所述的纳米浆料，所述制备方法，包括：
    将陶瓷材料分散于分散介质中，得到陶瓷分散液，所述分散介质中，水的含量为90wt％以上；
    将一维纳米材料分散于所述陶瓷分散液，得到指定分散液；
    将线性亲水聚合物加入所述指定分散液，得到指定溶液；
    将胶黏剂加入所述指定溶液，得到纳米浆料。
  10. 根据权利要求9所述的制备方法，其特征在于，将线性亲水聚合物加入所述指定分散液之后，还包括：
    通过指定压力的均质和/或指定速度的搅拌，对已加入所述线性亲水聚合物的指定分散液进行分散，并使所述线性亲水聚合物附着于所述一维纳米材料。
  11. 一种电池隔膜，其特征在于，包括基膜和涂层，
    所述涂层是指定纳米浆料涂覆于所述基膜至少一表面而形成的；
    所述指定纳米浆料为权利要求1至8任一项所述的纳米浆料或者权利要求9所述的制备方法制备而成的纳米浆料。
  12. 一种电池隔膜，其特征在于，包括：基膜与涂层，所述涂层中包含陶瓷材料、一维纳米材料与线性亲水聚合物，其中，所述一维纳米材料与所述陶瓷材料的质量比处于0.01％至20％的区间范围内，所述陶瓷材料的粒径处于5-500nm的区间范围内，所述线性亲水聚合物附着所述一维纳米材料并连接所述陶瓷材料。
  13. 一种电池，其特征在于，包括权利要求11或12所述的电池隔膜。
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