CN113131092B - Battery diaphragm and battery - Google Patents
Battery diaphragm and battery Download PDFInfo
- Publication number
- CN113131092B CN113131092B CN202110422324.4A CN202110422324A CN113131092B CN 113131092 B CN113131092 B CN 113131092B CN 202110422324 A CN202110422324 A CN 202110422324A CN 113131092 B CN113131092 B CN 113131092B
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- Prior art keywords
- battery
- base layer
- diaphragm
- separator
- temperature
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a battery diaphragm and a battery, wherein the battery diaphragm comprises a diaphragm base layer and high-temperature micro-curing coatings arranged on two surfaces of the diaphragm base layer, and raw material components of the high-temperature micro-curing coatings comprise oxide electrolyte, polymer electrolyte, a curing agent and high-temperature curable polymer; under the melting point of the diaphragm base layer, the high-temperature curable polymer is subjected to a crosslinking curing reaction under the action of a curing agent to form a network structure; and the melting point of the polymer electrolyte is lower than or equal to that of the separator base layer. Therefore, the battery diaphragm has excellent heat resistance and ion conduction performance, so that the safety performance of the lithium ion battery can be improved, and the electrical performance of the battery in a long-circulating state can be improved.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a battery diaphragm and a battery.
Background
In recent years, the demand of lithium ion batteries for energy density is higher, the safety performance problem of the batteries is more prominent, and under the abuse conditions of extrusion, needling, overcharge and the like, the short circuit occurs inside the batteries, and a large amount of heat is accumulated to cause thermal runaway so as to cause fire and explosion.
The safety performance of the lithium ion battery is more and more emphasized, the diaphragm mainly plays a role in isolating positive and negative electrode materials and conducting lithium ions, and the quality of the self thermal performance of the diaphragm plays a key role in the safety performance and the electrical performance of the lithium ion battery. The diaphragm applied to the current market is mainly a polyolefin diaphragm, the melting point range of the diaphragm is 130-165 ℃, when the internal temperature of a battery core rises rapidly and exceeds the melting temperature, the diaphragm can be melted to cause large-area short circuit and thermal runaway, and further heat is accelerated to accumulate, internal high pressure and high temperature are generated, and combustion and explosion are caused. Therefore, it is necessary to develop a separator having excellent heat resistance and ion conductivity, which can improve the safety of a lithium ion battery.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. To this end, the invention provides a battery diaphragm and a battery.
In a first aspect of the invention, a battery diaphragm is provided, which comprises a diaphragm base layer and a high-temperature micro-curing coating arranged on at least one surface of the diaphragm base layer, wherein the raw material components of the high-temperature micro-curing coating comprise an oxide electrolyte, a polymer electrolyte, a curing agent and a high-temperature curable polymer; at the melting temperature of the diaphragm base layer, the high-temperature curable polymer is subjected to a crosslinking curing reaction under the action of the curing agent to form a network structure; and the melting point of the polymer electrolyte is lower than or equal to the melting temperature of the separator base layer.
The battery separator provided by the embodiment of the invention has at least the following beneficial effects: the battery diaphragm is provided with a high-temperature micro-curing coating formed by compounding raw material components including an oxide electrolyte, a polymer electrolyte, a curing agent and a high-temperature curable polymer on at least one surface of a diaphragm base layer, wherein the ion conductivity of the battery diaphragm can be effectively improved by adopting the oxide electrolyte and the polymer electrolyte, the battery diaphragm can be applied to the construction of a battery, and when the temperature of the battery exceeds the normal working temperature (namely the melting point of the diaphragm base layer), the high-temperature micro-curing polymer can be subjected to high-temperature micro-curing under the action of the curing agent, and the high-temperature curable polymer can be subjected to cross-linking curing reaction under the action of the curing agent to form tight network connection between the oxide electrolyte, so that the integrity of the shape of the diaphragm can be kept; the polymer electrolyte can melt and flow to further plug the pores of the diaphragm substrate, so that the positive and negative electrodes are in an open circuit state, the occurrence of short circuit in the battery is effectively prevented, and the heat-resistant safety performance of the battery is improved. Therefore, the battery diaphragm has excellent heat resistance and ion conduction performance, and the safety performance of the lithium ion battery can be further improved.
In some embodiments of the present invention, in the raw material components of the high temperature micro-curing coating, the mass ratio of the oxide electrolyte, the polymer electrolyte, the curing agent and the high temperature curable polymer is (40-80): (0.4-24): (0.5-6): (10-40).
In some embodiments of the present invention, the polymer electrolyte is selected from at least one of polyether polymers, polyamine polymers, polythioether polymers, polyacrylate polymers, polyacrylonitrile polymers.
In some embodiments of the invention, the high temperature curable polymer is selected from at least one of polyethylene glycol methyl ether methacrylate, vinylene carbonate, ethylene vinyl carbonate, acrylic, polyurethane, unsaturated polyester.
In some embodiments of the present invention, the curing agent is selected from at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone, azobisisobutyronitrile, aziridine, isocyanate, peroxide, polycarbodiimide.
In some embodiments of the invention, the oxide electrolyte is selected from at least one of lithium titanium aluminum phosphate, lithium germanium aluminum phosphate, lithium lanthanum zirconium oxygen, lithium lanthanum titanium oxygen, lithium lanthanum zirconium tantalum oxygen, lithium lanthanum zirconium aluminum oxygen.
In some embodiments of the present invention, the melting point of the separator base layer is 130 to 165 ℃.
In some embodiments of the invention, the separator base layer is selected from a PP separator, a PE separator, or a PP/PE composite separator.
In some embodiments of the present invention, the high temperature micro-cured coating has a thickness of 2 to 6 μm.
In a second aspect of the invention, a battery is provided, which comprises any one of the battery separators provided in the first aspect of the invention. The battery may be a solid-state battery or a solid-liquid hybrid battery.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The embodiment provides a battery diaphragm, which comprises a diaphragm base layer and high-temperature micro-curing coatings coated on the two side surfaces of the diaphragm base layer, wherein the raw material components of the high-temperature micro-curing coatings comprise oxide electrolyte, polymer electrolyte, a curing agent and high-temperature curable polymer. Wherein the thickness of a single surface of the high-temperature micro-curing coating is 3 mu m, and the mass ratio of the oxide electrolyte to the polymer electrolyte to the curing agent to the high-temperature curable polymer is 60: 10: 1: 39; the diaphragm base layer is a PE diaphragm with the thickness of 12 mu m, the oxide electrolyte is titanium aluminum lithium phosphate, the polymer electrolyte is PEO modified polymer, the curing agent is azobisisobutyronitrile, and the high-temperature curable polymer is vinylene carbonate
Example 2
The embodiment provides a battery diaphragm, which comprises a diaphragm base layer and high-temperature micro-curing coatings coated on the two side surfaces of the diaphragm base layer, wherein the raw material components of the high-temperature micro-curing coatings comprise oxide electrolyte, polymer electrolyte, a curing agent and high-temperature curable polymer. Wherein the thickness of a single surface of the high-temperature micro-curing coating is 2 mu m, and the mass ratio of the oxide electrolyte to the polymer electrolyte to the curing agent to the high-temperature curable polymer is 45: 15: 5: 35; the diaphragm base layer is a PP diaphragm with the thickness of 12 mu m, the oxide electrolyte is lithium lanthanum zirconium tantalum oxygen, the polymer electrolyte is PVDF-HFP modified polymer, the curing agent is aziridine, and the high-temperature curable polymer is acrylic resin.
Comparative example 1
This comparative example provides a battery separator that differs from example 1 in that: this comparative example uses PVDF binder instead of the curing agent and high temperature curable polymer in example 1 and replaces the polymer electrolyte with the oxide electrolyte entirely, with the remaining parameters unchanged.
Comparative example 2
This comparative example provides a battery separator that differs from example 2 in that: this comparative example employed PVDF binder in place of the curing agent and high temperature curable polymer in example 2 and replaced the polymer electrolyte entirely with an oxide electrolyte, with the remaining parameters unchanged.
Test examples
The performance of the battery separator prepared in each example and comparative example, including ionic conductivity and thermal shrinkage (including transverse shrinkage and longitudinal shrinkage), was tested by the following specific test methods:
1. testing the thermal shrinkage rate: cutting a battery diaphragm into a sample with the size of 100nm x 100nm, horizontally clamping by adopting a clamping plate, then placing the sample in an oven with the temperature of 180 ℃, keeping for 30min, respectively measuring the transverse size and the longitudinal size after baking, and then according to a formula: the shrinkage rate was (100-size after baking)/100, and the transverse shrinkage rate and the longitudinal shrinkage rate were calculated accordingly.
2. And (3) ionic conductivity test: putting a battery diaphragm in electrolyte LiPF with the concentration of 1M6(ethylene carbonate EC: methylethyl carbonate EMC: diethyl carbonate DEC ═ 3:3: 4) was immersed in the electrolyte, and then 3 layers of the laminated battery separators were placed in 1M LiPF containing EC: EMC: DEC ═ 3:3:46In the electricity buckling shell of the electrolyte, testing an alternating current impedance resistor, and then calculating the ionic conductivity of the battery diaphragm by the following formula: the ionic conductivity is the thickness/(resistance value multiplied by the area) of the battery diaphragm, wherein the thickness of the battery diaphragm is the thickness of the diaphragm base layer plus the thickness of the single side of the high-temperature micro-curing coating multiplied by 2.
The performance test was performed on each of the example and comparative battery separators using the above methods, and the results are shown in table 1.
TABLE 1
As can be seen from the above, in examples 1 and 2, the heat shrinkage rate of the battery separator was significantly reduced and the heat resistance of the battery separator was improved by providing the high-temperature micro-cured coating on the surface of the separator base layer. In comparative examples 1 and 2, PVDF is used as a coating binder alone, and the heat shrinkage performance and the high temperature resistance of the battery separator are far lower than those of the battery separators in examples 1 and 2; in addition, in examples 1 to 2, the addition of the polymer electrolyte can serve as a binder in the high-temperature micro-cured coating and can improve the ionic conductivity.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (8)
1. The battery diaphragm is characterized by comprising a diaphragm base layer and high-temperature micro-curing coatings arranged on two surfaces of the diaphragm base layer, wherein the high-temperature micro-curing coatings comprise the following raw material components in percentage by mass (40-80): (0.4-24): (0.5-6): (10-40) an oxide electrolyte, a polymer electrolyte, a curing agent and a high-temperature curable polymer, wherein the high-temperature curable polymer is selected from at least one of polyethylene glycol methyl ether methacrylate, vinylene carbonate, ethylene vinyl carbonate, acrylic resin, polyurethane and unsaturated polyester; under the melting point of the diaphragm base layer, the high-temperature curable polymer is subjected to a crosslinking curing reaction under the action of the curing agent to form a network structure; and the melting point of the polymer electrolyte is lower than or equal to the melting point of the separator base layer.
2. The battery separator according to claim 1, wherein the polymer electrolyte is selected from at least one of polyether polymers, polyamine polymers, polythioether polymers, polyacrylate polymers, and polyacrylonitrile polymers.
3. The battery separator according to claim 1, wherein the curing agent is at least one selected from the group consisting of 2-hydroxy-2-methyl-1-phenyl-1-propanone, azobisisobutyronitrile, aziridine, isocyanate, peroxide, and polycarbodiimide.
4. The battery separator according to claim 1 wherein the oxide electrolyte is selected from at least one of lithium titanium aluminum phosphate, lithium germanium aluminum phosphate, lithium lanthanum zirconium oxygen, lithium lanthanum titanium oxygen, lithium lanthanum zirconium tantalum oxygen, lithium lanthanum zirconium aluminum oxygen.
5. The battery separator according to claim 1, wherein the melting point of the separator base layer is 130 to 165 ℃.
6. The battery separator of claim 5, wherein the separator base layer is selected from a PP separator, a PE separator, or a PP/PE composite separator.
7. The battery separator according to any of claims 1 to 6, wherein the thickness of the high temperature micro-cured coating is 2 to 6 μm.
8. A battery comprising the battery separator of any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110422324.4A CN113131092B (en) | 2021-04-20 | 2021-04-20 | Battery diaphragm and battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110422324.4A CN113131092B (en) | 2021-04-20 | 2021-04-20 | Battery diaphragm and battery |
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| Publication Number | Publication Date |
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| CN113131092A CN113131092A (en) | 2021-07-16 |
| CN113131092B true CN113131092B (en) | 2022-06-07 |
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| CN202110422324.4A Active CN113131092B (en) | 2021-04-20 | 2021-04-20 | Battery diaphragm and battery |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114784459B (en) * | 2022-06-17 | 2022-09-13 | 宁波长阳科技股份有限公司 | Three-layer co-extrusion diaphragm with high heat resistance and high strength and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101344939B1 (en) * | 2011-12-13 | 2013-12-27 | 주식회사 코캄 | A complex separator with excellent heat resistance for lithium secondary batteries and Lithium secondary batteries comprising the same |
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| CN113131092A (en) | 2021-07-16 |
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