CN112993490B - Lithium battery diaphragm and preparation method and application thereof - Google Patents
Lithium battery diaphragm and preparation method and application thereof Download PDFInfo
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- CN112993490B CN112993490B CN202110237630.0A CN202110237630A CN112993490B CN 112993490 B CN112993490 B CN 112993490B CN 202110237630 A CN202110237630 A CN 202110237630A CN 112993490 B CN112993490 B CN 112993490B
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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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- 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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Abstract
The invention provides a lithium battery diaphragm, a preparation method and application thereof, and relates to the technical field of lithium batteries. A lithium battery diaphragm comprises a base film and an organic elastic material coating covered on the base film; the tensile strength of the diaphragm in the transverse direction and the longitudinal direction is 200-300MPa, the elongation at break is 80% -150%, and the puncture resistance is above 950 GF. The organic elastic material in the separator includes at least one of an acrylic resin, a hydrogenated styrene-butadiene block copolymer, and a thermoplastic polyurethane elastomer rubber. The lithium battery diaphragm has higher mechanical strength, and improves the tensile strength and puncture resistance of the diaphragm in the mechanical directions (MD and TD). The organic elastic material coating resists electrolyte corrosion, and when external force impacts the battery, the coating can ensure that the anode material and the cathode material are not in short circuit, thereby improving the safety of the lithium ion battery.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a lithium battery diaphragm and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high voltage, high specific energy density, long cycle life, small self-discharge, safety, no memory effect and the like, and is applied to various fields. In order to avoid contact between the positive electrode and the negative electrode in the lithium ion battery, the positive electrode and the negative electrode are required to be separated from each other by a diaphragm, so that the battery is prevented from being short-circuited. The separator plays an important role in lithium ion batteries, and the separator of the lithium ion batteries has the following defects:
(1) poor mechanical properties;
(2) the liquid absorption rate is low.
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the present invention is to provide a lithium battery separator, so as to solve the technical problems of poor mechanical properties and low liquid absorption rate of the lithium battery separator in the prior art.
The second object of the invention is to provide the preparation method of the lithium battery diaphragm, which has simple process and strong process controllability.
The third object of the invention is to provide the application of the lithium battery diaphragm in the lithium battery, provide the diaphragm material with high safety and high mechanical property for the lithium battery, and improve the conductivity and safety of the lithium battery.
In order to solve the technical problems, the invention adopts the following technical scheme:
the first aspect of the invention provides a lithium battery separator comprising a base film and an organic elastic material coating covered on the base film; the tensile strength of the diaphragm in the transverse direction and the longitudinal direction is 200-300MPa, the elongation at break is 80% -150%, and the puncture resistance is above 950 GF.
Further, the organic elastic material coating comprises an organic elastic material;
preferably, the organic elastic material includes at least one of an acrylic resin, a hydrogenated styrene-butadiene block copolymer, and a thermoplastic polyurethane elastomer rubber.
Further, the thickness of the organic elastic material coating layer is 1-15 μm.
Further, the acrylic resin is of the type of japanese rayleigh 620B;
preferably, the hydrogenated styrene-butadiene block copolymer is of the type U.S. koteng 1651;
preferably, the thermoplastic polyurethane elastomer rubber is of the type De Kogyo 385SX.
Further, the base film comprises a polyolefin separator;
preferably, the polyolefin separator includes one of a polypropylene separator, a polyethylene separator, or a composite separator composed of polypropylene and polyethylene.
Further, the organic elastic material coating is mainly formed by coating and drying an organic elastic material solution;
preferably, the solvent in the organic elastic material solution includes at least one of water, ethanol and n-amyl acetate.
Further, the mass ratio of the organic elastic material in the organic elastic material solution is 20-80%, and the balance is solvent;
preferably, the mass ratio of the organic elastic material in the organic elastic material solution is 30-50%, and the balance is solvent.
The second aspect of the invention provides a preparation method of the lithium battery diaphragm, which is characterized in that the lithium battery diaphragm is obtained by coating an organic elastic material solution on the surface of a base film and drying;
wherein an organic elastic material solution is coated on at least one surface of the base film.
Further, the organic elastic material solution is obtained by uniformly dispersing the organic elastic material in a solvent;
preferably, the dispersing means comprises stirring;
preferably, the stirring speed is 500-1000r/min, and the stirring time is 1-6h;
preferably, the drying temperature is 50-70 ℃ and the drying time is 5-60min.
The third aspect of the invention provides the lithium battery separator of the first aspect and the application of the lithium battery separator prepared by the preparation method of the second aspect in a lithium battery.
Compared with the prior art, the invention has the following beneficial effects:
1. the lithium battery diaphragm provided by the invention improves the flexibility of the diaphragm base film, so that the diaphragm has good mechanical properties, the tensile strength of the mechanical properties in the transverse direction and the longitudinal direction is 200-300MPa, the elongation at break is 80% -150%, the puncture resistance strength can reach over 950GF, and the liquid absorption capacity can reach 1.06mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The adhesion capability between the diaphragm and the pole piece is increased, and the adsorption and retention capability of the diaphragm to electrolyte is improved, so that the safety performance and the electrical performance of the battery are improved.
2. The preparation method of the lithium battery diaphragm provided by the invention has the advantages of simple process, convenience in operation and strong process controllability, and is suitable for large-scale industrial production.
3. The lithium battery manufactured by the lithium battery diaphragm provided by the invention has good thermal stability, and the positive and negative electrode materials are not shorted under the abuse conditions of puncture, impact, extrusion and the like of the battery, so that the safety of the battery is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is a diagram showing the structure of a lithium battery separator provided in example 1;
fig. 2 is a photograph showing puncture resistance of the organic elastic material coating of the lithium battery separator provided in example 4.
Wherein, 1-the organic elastic material coating; 2-base film; 3-holes.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustration of the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The lithium ion battery mainly comprises a positive electrode material, a negative electrode material, electrolyte, a diaphragm, and a packaging material. The diaphragm plays a role of electronic insulation between the anode and the cathode and provides a lithium ion migration micropore channel, and is a key material for ensuring the safety of a battery system and influencing the performance of the battery. Although the separator does not directly participate in electrode reaction, it affects the dynamic process of the battery, and determines the charge and discharge, cycle life, rate and other performances of the battery. The tensile strength of the separator in the TD direction is much lower than in the MD direction. Under the action of external force, the TD direction is extremely easy to crack, and the safety problem of the battery is caused.
According to the first aspect of the invention, the lithium battery diaphragm comprises a base film and an organic elastic material coating covered on the base film; the tensile strength of the diaphragm in the transverse direction and the longitudinal direction is 200-300MPa, the elongation at break is 80% -150%, and the puncture resistance is above 950 GF.
The lithium battery diaphragm provided by the invention improves the tensile strength of the diaphragm in the mechanical direction (MD and TD), and can reach 200-300MPa, while the tensile strength of the diaphragm in the prior art is about 150 MPa. The elongation at break is 80% -150%, the puncture resistance is above 950GF, the puncture resistance of the diaphragm is obviously improved, the damage to the diaphragm in the electric stress and assembly process is prevented, and the use safety is ensured in the battery use process.
The function of the separator in a lithium ion battery is mainly embodied in two aspects. Firstly, provide safety guarantee for the battery. The separator material must have good insulation properties to prevent the positive and negative electrodes from contacting and shorting or being pierced by burrs, particles, dendrites, so that the separator needs to have a certain tensile and piercing strength, be not easy to tear, and basically maintain dimensional stability under sudden high temperature conditions, and not melt shrinkage to cause large-area short circuit and thermal runaway of the battery. And secondly, providing a micropore channel for realizing charge and discharge functions and multiplying power performance for the lithium ion battery. Thus, the separator must be a film having a high porosity and uniform distribution of micropores.
The mechanical strength of the lithium battery diaphragm comprises tensile strength and puncture strength, and the tensile strength requires that the diaphragm cannot cause damage to the diaphragm during coating and winding; the greater the piercing strength is, the more difficult the burrs and protruding particles on the pole piece pierce through the diaphragm, or the diaphragm is pierced when lithium dendrites appear on the battery, so that the short circuit of the battery is avoided, and the safety of the battery is ensured.
The tensile strength is a critical value for transition of the diaphragm from uniform plastic deformation to local concentrated plastic deformation, and is also the maximum bearing capacity of the diaphragm under static stretching conditions. The tensile strength characterizes the resistance of the diaphragm to the greatest uniform plastic deformation, the deformation of the diaphragm is uniform and consistent before the diaphragm is subjected to the greatest tensile stress, but after exceeding, the diaphragm starts to neck, i.e. concentrated deformation occurs. The tensile strength reflects the fracture resistance of the separator.
Further, the organic elastic material coating comprises an organic elastic material;
preferably, the organic elastic material includes at least one of an acrylic resin, a hydrogenated styrene-butadiene block copolymer, and a thermoplastic polyurethane elastomer rubber.
The lithium battery diaphragm material provided by the invention comprises a base film and an organic elastic material coating coated on the base film. The coating covers the holes on the base film, so that the electrolyte of the anode and the cathode is separated; the coating has good wettability to electrolyte and sufficient liquid absorption and moisture retention capacity. In addition, the organic coating has higher mechanical strength, and is compounded with the base film, so that the tensile strength of the diaphragm in the mechanical direction (MD and TD) is improved, and the puncture resistance of the diaphragm is obviously improved.
The organic elastic material coating improves the wettability of the separator to the electrolyte, promotes the closed cell function of the separator, improves the extrusion resistance of the separator and reduces the risk of penetration by lithium dendrites.
Acrylic resins are a generic term for polymers of acrylic acid, methacrylic acid and derivatives thereof. After the coating made of acrylic resin is dried, a porous structure can be formed, so that the diaphragm has stronger liquid absorption and electrode bonding performance.
The hydrogenated styrene-butadiene block copolymer is a hot melt rubber having the formula (C 8 H 8 .C 4 H 6 ) x, which does not contain unsaturated double bonds, has good chemical stability and mechanical properties.
Thermoplastic polyurethane elastomer rubbers, the molecules of which are substantially linear, have little or no chemical cross-linking. The linear polyurethane molecular chains have physical cross-links formed by a plurality of hydrogen bonds, and the hydrogen bonds play a role in strengthening the morphology, so that the thermoplastic polyurethane elastomer rubber has the advantages of high modulus, high strength, wear resistance, chemical resistance, hydrolysis resistance, high temperature resistance and mold resistance.
Further, the thickness of the organic elastic material coating layer is 1-15 μm.
In a specific embodiment of the invention, the coating thickness is 1-25 μm and the thickness of the organic elastic material coating formed after drying is 1-15 μm.
The thickness of the organic elastic material coating influences the thickness of the lithium battery diaphragm, and the thinner the diaphragm thickness is, the smaller the internal resistance of the battery is, so that more space can be reserved for electrode materials; however, the thickness is too thin, the mechanical property is affected, and the battery is more easily pierced by large particles, pole piece burrs and dendrites, so that the safety coefficient of the battery is reduced. In a preferred embodiment of the invention, the thickness of the organic elastomeric coating is typically, but not limited to, 1 μm,5 μm,10 μm and 15 μm.
Further, the acrylic resin is of the type of japanese rayleigh 620B;
preferably, the hydrogenated styrene-butadiene block copolymer is of the type U.S. koteng 1651;
preferably, the thermoplastic polyurethane elastomer rubber is of the type De Kogyo 385SX.
Further, the base film comprises a polyolefin separator.
The polyolefin diaphragm can provide good mechanical property and chemical stability within a reasonable cost range, has high-temperature self-closing property, and ensures the safety of the lithium ion battery in daily use.
Preferably, the polyolefin separator includes one of a polypropylene separator, a polyethylene separator, or a composite separator composed of polypropylene and polyethylene.
The composite diaphragm not only has excellent mechanical properties, but also has certain thermal closed pore performance, and the difference of melting points of PE and PP is utilized. When the internal temperature of the battery rises, the PE melting point is reached firstly, then the PE diaphragm is melted and the micropores are blocked, lithium ions cannot pass through, so that the battery cannot continue to work, thermal runaway is prevented, meanwhile, the temperature does not reach the PP melting point, so that the PP layer is not influenced by the temperature, the integral shape of the diaphragm can be maintained unchanged, the function of the diaphragm is continuously acted, and the contact of the positive pole and the negative pole is prevented.
Further, the organic elastic material coating is mainly formed by coating and drying an organic elastic material solution;
preferably, the solvent in the organic elastic material solution includes at least one of water, ethanol and n-amyl acetate.
The solvent in the organic elastomer solution dilutes the organic elastomer, allowing the thickness of the coating to be easily controlled and removed during subsequent drying.
Further, the mass ratio of the organic elastic material in the organic elastic material solution is 20% -80%, and the balance is solvent.
In particular embodiments of the present invention, the mass percent of the organic elastomeric material is typically, but not limited to, 20%, 40%, 60% or 80%.
Preferably, the mass ratio of the organic elastic material in the organic elastic material solution is 30-50%, and the balance is solvent.
In a preferred embodiment of the invention, the mass percentage of the organic elastic material is typically, but not limited to, 30%, 40% or 50%.
The second aspect of the invention provides a preparation method of the lithium battery diaphragm, which is characterized in that the lithium battery diaphragm is obtained by coating an organic elastic material solution on the surface of a base film and drying;
wherein an organic elastic material solution is coated on at least one surface of the base film.
In a specific embodiment of the present invention, the organic elastic material solution is coated on one surface or both surfaces of the base film.
Further, the organic elastic material solution is obtained by uniformly dispersing the organic elastic material in a solvent.
Preferably, the dispersing means comprises stirring;
preferably, the stirring speed is 500-1000r/min, and the stirring time is 1-6h.
In particular embodiments of the present invention, the stirring speed is typically, but not limited to, 500r/min,800r/min or 1000r/min; the stirring time is typically, but not limited to, 1h, 3h or 6h.
Preferably, the drying temperature is 50-70 ℃ and the drying time is 5-60min.
The third aspect of the invention provides the lithium battery separator of the first aspect and the application of the lithium battery separator prepared by the preparation method of the second aspect in a lithium battery.
The lithium battery manufactured by the lithium battery diaphragm provided by the invention ensures that the anode material and the cathode material are not short-circuited when the battery is impacted by external force, and has good safety.
Some embodiments of the present invention will be described in detail below with reference to examples. The following embodiments and features of the embodiments may be combined with each other without conflict.
The specifications and types of the raw materials used in the examples and comparative examples in the present invention are shown in the following Table 1, and are commercially available as not illustrated in the tables, and the parts used in the examples and comparative examples are parts by mass.
TABLE 1 raw materials specification and model Meter
| Name of the name | Model number | Manufacturer/component |
| Acrylic resin | 620B | Japanese Rui Wen |
| Hydrogenated styrene-butadiene block copolymers | G1651 | U.S. Koteng |
| Thermoplastic polyurethane elastomer rubber | 385SX | German Korschment |
Example 1
This embodiment provides a lithium battery separator, the structure of which is shown in fig. 1, which is mainly composed of a base film 2 and an organic elastic material coating layer 1 attached to the surface of the base film, wherein holes 3 are present in the base film. The preparation method comprises the following specific steps:
and 3, drying the diaphragm prepared in the step 2 at 60 ℃ for 1h to obtain the lithium battery diaphragm.
Example 2
The embodiment provides a lithium battery diaphragm, which comprises the following specific preparation steps:
and 3, drying the diaphragm prepared in the step 2 at 60 ℃ for 1h to obtain the lithium battery diaphragm.
Example 3
The embodiment provides a lithium battery diaphragm, which comprises the following specific preparation steps:
and 3, drying the diaphragm prepared in the step 2 at 60 ℃ for 1h to obtain the lithium battery diaphragm.
Example 4
The embodiment provides a lithium battery diaphragm, which comprises the following specific preparation steps:
and 3, drying the diaphragm prepared in the step 2 at 60 ℃ for 1h to obtain the lithium battery diaphragm.
Example 5
The present example provided a lithium battery separator, which was different from example 4 in that 10 parts of acrylic resin was added to 90 parts of water and mixed, and the remaining steps were the same as example 4, and no detailed description thereof was given.
Example 6
The present example provided a lithium battery separator, which was different from example 4 in that 30 parts of acrylic resin was added to 70 parts of water and mixed, and the remaining steps were the same as example 4, and no detailed description thereof was given.
Example 7
The present example provided a lithium battery separator, which was different from example 4 in that 90 parts of acrylic resin was added to 10 parts of water and mixed, and the remaining steps were the same as example 4, and no detailed description thereof was given.
Example 8
The present example provided a lithium battery separator, which was different from example 4 in that 50 parts of acrylic resin was added to 50 parts of ethanol and mixed, and the remaining steps were the same as example 4, and no detailed description thereof was given.
Example 9
The present example provided a lithium battery separator, which was different from example 4 in that 50 parts of acrylic resin was added to 50 parts of n-amyl acetate and mixed, and the remaining steps were the same as example 4, and will not be described again.
Example 10
The difference between the lithium battery separator provided in this embodiment and embodiment 4 is that the thickness of the lithium battery separator formed by drying the organic elastic material coating is 15 μm, and the other steps are the same as those in embodiment 4, and are not described here again.
Example 11
The difference between the lithium battery separator provided in this embodiment and embodiment 4 is that the thickness of the lithium battery separator formed by drying the organic elastic material coating is 30 μm, and the other steps are the same as those in embodiment 4, and are not described here again.
Example 12
The present embodiment provides a lithium battery separator, which is different from embodiment 4 in that the organic elastic material solution is uniformly coated on the front and back sides of the 12 μm polyethylene film base film, and the other steps are the same as embodiment 4, and are not described herein.
Example 13
The embodiment provides a lithium battery diaphragm, which comprises the following specific preparation steps:
step 4, uniformly coating the organic elastic material solution on one surface of a polyethylene film base film with the thickness of 12 mu m;
and 5, drying the diaphragm prepared in the step 4 at 60 ℃ for 1h to obtain the lithium battery diaphragm.
Comparative example 1
This comparative example provides a lithium battery separator which is a polyethylene film without a composite coating layer and has a thickness of 12 μm.
Comparative example 2
The comparative example provides a lithium battery separator, which comprises the following specific preparation steps:
And 2, spraying the ceramic powder mixture obtained in the step 1 on two sides of a polyethylene film base film with the thickness of 12 mu m, wherein the spraying thickness is 1 mu m, and obtaining the lithium battery diaphragm with the ceramic powder sprayed with the polyethylene film.
Test example 1
Lithium battery separators obtained in examples 1-11 and comparative examples 1-2 were assembled with positive and negative electrode sheets to prepare lithium batteries, and electrochemical tests were performed on the obtained lithium batteries. The test contents include a tensile strength test, a puncture resistance test and a liquid absorption amount test. The specific test method is as follows:
tensile strength test: the diaphragm is placed on a cutting machine to be cut into strips with the width of 15mm, and marked at the interval of 10cm between the test sample strips, the diaphragm sample is fixed on a universal testing machine to start measurement, the stress-strain curve is recorded in the process that the diaphragm is broken, the tensile strength value of the diaphragm sample is obtained, the test is repeated for 5 times for taking the average value, and the result is shown in Table 2.
Puncture resistance strength test: the membrane samples were mounted on a universal tester during testing, the membrane samples were punched with a 2mm diameter needle device at a speed of 50mm/min, stress strain curves were recorded, puncture strength values for the membrane samples were obtained, the test was repeated 5 times for each group of samples, and the results are shown in Table 2. Fig. 2 is a graph showing puncture resistance of the lithium battery separator provided in example 4.
Liquid absorption test: in the test, the diaphragm sample is cut into a certain size, the diaphragm sample is soaked in electrolyte for 0.5h at normal temperature, the weight difference of the diaphragm sample in unit area before and after soaking is the liquid absorption amount, and the obtained results are shown in Table 2.
Table 2 diaphragm performance test table
Test example 2
The organic elastic material coating layer obtained in example 4 was vertically fixed to a jig, and the organic elastic material coating layer was slowly pierced with a ballpoint pen. A photograph of its deformation was taken. As can be seen from fig. 2, the organic elastic material coating has very high deformation elongation and puncture resistance, which proves that the lithium battery separator provided by the invention has good mechanical properties.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (7)
1. The lithium battery diaphragm is characterized by comprising a base film and an organic elastic material coating covered on the base film; the tensile strength of the diaphragm in the transverse direction and the longitudinal direction is 200-300MPa, the elongation at break is 80% -150%, the puncture resistance strength is above 950GF, and the liquid absorption capacity can reach 1.06mg/cm 2 ；
The thickness of the organic elastic material coating is 1-15 mu m;
the organic elastic material coating is formed by coating and drying an organic elastic material solution, wherein the mass ratio of the organic elastic material in the organic elastic material solution is 20% -80%, and the balance is a solvent;
the organic elastic material is one of acrylic resin, hydrogenated styrene-butadiene block copolymer and thermoplastic polyurethane elastomer rubber;
the solvent of the organic elastic material solution is at least one of water, ethanol and n-amyl acetate.
2. The lithium battery separator of claim 1, wherein the base film comprises a polyolefin separator.
3. The lithium battery separator according to claim 2, wherein the polyolefin separator comprises one of a polypropylene separator, a polyethylene separator, or a composite separator composed of polypropylene and polyethylene.
4. The lithium battery diaphragm according to claim 1, wherein the mass ratio of the organic elastic material in the organic elastic material solution is 30% -50%, and the balance is solvent.
5. The method for preparing a lithium battery separator according to any one of claims 1 to 4, wherein the lithium battery separator is obtained after the organic elastic material solution is coated on the surface of the base film and dried;
wherein an organic elastic material solution is coated on at least one surface of the base film.
6. The method for producing a lithium battery separator according to claim 5, wherein the organic elastic material solution is obtained by uniformly dispersing the organic elastic material in a solvent;
the dispersing mode comprises stirring;
the stirring speed is 500-1000r/min, and the stirring time is 1-6h;
the drying temperature is 50-70deg.C, and the drying time is 5-60min.
7. Use of a lithium battery separator according to any one of claims 1-4 or a lithium battery separator prepared by the preparation method of claim 5 or 6 in a lithium battery.
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| CN114243203B (en) * | 2021-12-01 | 2024-06-21 | 远景动力技术(江苏)有限公司 | High-elongation diaphragm, preparation method thereof and lithium ion battery |
| CN114243221B (en) * | 2021-12-23 | 2022-10-11 | 中材锂膜有限公司 | High-elasticity deformation diaphragm and preparation method thereof |
| CN114976489B (en) * | 2022-07-01 | 2024-04-05 | 珠海冠宇电池股份有限公司 | Coating, separator comprising same and battery |
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