CN112117420A - Battery separator, preparation method thereof and lithium ion battery - Google Patents
Battery separator, preparation method thereof and lithium ion battery Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
Abstract
The invention provides a battery separator, a preparation method thereof and a lithium ion battery, wherein the battery separator comprises a separator substrate and a conductive coating coated on at least one surface of the substrate, the raw material of the conductive coating comprises an adhesive and a conductive material, and the shape of the conductive material comprises at least one of zero dimension, one dimension and two dimensions. The invention can effectively solve the problem of static electricity generated in the use process of the partition plate, reduce the foreign matter adsorption probability and improve the comprehensive quality of the battery, such as safety, cyclicity and the like.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a battery separator, a preparation method thereof and a lithium ion battery formed by adopting the separator.
Background
The lithium ion battery has the characteristics of high energy density, long cycle life, no memory effect, environmental friendliness and the like, and is widely applied to products such as consumer electronics and electric tools as energy storage equipment. The battery separator, as an important component of a lithium ion battery, determines characteristics of the battery, such as an interface structure, internal resistance and the like, and directly influences performances of the battery, such as cycle, capacity, safety and the like.
The current lithium ion battery mainly adopts a porous polymer substrate as a separator (or called diaphragm) which is arranged between a positive pole piece and a negative pole piece, and in the use process of the lithium ion battery, along with the progress of charging and discharging, the interface between the separator and the pole pieces is easy to change, so that the gap between the separator and the pole pieces is increased, and the problems of battery capacity, service life reduction and the like are caused. The glue-coated partition board can effectively improve the gap problem between the partition board and the pole piece, and the partition board which is commonly used at the present stage is mainly a non-water system glue-coated partition board (generally, a binder coating (or called a glue coating) is coated on the surface of a polymer substrate), has good electrolyte wettability and pole piece bonding force, can improve the deformation problem of a battery cell, and can inhibit the increase of the gap between the partition board and the pole piece interface, thereby improving the safety and the cycle performance of the battery cell.
However, the nonaqueous gluing separator often produces a large electrostatic effect in the use process, which not only seriously affects the normal operation of the production process when the lithium ion battery is wound, but also easily adsorbs dust, which affects the battery quality, and the current solution to the electrostatic problem mainly includes: (1) static electricity is eliminated by neutralizing or introducing the charge to the ground by using an additional device (such as an ion fan, a static elimination bar and the like) in the winding process of the lithium ion battery, however, the static electricity on the gluing separator can be eliminated only partially or temporarily in such a way, and the separator still generates static electricity if friction occurs in the subsequent production process and cannot eliminate the static electricity from the source; (2) the antistatic agent is added into the glue coating layer, the antistatic agent is generally a surfactant with both polar and nonpolar groups, and polar hydrophilic groups of the antistatic agent can absorb a small amount of water on the surface of the separator to achieve the purpose of removing static electricity.
Therefore, how to avoid the generation of side effects such as static electricity and the like and ensure the comprehensive quality of the lithium ion battery on the basis of effectively solving the problem of the gap between the separator and the pole piece still remains a technical problem to be solved by the technical personnel in the field.
Disclosure of Invention
The invention provides a battery separator, which at least solves the problems of static electricity and the like in the prior art.
The invention also provides a preparation method of the battery separator, which can be used for preparing the separator and has the advantages of simple preparation process and the like.
The invention also provides a lithium ion battery which is formed by adopting the battery separator and has good comprehensive performances such as safety, cyclicity and the like.
In one aspect of the present invention, there is provided a battery separator comprising a separator substrate and a conductive coating coated on at least one surface of the substrate, the raw material of the conductive coating comprising a binder and a conductive material, the conductive material having a shape comprising at least one of zero dimension, one dimension, and two dimensions.
According to the battery separator provided by the invention, the conductive coating formed by the adhesive and the conductive material is coated on the substrate of the separator (which is equivalent to introducing the conductive material into the traditional adhesive coating), so that the generation of static electricity can be effectively avoided on the basis of relieving the gap between the separator and the pole piece, particularly, the conductive material is distributed according to the specific shape, a microscopic network morphology (or a conductive network) is formed in the conductive coating, the electron transfer can be accelerated, the static electricity problem is further effectively improved, and the battery formed by the separator has good safety, cyclicity and other qualities.
According to the study of the present invention, in the conductive coating, the content of the conductive material is not less than 0.01% by mass, for example, may be 0.01 to 99% by mass, further may be not less than 0.1% by mass, further may be not less than 0.4% by mass, or 0.5% by mass, or 0.8% by mass, further may be not less than 1% by mass. In one embodiment, the conductive material may specifically be contained in the conductive coating in an amount of 0.1 to x%, further 0.4 to x%, further 0.5 to x% or 0.8 to x%, further 1 to x%; in this case, x% may be any value of 3 to 50%, for example, 3%, 10%, 20%, 30%, 40%, 50%, or the like.
In the present invention, the conductive material (or called low resistance material) may be at least one selected from a carbon material, a conductive polymer, a metal material, and a metal compound material, and/or the binder may be at least one selected from polyvinylidene fluoride (PVDF), a vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polymethyl acrylate, butyl acrylate-acrylonitrile copolymer, polyacrylonitrile, an ethylene-acrylic acid copolymer, polyethyl acrylate, and sodium carboxymethyl cellulose (CMC). The conductive materials (or called low-resistance materials) have good stability and compatibility, impurities cannot be introduced into the battery, and the excellent performance of the battery can be further ensured; the carbon material has abundant micropores and surface functional groups, has good mechanical properties, and is beneficial to the transmission of lithium ions and the infiltration of electrolyte, so that in some preferred embodiments of the invention, the carbon material can be selected as a conductive material.
Specifically, the zero-dimensional conductive material may be at least one selected from the group consisting of conductive carbon black, super P, conductive graphite, ketjen black, acetylene black, activated carbon, hierarchical pore carbon, metal nanoparticles, metal oxide nanoparticles, and conductive polymer particles; and/or, the one-dimensional conductive material may be in a fiber shape, a tube shape, a rod shape, or the like, and may be specifically selected from at least one of a carbon nanotube, a carbon nanofiber, a metal nanowire, a metal fiber, a metal nanobelt, a metal oxide nanorod, and a one-dimensional conductive polymer; and/or the two-dimensional conductive material can be at least one selected from graphene, layered graphite, Mxene, carbon nanosheets, conductive polymer nanosheets, metal nanosheets and two-dimensional metal oxides.
In the conductive coating, the conductive material is randomly distributed in the conductive coating in the form of the units with the certain shape, some units are mutually contacted to form a conductive channel (for example, the conductive channel is formed by constructing points (the unit shape is zero dimension), lines (the unit shape is one dimension), surfaces (the unit shape is two dimensions) or point surfaces (the unit shape is zero dimension and two dimensions), point lines (the unit shape is zero dimension and one dimension), line surfaces (the unit shape is one dimension and two dimensions), point line surfaces (the unit shape is zero dimension, one dimension and two dimensions), and the like), some units are not directly contacted, but electrons are transferred to the conductive channel through a tunnel effect and field emission to form a three-dimensional conductive network. In the implementation process of the invention, the conductive material with the corresponding unit shape can be adopted, and the conductive material and the binder form slurry to be coated on the separator substrate to form the conductive coating, for example, in the conductive coating formed by the conductive material with the zero dimension and the one dimension of the units, the unit shape of the conductive material is also the corresponding zero dimension and the one dimension.
In the above conductive material, the mass content of each shape of the conductive material may be 0-100%, for example, in an embodiment, the shape of the conductive material is zero-dimensional and one-dimensional (that is, the conductive material is composed of a zero-dimensional conductive material and a one-dimensional conductive material), wherein the mass content of the zero-dimensional conductive material is about 50%, and the balance is the one-dimensional conductive material.
According to a further development of the present invention, the shape of the conductive material includes at least one dimension and/or two dimensions, such as one dimension or two dimensions or zero dimension and one dimension or zero dimension and two dimensions or one dimension and two dimensions or zero dimension, one dimension and two dimensions, which is more beneficial for improving the static electricity problem of the battery separator. In specific implementation, in the conductive material, the mass content of the one-dimensional conductive material may be 1 to 100%, further 10 to 100%, for example, 20 to 100% or 30 to 100%; and/or, in the conductive material, the mass content of the two-dimensional conductive material may be 1 to 100%, further may be 10 to 100%, and for example may be 20 to 100% or 30 to 100%.
In one embodiment of the invention, the shape of the conductive material comprises three shapes of zero dimension, one dimension and two dimensions, which not only can effectively improve the static problem of the battery separator, but also is beneficial to further improving the comprehensive properties of the battery formed by the separator, such as rate capability, cycle performance and the like. In the conductive material, the mass content of the conductive material in each shape may be 1 to 50%, further 10 to 50% or 20 to 50%, for example 20 to 40% or 25 to 35% or 30 to 35%, respectively.
In general, the particle size of the zero-dimensional conductive material can be 100nm-10 μm; and/or the cross-sectional dimension (usually referring to the largest cross-sectional dimension, e.g., the cross-sectional diameter when the cross-section is circular) of the one-dimensional conductive material is 1nm to 10 μm and the length is 100nm to 100 μm; and/or the two-dimensional conductive material has a thickness of 1nm-10 μm, a length of 100nm-100 μm and a width of 100nm-100 μm. The present invention may form the conductive material into a shape of zero dimension, one dimension, two dimensions, etc. by using a method that is conventional in the art, or directly use the conductive material having the shape, which is not particularly limited.
Further, the thickness of the conductive coating layer may be 0.5 μm to 10 μm.
The separator substrate of the present invention may be a conventional separator substrate in the art, such as a porous polymer substrate or a separator substrate formed by coating a ceramic coating layer on a porous polymer substrate, etc., and a conductive coating layer is coated on the separator substrate to form the battery separator (i.e., a composite porous separator) of the present invention. In one embodiment of the present invention, the separator substrate includes a porous polymer substrate and a ceramic coating layer (or inorganic particle layer) applied on at least one surface of the substrate, and the ceramic coating layer is applied on the porous polymer substrate, which is beneficial to improve the thermal stability of the separator. Wherein, when the separator base body is formed of a porous polymer substrate and a ceramic coating layer coated on one surface thereof, the conductive coating layer may be coated on the other surface of the porous polymer substrate and/or on the surface of the ceramic coating layer.
Specifically, the porous polymer substrate may be a porous polymer substrate that is conventional in the art, such as a polyolefin porous substrate, and in one embodiment of the present invention, the porous polymer substrate may be a single-layer or multi-layer (e.g., two-layer) porous film formed by polyethylene and/or polypropylene, and the thickness of the porous polymer substrate may be generally 3 to 20 μm; the raw material of the ceramic coating may generally include inorganic particulate material (or ceramic particulate material, ceramic particulate material) and organic binder, wherein the mass content of the inorganic particulate material may be 50% to 99%, and the balance is organic binder. Specifically, the inorganic particulate material may include at least one of silica, boehmite, alumina, zinc oxide, zirconium dioxide, titanium oxide, magnesium oxide; the organic binder may be at least one of sodium carboxymethylcellulose (CMC), polyvinylidene fluoride (PVDF), polyacrylonitrile, polyvinyl alcohol, styrene-butadiene rubber, polyurethane, polyacrylate, ethylene-vinyl acetate copolymer (EVA), and ethylene-acrylic acid copolymer.
In another aspect of the present invention, a method for preparing the above separator is also provided, including: coating slurry containing a conductive material and a binder on at least one surface of a separator substrate to form a conductive coating, thereby obtaining a battery separator; wherein the shape of the conductive material comprises at least one of zero, one, and two dimensions.
Specifically, the components such as the conductive material and the binder may be dispersed in the solvent to uniformly disperse the components to form a mixed slurry (i.e., the slurry) having a uniform texture; after the slurry is coated on at least one surface of the separator substrate, it may be dried at 55 to 65 ℃, for example, in a vacuum oven, to remove the solvent therein to form a conductive coating, and in practice, it may be dried for 10 to 18 hours or 12 to 18 hours. The solvent used may be, for example, N-methylpyrrolidone (NMP) which is a conventional solvent in the art, and the present invention is not particularly limited thereto.
In one embodiment of the present invention, the separator substrate includes a porous polymer substrate and a ceramic coating layer coated on at least one surface of the substrate, and in particular, a slurry containing a ceramic particulate material may be coated on at least one surface of the porous polymer substrate, dried to remove a solvent to form a ceramic coating layer, and then a conductive coating layer may be coated on a surface of the ceramic coating layer and/or another surface of the porous polymer substrate to manufacture a battery separator.
In the present invention, the coating method (coating method of the ceramic coating and the conductive coating) may be a conventional coating method in the art, such as gravure coating, transfer coating, casting coating, extrusion coating, or spray coating, and the present invention is not particularly limited thereto.
In another aspect of the invention, a lithium ion battery is also provided, which uses the above battery separator.
Specifically, the lithium ion battery of the present invention includes a positive plate, a negative plate, and the above-mentioned battery separator located between the positive plate and the negative plate, which may be, for example, a wound lithium ion battery, and may be formed according to a conventional preparation process in the art, generally, the positive plate, the battery separator, and the negative plate are stacked in order, and then wound into a bare cell, the bare cell is placed in an outer packaging foil, after top sealing and side sealing, an electrolyte is injected into a dried battery precursor, and then the lithium ion battery is obtained through procedures of vacuum packaging, standing, formation, shaping, and the like; among them, the conventional electrolyte in the art can be used, and the raw materials thereof may include, for example, lithium-containing materials such as lithium hexafluorophosphate, Ethylene Carbonate (EC), diethyl carbonate (DEC), Propylene Carbonate (PC), etc.; the procedures of vacuum packaging, standing, formation, shaping and the like can be conventional in the field, and the invention is not particularly limited to this and is not described in detail.
In an embodiment of the present invention, the positive electrode sheet may include a positive electrode current collector and a positive electrode functional layer coated on the positive electrode current collector, and raw materials of the positive electrode functional layer may include a lithium-containing active material, a conductive agent, a binder, and the like; the positive electrode current collector may be an aluminum foil or other positive electrode current collector commonly used in the art, the lithium-containing active material, the conductive agent, and the binder may be conventional in the art, for example, the lithium-containing active material may be lithium cobaltate or the like, the conductive agent may be acetylene black or the like, and the binder may be polyvinylidene fluoride (PVDF) or the like. The positive plate can be prepared by a conventional method in the field, and in the specific implementation, slurry containing a functional layer raw material can be coated on a positive current collector, and the positive plate is prepared after the processes of drying, rolling, cutting, welding lugs and the like; the solvent for forming the above slurry may be N-methylpyrrolidone (NMP) or the like which is conventional in the art.
In an embodiment of the present invention, the negative electrode sheet may include a negative electrode current collector and a negative electrode functional layer coated on the negative electrode current collector, the negative electrode current collector may be a copper foil and other negative electrode current collectors commonly used in the art, and the raw materials of the negative electrode functional layer include a negative electrode active material (such as artificial graphite and the like), a conductive agent (such as acetylene black and the like), a binder (such as Styrene Butadiene Rubber (SBR) and the like), a thickening agent (such as sodium carboxymethylcellulose and the like), and may also be conventional in the art, and the negative electrode sheet may be prepared according to a conventional method in the art, and in a specific implementation, for example, a slurry containing the raw materials of the functional layer may be coated on the negative electrode current collector, and the negative electrode sheet is prepared; the solvent for forming the above slurry may be water or the like which is conventional in the art.
The process conditions of coating, drying, rolling, cutting, welding the tabs and the like are conventional in the field, and the invention is not limited to the process conditions and is not described in detail.
The implementation of the invention has at least the following beneficial effects:
according to the battery separator provided by the invention, the conductive coating is coated on the separator substrate, and the conductive materials in the conductive coating are distributed in a specific shape to form a conductive network, so that charge transfer is facilitated, the generation of static electricity is effectively avoided/inhibited, the problems of winding, wrinkling, knot formation, foreign matter adsorption and the like of the separator caused by the static electricity of the separator are reduced, and the safety, the cyclicity and other qualities of a battery formed by adopting the separator are ensured.
The preparation method of the battery separator provided by the invention can be used for preparing the separator, has the advantages of simple preparation process and the like, and is beneficial to industrial production.
The lithium ion battery provided by the invention is formed by adopting the battery separator, has good comprehensive performances such as safety, cyclicity and the like, and is beneficial to practical industrial application.
Drawings
FIG. 1 is a schematic cross-sectional view of a battery separator according to an embodiment of the invention;
FIGS. 2 and 3 are a schematic view of a microscopic surface of a conductive coating (conductive material is one-dimensional) and a schematic view of a cross section perpendicular to the thickness direction of the conductive coating, respectively, according to an embodiment of the present invention;
FIGS. 4 and 5 are respective microscopic morphology images of the conductive coating according to an embodiment of the present invention observed by Scanning Electron Microscopy (SEM);
FIGS. 6 and 7 are a schematic surface microscopic view and a schematic cross-sectional view perpendicular to the thickness direction of the conductive coating layer, respectively, of another embodiment of the present invention (the conductive material is zero-dimensional);
fig. 8 and 9 are a schematic surface microscopic view and a schematic cross-sectional view perpendicular to the thickness direction of the conductive coating layer, respectively, of a conductive coating layer (conductive material is two-dimensional) according to still another embodiment of the present invention.
Fig. 10 and 11 are a schematic surface microscopic view and a schematic cross-sectional view perpendicular to the thickness direction of the conductive coating layer, respectively, of a conductive coating layer (conductive material is zero-dimensional and one-dimensional) according to still another embodiment of the present invention.
FIGS. 12 and 13 are respective microscopic morphology images of the conductive coating according to an embodiment of the present invention observed by Scanning Electron Microscopy (SEM);
FIGS. 14 and 15 are respectively a microscopic view of the surface of a conductive coating (conductive material is zero-dimensional, one-dimensional, and two-dimensional) and a schematic cross-sectional view perpendicular to the thickness direction of the conductive coating according to still another embodiment of the present invention;
FIG. 16 is a schematic cross-sectional view of a comparative battery separator according to the present invention;
FIGS. 17 and 18 are respective microscopic morphology images of a pair of scaled conductive coatings of the present invention observed via Scanning Electron Microscopy (SEM);
Detailed Description
In order to make the above and other objects, features and advantages of the present invention more apparent, the following detailed description is given of specific embodiments.
In the following examples, the processes related to the preparation of the positive electrode sheet, the negative electrode sheet and the battery, such as coating, drying, rolling, cutting, tab welding, vacuum packaging, standing, formation, shaping, etc., are performed according to conventional methods in the art unless otherwise specified, and the following examples are not repeated.
Example 1
As shown in fig. 1, the battery separator (hereinafter, referred to as a composite porous separator) provided in the present embodiment includes a porous polymer substrate, a ceramic coating layer (having a thickness of about 2 μm) applied to one surface of the porous polymer substrate, a conductive coating layer (having a thickness of about 1 μm) applied to the other surface of the porous polymer substrate, and a conductive coating layer (having a thickness of about 1 μm) applied to the surface of the ceramic coating layer; as shown in fig. 2 and 3, the shape of the conductive material in the conductive coating is one-dimensional, so as to build a conductive network; the conductive material content in the conductive coating is about 1.34%.
The battery provided in this example was formed using the composite porous separator described above.
The electrical composite porous separator and the battery formed by using the same of the present embodiment are specifically manufactured according to the following processes:
1. preparation of composite porous separator
Using a polyolefin porous membrane as a porous polymer substrate (porous substrate), and thoroughly mixing an alumina ceramic particle material with a polyvinylidene fluoride solution to obtain a slurry containing the ceramic particle material; then, coating the slurry on one surface of a porous polymer substrate in a gravure coating mode, and fully drying to obtain a ceramic coating with the thickness of 2 microns;
dispersing polyvinylidene fluoride and carbon nanotubes (one-dimensional) in NMP according to the mass ratio of 1:0.0136, and uniformly stirring to obtain black slurry with uniformly dispersed conductive materials; wherein, the diameter of the carbon nano tube (one dimension) is about 7-11nm, and the length is about 5-20 μm.
And coating the black slurry on the other surface of the porous polymer substrate and the surface of the ceramic coating in a gravure coating mode, and fully drying to respectively obtain the conductive coatings with the thickness of 1 mu m.
The battery separator of the present embodiment was observed by SEM, and the obtained microscopic morphology is shown in fig. 4 and 5, and it can be seen that one-dimensional carbon nanotubes are distributed in the conductive coating, and are interlaced to form a conductive network.
2. Preparation of positive plate
Lithium cobaltate, acetylene black, polyvinylidene fluoride (PVDF) were mixed in 96: 2: 2 in NMP to form anode slurry, coating the anode slurry on an anode current collector, and then drying, rolling, cutting into pieces and welding tabs to obtain the anode piece.
3. Preparation of negative plate
Mixing artificial graphite, acetylene black, Styrene Butadiene Rubber (SBR) and sodium carboxymethylcellulose (CMC) according to a ratio of 96: 1.5: 1.5: 1 in deionized water to form negative electrode slurry, coating the negative electrode slurry on a negative electrode current collector, and then drying, rolling, cutting and welding a tab to obtain the negative electrode sheet.
4. Preparation of the electrolyte
In a glove box under an inert gas atmosphere, Ethylene Carbonate (EC), diethyl carbonate (DEC), Propylene Carbonate (PC) were mixed in the following ratio of 30: 65: 5 to obtain a mixed solution; then, 15% of lithium hexafluorophosphate was added to the mixed solution based on the total mass of the electrolyte.
5. Preparation of the Battery
And sequentially winding the positive plate, the composite porous partition plate and the negative plate into a bare cell, placing the bare cell in an outer packaging foil, performing top sealing and side sealing, injecting electrolyte into the dried battery, and performing vacuum packaging, standing, formation, shaping and other processes to obtain the lithium ion battery.
Example 2
The battery separator and the battery formed by the separator provided in the embodiment are different from the battery in embodiment 1 only in that: the amount (i.e., content) of conductive material added to the conductive coating is about 0.89%;
the corresponding preparation processes differ only in that: in the step 1, the mass ratio of the polyvinylidene fluoride to the carbon nano tube is 1: 0.0090.
Example 3
The battery separator and the battery formed by the separator provided in the embodiment are different from the battery in embodiment 1 only in that: the addition amount of the conductive material in the conductive coating is about 0.45%;
the corresponding preparation processes differ only in that: in the step 1, the mass ratio of the polyvinylidene fluoride to the carbon nano tubes is 1: 0.0045.
Example 4
The battery separator and the battery formed by the separator provided in the embodiment are different from the battery in embodiment 1 only in that: the addition amount of the conductive material in the conductive coating is about 2.65%;
the corresponding preparation processes differ only in that: in the step 1, the mass ratio of the polyvinylidene fluoride to the carbon nano tube is 1: 0.0272.
Example 5
The present embodiment provides a battery separator and a battery formed by using the same, which is different from embodiment 1 only in that: as shown in fig. 6 and 7, the shape of the conductive material in the conductive coating is zero-dimensional;
the corresponding preparation processes differ only in that: in the step 1, polyvinylidene fluoride and super P (zero-dimensional) are dispersed in NMP according to the mass ratio of 1:0.0136, and uniformly stirred to obtain black slurry with uniformly dispersed conductive materials; wherein the particle size of the super P is about 50 nm.
Example 6
The present embodiment provides a battery separator and a battery formed by using the same, which is different from embodiment 1 only in that: as shown in fig. 8 and 9, the shape of the conductive material in the conductive coating is two-dimensional;
the corresponding preparation processes differ only in that: in the step 1, polyvinylidene fluoride and graphene (two-dimensional) are dispersed in NMP according to the mass ratio of 1:0.0136, and are uniformly stirred to obtain black slurry with uniformly dispersed conductive materials; wherein the graphene (two-dimensional) has a thickness of about 0.8-1.5nm, a length of about 0.5-5 μm, and a width of about 0.5-5 μm.
Example 7
The present embodiment provides a battery separator and a battery formed by using the same, which is different from embodiment 1 only in that: as shown in fig. 10 and 11, the shape of the conductive material in the conductive coating is zero-dimensional and one-dimensional;
the corresponding preparation processes differ only in that: in the step 1, polyvinylidene fluoride, carbon nano tubes (one-dimensional) and super P (zero-dimensional) are dispersed in NMP according to the mass ratio of 1:0.0068:0.0068, and black slurry with uniformly dispersed conductive materials is obtained after uniform stirring; wherein the particle size of the super P is about 50 nm.
The battery separator of the present embodiment was observed by SEM, and the obtained microscopic morphology is shown in fig. 12 and 13, and it can be seen that one-dimensional carbon nanotubes and zero-dimensional super P are distributed in the conductive coating, and are interlaced to form a conductive network.
Example 8
The present embodiment provides a battery separator and a battery formed by using the same, which is different from embodiment 1 only in that: as shown in fig. 14 and 15, the shape of the conductive material in the conductive coating is zero-dimensional, one-dimensional, and two-dimensional;
the corresponding preparation processes differ only in that: in the step 1, polyvinylidene fluoride, graphene (two-dimensional), carbon nano tubes (one-dimensional) and super P (zero-dimensional) are dispersed in NMP according to the mass ratio of 1:0.0045:0.0045:0.0045, and are uniformly stirred to obtain black slurry with uniformly dispersed conductive materials; wherein the graphene (two-dimensional) has a thickness of about 0.8-1.5nm, a length of about 0.5-5 μm, and a width of about 0.5-5 μm; the particle size of super P is about 50 nm.
Comparative example 1
As shown in fig. 16, this comparative example provides a battery separator including a porous polymer substrate, a ceramic coating layer (having a thickness of about 2 μm) applied to one surface of the porous polymer substrate, a rubber coating layer (having a thickness of about 1 μm) applied to the other surface of the porous polymer substrate, and a rubber coating layer (having a thickness of about 1 μm) applied to the surface of the ceramic coating layer. The battery provided in this comparative example was formed using the above-described battery separator.
The comparative battery separator was prepared by a process different from that of example 1 only in that: dispersing polyvinylidene fluoride with the same mass in NMP, and uniformly stirring to obtain colorless transparent slurry; and coating the slurry on the other surface of the porous polymer substrate and the surface of the ceramic coating, and fully drying to obtain glue coating layers with the thickness of 1 mu m respectively. The battery separator of this comparative example was observed by SEM, and the obtained microscopic morphology is shown in fig. 17 and 18, and it can be seen that a significant pore structure was distributed in the rubber coating layer, and no other additives were present on the surface.
Performance evaluation:
the physical properties such as static electricity test values, peeling forces, adhesive forces, etc., of the battery separators of the respective examples and comparative examples were measured as shown in table 1, and the rate performance and cycle performance of the batteries of the respective examples and comparative examples were measured as shown in table 2.
Wherein, the static electricity test: placing the diaphragm (namely the battery separator) on an antistatic table surface, and testing by using a static tester SIMCO; peeling force: testing by using a universal tensile tester; binding power: testing by adopting a plastic packaging machine and a universal tensile tester;
the multiplying power performance test process: testing the voltage, the internal resistance and the thickness of the sample at 25 ℃, fully charging at 0.7 ℃ in a constant temperature room, stopping the current at 0.025 ℃, standing for 10min, and discharging at 2C multiplying power to the lower limit voltage;
the cycle performance test process: testing the voltage, the internal resistance, the thickness and the direct current internal resistance of the sample at 25 ℃, discharging to the lower limit voltage at 0.2 ℃, standing for 10min, charging to 4.2V at 1C, fully charging at 0.7C, discharging to the lower limit voltage at 0.7C, and repeating the steps of charging and discharging again.
TABLE 1 Battery separator Performance for examples 1-8 and comparative example 1
| Examples | Static electricity test value (kV) | Peel force (N/m) | Adhesive force (N/m) |
| Example 1 | 0.01 | 38 | 7.0 |
| Example 2 | 0.04 | 43 | 7.3 |
| Example 3 | 0.4 | 47 | 7.7 |
| Example 4 | 0.01 | 33 | 6.3 |
| Example 5 | 0.03 | 31 | 6.0 |
| Example 6 | 0.01 | 28 | 4.3 |
| Example 7 | 0.01 | 35 | 6.4 |
| Example 8 | 0.01 | 29 | 5.5 |
| Comparative example 1 | 3.9 | 51 | 8.0 |
TABLE 2 Battery Performance of examples 1-8 and comparative example 1
| Examples | Rate capability | Cycle performance |
| Example 1 | 78.67％ | 94.43％ |
| Example 2 | 78.48％ | 94.81％ |
| Example 3 | 77.47％ | 92.64％ |
| Example 4 | 78.86％ | 93.68％ |
| Example 5 | 78.48％ | 93.56％ |
| Example 6 | 79.57％ | 93.86％ |
| Example 7 | 79.33％ | 94.39％ |
| Example 8 | 79.85％ | 94.57％ |
| Comparative example 1 | 75.41％ | 92.51％ |
As can be seen from tables 1 and 2, the battery separators of examples 1 to 8 have excellent antistatic properties, while ensuring good physical properties such as peel strength and adhesive strength, and satisfying the use requirements, compared to comparative example 1, so that the batteries formed using the battery separators of examples 1 to 8 have good safety, while also exhibiting good comprehensive qualities such as rate capability and cycle performance.
Claims (10)
1. A battery separator is characterized by comprising a separator base body and a conductive coating coated on at least one surface of the base body, wherein the raw material of the conductive coating comprises a binder and a conductive material, and the shape of the conductive material comprises at least one of zero dimension, one dimension and two dimensions.
2. The battery separator according to claim 1, wherein the conductive coating layer contains a conductive material in an amount of not less than 0.01% by mass.
3. The battery separator according to claim 2, wherein the conductive coating layer contains the conductive material in an amount of not less than 0.5% by mass.
4. The battery separator according to any of claims 1-3, wherein the conductive material is selected from at least one of a carbon material, a conductive polymer, a metal material, a metal compound material, and/or the binder is selected from at least one of polyvinylidene fluoride, a vinylidene fluoride-hexafluoropropylene copolymer, a polyacrylate, a butyl acrylate-acrylonitrile copolymer, polyacrylonitrile, an ethylene-acrylic acid copolymer, and sodium carboxymethylcellulose.
5. The battery separator according to claim 1 or 4, wherein the zero-dimensional conductive material is selected from at least one of conductive carbon black, super P, conductive graphite, Ketjen black, acetylene black, activated carbon, hierarchical pore carbon, metal nanoparticles, metal oxide nanoparticles, and conductive polymer particles;
and/or the one-dimensional conductive material is selected from at least one of carbon nano tubes, carbon nano fibers, metal nano wires, metal fibers, metal nano belts, metal oxide nano rods and one-dimensional conductive polymers;
and/or the two-dimensional conductive material is selected from at least one of graphene, layered graphite, Mxene, carbon nano-sheets, conductive polymer nano-sheets, metal nano-sheets and two-dimensional metal oxide.
6. The battery separator according to claim 1 or 5, wherein the particle size of the zero-dimensional conductive material is 100nm to 10 μm; and/or the diameter of the one-dimensional conductive material is 1nm-10 μm, and the length is 100nm-100 μm; and/or the two-dimensional conductive material has the thickness of 1nm-10 μm, the length of 100nm-100 μm and the width of 100nm-100 μm.
7. The battery separator according to any of claims 1-6, wherein the conductive coating has a thickness of 0.5 μm to 10 μm.
8. The battery separator of any of claims 1-7, wherein the separator matrix comprises a porous polymeric substrate and a ceramic coating applied to at least one surface of the substrate.
9. A method of making a battery separator as claimed in any of claims 1 to 8, comprising: coating slurry containing a conductive material and a binder on at least one surface of a separator substrate to form a conductive coating, thereby obtaining a battery separator; wherein the shape of the conductive material comprises at least one of zero, one, and two dimensions.
10. A lithium ion battery, characterized in that the battery separator according to any one of claims 1 to 8 is used.
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