CN115224440A - Ultrathin high-performance composite diaphragm for lithium ion battery and preparation method thereof - Google Patents
Ultrathin high-performance composite diaphragm for lithium ion battery and preparation method thereof Download PDFInfo
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- CN115224440A CN115224440A CN202210976382.6A CN202210976382A CN115224440A CN 115224440 A CN115224440 A CN 115224440A CN 202210976382 A CN202210976382 A CN 202210976382A CN 115224440 A CN115224440 A CN 115224440A
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- boron nitride
- lithium ion
- ion battery
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Inorganic Chemistry (AREA)
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- Manufacturing & Machinery (AREA)
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Abstract
The invention relates to the field of lithium battery diaphragms, and discloses an ultrathin high-performance composite diaphragm for a lithium ion battery, which comprises the following components in percentage by weight: the invention relates to a base film and a boron nitride nanosheet coating coated on one side or two sides of the base film, wherein the boron nitride nanosheet coating comprises a binder and boron nitride powder, and compared with the prior art, the invention has the beneficial effects that: compared with the traditional diaphragm coated by inorganic materials, the diaphragm has the advantages of light weight and thin thickness, and simultaneously has good chemical stability and thermal conductivity, thereby ensuring the long-time work of the lithium ion battery.
Description
Technical Field
The invention relates to the field of lithium battery diaphragms, in particular to an ultrathin high-performance composite diaphragm for a lithium ion battery and a preparation method thereof.
Background
The lithium ion battery is widely applied due to the advantages of high energy density, high charging speed, long cycle life, no pollution to the environment and the like, and becomes a key component of electronic products, new energy vehicles and industrial energy storage equipment, but the potential safety hazard problem of the lithium ion battery greatly limits the production and the use of the lithium ion battery.
Thermal runaway is a major cause of safety accidents in lithium ion batteries. In a lithium ion battery, a separator is one of its main constituent components, and has ion conductivity and electronic insulation. The diaphragm mainly takes the polypropylene (PP) and the Polyethylene (PE) of polyolefin as main materials, and its mechanical properties and thermal stability are relatively poor, and when the lithium ion battery appears thermal runaway because of defect or abuse, because the existence of internal stress, the diaphragm often can shrink and melt, leads to the inside short circuit that takes place of battery, can further aggravate the thermal runaway of lithium cell, finally leads to lithium cell burning or explosion. Therefore, the stability and mechanical properties of the separator are critical to the safety of the lithium ion battery.
The modified lithium ion battery diaphragm can effectively relieve and inhibit the heat effect and reduce the flammability, and is a simple method for improving the thermal stability of the battery. The ideal separator should have high chemical stability, good interfacial stability, excellent electrolyte wettability, excellent thermal stability and mechanical strength. At present, there are three ways to improve the safety of lithium ion battery separators: (1) Designing and preparing a novel safety diaphragm from the structure; (2) doping or coating an inorganic material in the separator; (3) The polymer with high melting point is doped in the preparation process of the traditional diaphragm. However, the organic material used for modifying the lithium battery diaphragm has the defects of high cost, great environmental hazard and the like, and the inorganic material such as metal oxide, nitride and hydroxide can obviously improve the capacity, safety performance and cycle performance of the battery for modifying the lithium battery diaphragm. In addition, the thickness of the traditional base film and the coating thereof is relatively large, and if the thickness of the diaphragm and the coating is reduced, the usage amount of electrode materials can be effectively increased, and the volume energy density of the battery is improved.
Disclosure of Invention
In order to overcome the defects, the invention develops the ultrathin lithium battery diaphragm based on inorganic material coating, is expected to solve the safety problem of the lithium battery, improves the energy density of the battery, and is more widely applied to the assisted new energy automobile.
An ultra-thin high performance composite separator for lithium ion batteries, comprising: the coating comprises a base film and a boron nitride nanosheet coating coated on one side or two sides of the base film, wherein the boron nitride nanosheet coating comprises a binder and boron nitride powder.
As one improvement of the technical scheme, the base film is a polyethylene film or a polypropylene film with the thickness of 5-9 μm and the porosity of 30-55%.
As one improvement of the technical scheme, the particle size of the boron nitride powder is 200-2000 nm, and the thickness of the boron nitride coating is 0.01-1 μm.
As one improvement of the above technical solution, the binder includes PVDF or an aqueous binder, and the mass ratio of the binder to the boron nitride powder is 5.
As one improvement of the technical scheme, the boron nitride coating also contains nano alumina particles, the particle size of the nano alumina particles is 100-500nm, and the mass ratio of the alumina particles to the boron nitride powder is 0-5-10.
A preparation method of an ultrathin high-performance composite diaphragm for a lithium ion battery comprises the following steps:
(1) Mixing boron nitride powder with an organic solvent for ultrasonic stripping for 12-24 hours to prepare boron nitride nanosheets;
(2) Adding a binder into the boron nitride nanosheet prepared in the step (1), and mixing to prepare boron nitride coating slurry;
(3) Sending the base film into a coating device, and coating by using the boron nitride coating slurry prepared in the step (2);
(4) And (4) drying and rolling the battery diaphragm coated in the step (3) to obtain a finished product of the battery diaphragm coated with boron nitride.
As one improvement of the above technical solution, in the step (1), the specific steps of preparing the boron nitride nanosheet are: mixing boron nitride powder with an organic solvent, adding a dispersing agent, and then carrying out high-power ultrasonic stripping to obtain the boron nitride nanosheet.
As an improvement of the above technical solution, in the step (1), the boron nitride nanosheets and the alumina particles are mixed.
Compared with the prior art, the invention has the beneficial effects that: compared with the traditional diaphragm coated by inorganic materials, the diaphragm has the advantages of light weight and thin thickness, and simultaneously has good chemical stability and thermal conductivity, thereby ensuring the long-time work of the lithium ion battery.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a scanning electron micrograph of the present invention.
FIG. 2 is another SEM image of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1 and 2, in an embodiment of the present invention, an ultra-thin high performance composite separator for a lithium ion battery includes: the film comprises a base film and a boron nitride nanosheet coating coated on one side or two sides of the base film, wherein the boron nitride nanosheet coating comprises a binder and boron nitride powder, the base film is a polyethylene film or a polypropylene film with the thickness of 5-9 mu m and the porosity of 30-55%, the particle size of the boron nitride powder is 200-2000 nm, the thickness of the boron nitride coating is 0.01-1 mu m, the binder comprises PVDF or an aqueous binder, and the mass ratio of the binder to the boron nitride powder is 5;
the boron nitride coating also contains alumina particles with the particle size of 100-500nm, and the mass ratio of the alumina particles to the boron nitride powder is 0-5.
A preparation method of an ultrathin high-performance composite diaphragm for a lithium ion battery comprises the following steps:
(1) Mixing boron nitride powder and an organic solvent for ultrasonic stripping, wherein the ultrasonic time is 12-24 hours, preparing the boron nitride nanosheet, specifically, mixing the boron nitride powder and the organic solvent, adding a dispersing agent, and then carrying out high-power ultrasonic stripping to obtain the boron nitride nanosheet; in addition, alumina particles and boron nitride nanosheets can be added and mixed, and the mass ratio of the alumina particles to the boron nitride powder is 0-5;
(2) Adding a binder into the boron nitride nanosheet prepared in the step (1), stirring for 0.5-1 hour, and mixing to prepare boron nitride coating slurry;
(3) Conveying the base film into a coating device, and coating by using the boron nitride coating slurry prepared in the step (2);
(4) And (4) drying and rolling the battery diaphragm coated in the step (3) to obtain a finished product of the battery diaphragm coated with boron nitride.
Example 1:
(1) Mixing boron nitride powder and an organic solvent for ultrasonic stripping, wherein the ultrasonic time is 12-24 hours, preparing boron nitride nanosheets, specifically, mixing the boron nitride powder and the organic solvent, adding a dispersing agent, and then carrying out high-power ultrasonic stripping to obtain the boron nitride nanosheets; in addition, alumina particles and boron nitride nanosheets can be added and mixed, and the mass ratio of the alumina particles to the boron nitride powder is 0-5;
(2) Adding a binder into the boron nitride nanosheets prepared in the step (1), stirring for 0.5-1 hour, and mixing to prepare boron nitride coating slurry;
(3) Conveying the base film into a coating device, and coating by using the boron nitride coating slurry prepared in the step (2);
(4) And (4) drying and rolling the battery diaphragm coated in the step (3) to obtain a finished product of the battery diaphragm coated with boron nitride.
Comparative example 2:
comparative example 2 differs from comparative example 1 in that: in the step (1), the boron nitride powder is also mixed with nano alumina particles.
And (3) performance testing:
the lithium battery diaphragm performance test result is as follows:
it will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (8)
1. An ultra-thin high performance composite separator for a lithium ion battery, comprising: the coating comprises a base film and a boron nitride nanosheet coating coated on one side or two sides of the base film, wherein the boron nitride nanosheet coating comprises a binder and boron nitride powder.
2. The ultra-thin high-performance composite separator for the lithium ion battery according to claim 1, wherein: the base film is a polyethylene film or a polypropylene film with the thickness of 5-9 mu m and the porosity of 30-55%.
3. The ultra-thin high-performance composite separator for the lithium ion battery of claim 1, characterized in that: the particle size of the boron nitride powder is 200-2000 nm, and the thickness of the boron nitride nano coating is 0.01-1 μm.
4. The ultra-thin high-performance composite separator for the lithium ion battery of claim 1, characterized in that: the binder comprises PVDF or water-based binder, and the mass ratio of the binder to the boron nitride powder is 5.
5. The ultra-thin high-performance composite separator for the lithium ion battery according to claim 1, wherein: the boron nitride nano coating also contains alumina particles, the particle size of the alumina particles is 100-500nm, and the mass ratio of the alumina particles to the boron nitride powder is 0-5.
6. A preparation method of an ultrathin high-performance composite diaphragm for a lithium ion battery comprises the following steps:
(1) Mixing boron nitride powder with an organic solvent for ultrasonic stripping for 12-24 hours to prepare boron nitride nanosheets;
(2) Adding a binder into the boron nitride nanosheets prepared in the step (1), and mixing to prepare boron nitride coating slurry;
(3) Conveying the base film into a coating device, and coating by using the boron nitride coating slurry prepared in the step (2);
(4) And (4) drying and rolling the battery diaphragm coated in the step (3) to obtain a finished product of the battery diaphragm coated with boron nitride.
7. The preparation method of the ultrathin high-performance composite membrane for the lithium ion battery according to claim 6, characterized by comprising the following steps: in the step (1), the specific steps for preparing the boron nitride nanosheet are as follows: mixing boron nitride powder with an organic solvent, adding a dispersing agent, and carrying out high-power ultrasonic stripping to obtain the boron nitride nanosheet.
8. The preparation method of the ultrathin high-performance composite membrane for the lithium ion battery according to claim 7, characterized by comprising the following steps: in the step (1), the boron nitride nanosheets and alumina particles are mixed.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210976382.6A CN115224440A (en) | 2022-08-15 | 2022-08-15 | Ultrathin high-performance composite diaphragm for lithium ion battery and preparation method thereof |
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| CN202210976382.6A CN115224440A (en) | 2022-08-15 | 2022-08-15 | Ultrathin high-performance composite diaphragm for lithium ion battery and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115939669A (en) * | 2022-12-28 | 2023-04-07 | 广东比沃新能源有限公司 | High-stability lithium manganate battery and preparation method thereof |
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| CN104600231A (en) * | 2014-12-31 | 2015-05-06 | 北京鼎能开源电池科技股份有限公司 | Diaphragm provided with active nano boron nitride coating, and preparation method of diaphragm |
| CN108059725A (en) * | 2017-11-17 | 2018-05-22 | 陕西启源科技发展有限责任公司 | The preparation method of barium titanate/boron nitride/polyimides tri compound film |
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| CN111081951A (en) * | 2020-01-09 | 2020-04-28 | 重庆云天化纽米科技股份有限公司 | Ceramic coated battery separator and method of making same |
| WO2020179978A1 (en) * | 2019-03-07 | 2020-09-10 | 순천향대학교 산학협력단 | Secondary battery, fuel cell, separator for secondary battery or fuel cell, and method for manufacturing separator |
| CN112909436A (en) * | 2021-03-03 | 2021-06-04 | 合肥国轩高科动力能源有限公司 | Lithium ion battery composite diaphragm, preparation method thereof and lithium ion battery |
| CN113851646A (en) * | 2021-09-29 | 2021-12-28 | 江南大学 | Zinc ion battery cathode material based on boron nitride film and preparation method thereof |
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2022
- 2022-08-15 CN CN202210976382.6A patent/CN115224440A/en active Pending
Patent Citations (7)
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| CN104600231A (en) * | 2014-12-31 | 2015-05-06 | 北京鼎能开源电池科技股份有限公司 | Diaphragm provided with active nano boron nitride coating, and preparation method of diaphragm |
| CN108059725A (en) * | 2017-11-17 | 2018-05-22 | 陕西启源科技发展有限责任公司 | The preparation method of barium titanate/boron nitride/polyimides tri compound film |
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| CN113851646A (en) * | 2021-09-29 | 2021-12-28 | 江南大学 | Zinc ion battery cathode material based on boron nitride film and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115939669A (en) * | 2022-12-28 | 2023-04-07 | 广东比沃新能源有限公司 | High-stability lithium manganate battery and preparation method thereof |
| CN115939669B (en) * | 2022-12-28 | 2023-08-25 | 广东比沃新能源有限公司 | High-stability lithium manganate battery and preparation method thereof |
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