CN113921991B - High-safety diaphragm of lithium ion battery and preparation method and application thereof - Google Patents
High-safety diaphragm of lithium ion battery and preparation method and application thereof Download PDFInfo
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- CN113921991B CN113921991B CN202111170249.3A CN202111170249A CN113921991B CN 113921991 B CN113921991 B CN 113921991B CN 202111170249 A CN202111170249 A CN 202111170249A CN 113921991 B CN113921991 B CN 113921991B
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- ion battery
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- elastomer
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229920001971 elastomer Polymers 0.000 claims abstract description 63
- 239000000806 elastomer Substances 0.000 claims abstract description 55
- 239000002861 polymer material Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000005266 casting Methods 0.000 claims abstract description 9
- 238000009998 heat setting Methods 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000004014 plasticizer Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000001125 extrusion Methods 0.000 claims abstract description 4
- 239000002105 nanoparticle Substances 0.000 claims description 23
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical group CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 16
- -1 polytetrafluoroethylene Polymers 0.000 claims description 13
- 239000004743 Polypropylene Substances 0.000 claims description 8
- VGQXTTSVLMQFHM-UHFFFAOYSA-N peroxyacetyl nitrate Chemical group CC(=O)OO[N+]([O-])=O VGQXTTSVLMQFHM-UHFFFAOYSA-N 0.000 claims description 8
- 229920006254 polymer film Polymers 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 15
- 239000012528 membrane Substances 0.000 abstract description 11
- 239000011148 porous material Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 238000003487 electrochemical reaction Methods 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 abstract description 3
- 229920005597 polymer membrane Polymers 0.000 abstract description 2
- 230000000630 rising effect Effects 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001816 cooling Methods 0.000 description 12
- 239000000155 melt Substances 0.000 description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 6
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical group CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910005793 GeO 2 Inorganic materials 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a high-safety diaphragm of a lithium ion battery, a preparation method and application thereof, and belongs to the technical field of diaphragms of electrochemical batteries. The preparation method of the lithium ion battery high-safety diaphragm comprises the following steps: uniformly mixing the nano elastomer and the high polymer material, adding a pore-forming agent and a plasticizer, heating to obtain a mixture melt, and sequentially carrying out extrusion casting, biaxial stretching and heat setting to obtain a membrane material with the nano elastomer dispersed on the high polymer membrane; the nano elastomer on the diaphragm material gradually expands along with the rising volume of the ambient temperature, and when the temperature reaches a certain value, the aperture of the diaphragm is gradually reduced by the expanded nano elastomer until lithium ions cannot pass through, and the electrochemical reaction is stopped; when the ambient temperature is reduced, the nano elastomer gradually contracts, the nano micropores of the diaphragm gradually recover, the electrochemical reaction continues, the effect of opening and closing the pores is finally realized, and the safety and reliability of the lithium ion battery in the charging and discharging processes are effectively improved.
Description
Technical Field
The invention relates to the technical field of electrochemical battery diaphragms, in particular to a high-safety diaphragm of a lithium ion battery, and a preparation method and application thereof.
Background
Besides the positive electrode, the negative electrode and the electrolyte, the diaphragm material is also one of the key materials indispensable in the lithium battery, and has the main functions of separating the positive electrode from the negative electrode of the battery and enabling lithium ions to freely transmit between the positive electrode and the negative electrode. For the safety of the battery, the separator must be a very good insulator, while for the use of the battery, the separator must have a certain pore channel for the transport of ions. Therefore, the quality of the separator material directly affects the safety performance, capacity, and the like of the battery. In order to ensure the assembly and safety of the lithium ion battery, the lithium battery separator is required to have a certain physical strength.
When the lithium ion battery is overcharged or externally shorted, a severe exothermic reaction occurs inside the lithium ion battery. When the temperature approaches the melting point of the polymer, the micropores of the separator melt and close, so that the transmission of ions is blocked inside, and the battery is protected. The closing temperature is related to the melting point of the material used for the separator, and typically the melting point of the polyethylene material is between 128 and 135 ℃ and the melting point of the polypropylene material is between 150 and 165 ℃. When the internal temperature of the battery is raised by self-heating or external short circuit in the battery, the thermal melting stability of the diaphragm is continuously raised after the internal temperature exceeds the closing temperature, so that the diaphragm is broken in a large area, and the battery is completely short-circuited. From the safety point of view of lithium batteries, the separator should have a low closed cell temperature and a high rupture temperature.
Most of the current research focuses on the inorganic coating of the separator. The inorganic coating composite membrane is also called ceramic composite membrane, which uses polyolefin membrane as support membrane, such as PE (polyethylene) or PP (polypropylene), and inorganic particles with high temperature resistance, such as alumina (Al), are coated on the surface of the membrane 2 O 3 ) (Radiation Physics and Chemistry,2017, 132:65-70), silicon oxide (SiO) 2 ) (Journal of Membrane Science,2017, 535:151-157) or oxidationZirconium (ZrO) 2 ) (Journal of Power Sources,2018, 376:184-190), etc., to form a ceramic coating. Besides good high temperature resistance, the ceramic composite membrane is particularly easy to be wetted by electrolyte due to the fact that the inorganic particles on the surface have high specific surface area and surface energy, and meanwhile has a good retaining effect on the electrolyte. Therefore, ceramic membranes have developed very rapidly in recent years.
Up to now, some achievements have been made at home and abroad to improve the safety of lithium ion battery separator, but these researches have focused on the aspects of surface inorganic coating modification and new separator preparation process. The diaphragm prepared by the novel technology improves the electrochemical performance of the lithium ion battery to a certain extent, but has limited effect of improving the safety of the battery. Although the inorganic coating can improve the safety of the lithium ion battery, the surface firmness is poor, the coating on the surface of the diaphragm is easy to fall off, and meanwhile, the thickness of the diaphragm is increased to a certain extent, so that the performance of the lithium ion battery is influenced. In addition, when the ambient temperature reaches the diaphragm closed-cell temperature, the diaphragm is completely closed-cell, and the battery can be protected to prevent further deterioration, but a lithium ion transmission channel is closed, so that the lithium ion battery cannot continue to work, and waste and economic loss are caused. Although a great deal of research work is done by researchers, a lithium battery separator having high safety has not been fundamentally developed.
Disclosure of Invention
The invention aims to provide a high-safety diaphragm of a lithium ion battery, a preparation method and application thereof, which are used for solving the problems in the prior art.
In order to achieve the above object, the present invention provides the following solutions:
one of the technical schemes of the invention is as follows: a high safety diaphragm of lithium ion battery is composed of nanometer elastomer and polymer film, wherein the nanometer elastomer is dispersed in the polymer film;
the nano elastomer takes inorganic nano particles as an inner core and elastic high polymer material as an outer shell; the high-safety diaphragm of the lithium ion battery is schematically shown in fig. 1.
Further, the polymer film has a porous structure, and the porosity is 44.4% -48.6%.
Further, the inorganic nanoparticle includes B 2 O 3 、Al 2 O 3 、SiO 2 Or GeO 2 One or more of the nanoparticles; the elastic polymer material is rubber.
Further, the preparation of the nano elastomer specifically comprises the following steps: uniformly mixing inorganic nano particles and an elastic polymer material, adding a stabilizer, a solvent and a dispersing agent, and uniformly heating and dispersing to obtain the nano elastomer; the mass ratio of the elastic polymer material to the inorganic nano particles is 1:0.5 to 1.5.
Further, the mass ratio of the elastic polymer material to the inorganic nano particles is 1:0.6 to 1.2; the heating temperature is 150-170 ℃.
Further, the stabilizer is dibutyl tin dimaleate; the solvent is N, N Dimethylformamide (DMF); the dispersing agent is cetyl trimethyl ammonium bromide.
Further, the mass ratio of the inorganic nano particles to the stabilizer, the solvent and the dispersing agent is 1:0.03:0.2-0.8:0.02; the volume percent of the solvent is 80%.
The second technical scheme of the invention is as follows: the preparation method of the lithium ion battery high-safety diaphragm comprises the following steps: and uniformly mixing the nano elastomer and the high polymer material, adding a pore-forming agent and a plasticizer, heating to obtain a mixture melt, and sequentially carrying out extrusion casting, biaxial stretching and heat setting to obtain the lithium ion battery high safety diaphragm.
Further, the polymer material comprises one of polytetrafluoroethylene or polypropylene; the mass ratio of the high polymer material to the nano elastomer is 1:0.01 to 0.1.
Further, the mass ratio of the high polymer material to the nano elastomer is 1:0.02 to 0.07.
Further, the heating temperature is 160-350 ℃; the pore-forming agent is peroxyacetyl nitrate (PAN); the plasticizer is dibutyl phthalate (DBP).
Still further, the extrusion casting specifically includes: heating by an extruder, extruding from a die head through a die orifice, and passing through a cooling roller; the biaxial stretching specifically comprises: simultaneously stretching through a stretching die head in the longitudinal and transverse directions.
Further, the mass ratio of the polymer material to the pore-forming agent to the plasticizer is 1:0.15:0.15.
The third technical scheme of the invention: the application of the high safety diaphragm of the lithium ion battery in the preparation of the lithium ion battery.
The invention discloses the following technical effects:
(1) The high-safety diaphragm of the lithium ion battery consists of a nano elastomer and a high polymer film, wherein the nano elastomer is dispersed on the high polymer film; the nano elastomer on the high polymer membrane gradually expands along with the rising volume of the ambient temperature, and when the temperature reaches a certain value, the expanded nano elastomer causes the aperture of the membrane to gradually become smaller until lithium ions cannot pass through, and the electrochemical reaction is stopped; when the ambient temperature is reduced, the nano elastomer gradually contracts, the nano micropores of the diaphragm gradually recover, the electrochemical reaction continues, the effect of opening and closing the pores is finally realized, and the safety and reliability of the lithium ion battery in the charging and discharging processes are effectively improved.
(2) The lithium ion battery high-safety diaphragm material with the switching effect has the advantages of good air permeability, high wettability, strong tearing resistance, good antistatic performance, high safety, high performance and low cost.
(3) The preparation method provided by the invention is environment-friendly, pollution-free and low in process cost.
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 embodiments 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 other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a membrane material prepared by compounding a polymer material with a nanoelastomer;
FIG. 2 is a diagram of a field emission scanning electron microscope of the high safety diaphragm prepared in example 1 of the present invention;
FIG. 3 is a field emission Scanning Electron Microscope (SEM) image of the high safety diaphragm prepared in example 2 of the present invention.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
Example 1
The preparation method of the lithium ion battery high-safety diaphragm comprises the following steps:
(1) Preparation of nano elastomer: 1250g of rubber and 1000g B are weighed 2 O 3 After 30g of dibutyl tin dimaleate, 437.5mL of DMF and 20g of hexadecyl trimethyl ammonium bromide are added into the nano particles and uniformly mixed, the mixture is heated to 160 ℃ and uniformly stirred and dispersed, a proper amount of acetic acid is added to adjust the pH value of the solution to be=5, and the solution is dried for 3 hours by a vacuum drying oven, so that the nano elastomer with good heat shrinkage effect is prepared.
(2) Preparation of a high-safety diaphragm of a lithium ion battery: 1000g of polypropylene and 40g of nano elastomer are weighed, 150g of PAN and 150g of DBP are added, and the mixture is heated to 190 ℃ to obtain a melt; extruding and casting the melt from a die head, cooling the cast sheet on a cooling roller, taking the cooled cast sheet, biaxially stretching the cast sheet at 135 ℃, and finally performing heat setting at 80 ℃ to prepare the lithium ion battery high-safety diaphragm, wherein a field emission scanning electron microscope image is shown in figure 2, and the load rate of the nano elastomer is 3.84%.
Example 2
(1) Preparation of nano elastomer: weigh 909g rubber and 1000g Al 2 O 3 After 30g of dibutyl tin dimaleate, 437.5mL of DMF and 20g of hexadecyl trimethyl ammonium bromide are added into the nano particles and uniformly mixed, the mixture is heated to 160 ℃ and uniformly stirred and dispersed, a proper amount of acetic acid is added to adjust the pH value of the solution to be=5, and the solution is dried for 3 hours by a vacuum drying oven, so that the nano elastomer with good heat shrinkage effect is prepared.
(2) Preparation of a high-safety diaphragm of a lithium ion battery: 1000g of polytetrafluoroethylene and 60g of nano elastomer are weighed, 150g of PAN and 150g of DBP are added, and the mixture is heated to 350 ℃ to obtain a melt; extruding and casting the melt from a die head, cooling the cast sheet on a cooling roller, taking the cooled cast sheet, biaxially stretching the cast sheet at 135 ℃, and finally performing heat setting at 80 ℃ to prepare the lithium ion battery high-safety diaphragm, wherein a field emission scanning electron microscope image is shown in figure 3, and the load rate of the nano elastomer is 5.82%.
Example 3
(1) Preparation of nano elastomer: weighing 833.33g of rubber and 500g of Al 2 O 3 Nanoparticles and 500g SiO 2 After 30g of dibutyl tin dimaleate, 437.5mL of DMF and 20g of hexadecyl trimethyl ammonium bromide are added into the nano particles and uniformly mixed, the mixture is heated to 160 ℃ and uniformly stirred and dispersed, a proper amount of acetic acid is added to adjust the pH value of the solution to be=5, and the solution is dried for 3 hours by a vacuum drying oven, so that the nano elastomer with good heat shrinkage effect is prepared.
(2) Preparation of a high-safety diaphragm of a lithium ion battery: 1000g of polypropylene and 70g of nano elastomer are weighed, 150g of PAN and 150g of DBP are added, and the mixture is heated to 160 ℃ to obtain a melt; extruding and casting the melt from a die head, cooling the cast sheet on a cooling roller, taking the cooled cast sheet, biaxially stretching the cast sheet at 135 ℃, and finally performing heat setting at 80 ℃ to prepare the lithium ion battery high-safety diaphragm, wherein the load ratio of the nano elastomer is 6.81%.
Example 4
(1) Preparation of nano elastomer: 1666.67g of rubber, 500 and g B g of rubber are weighed 2 O 3 Nanoparticles, 333.33g SiO 2 Nanoparticles and 166.67g GeO 2 After 30g of dibutyl tin dimaleate, 437.5mL of DMF and 20g of hexadecyl trimethyl ammonium bromide are added into the nano particles and uniformly mixed, the mixture is heated to 160 ℃ and uniformly stirred and dispersed, a proper amount of acetic acid is added to adjust the pH value of the solution to be=5, and the solution is dried for 3 hours by a vacuum drying oven, so that the nano elastomer with good heat shrinkage effect is prepared.
(2) Preparation of a high-safety diaphragm of a lithium ion battery: 1000g of polypropylene and 20g of nano elastomer are weighed, 150g of PAN and 150g of DBP are added, and the mixture is heated to 160 ℃ to obtain a melt; extruding and casting the melt from a die head, cooling the cast sheet on a cooling roller, taking the cooled cast sheet, biaxially stretching the cast sheet at 135 ℃, and finally performing heat setting at 80 ℃ to prepare the lithium ion battery high-safety diaphragm, wherein the load ratio of the nano elastomer is 1.86%.
Example 5
(1) Preparation of nano elastomer: 1428.57g of rubber and 571.43g of SiO are weighed 2 Nanoparticles and 428.57g GeO 2 After 30g of dibutyl tin dimaleate, 437.5mL of DMF and 20g of hexadecyl trimethyl ammonium bromide are added into the nano particles and uniformly mixed, the mixture is heated to 160 ℃ and uniformly stirred and dispersed, a proper amount of acetic acid is added to adjust the pH value of the solution to be=5, and the solution is dried for 3 hours by a vacuum drying oven, so that the nano elastomer with good heat shrinkage effect is prepared.
(2) Preparation of a high-safety diaphragm of a lithium ion battery: 1000g of polytetrafluoroethylene and 50g of nano elastomer are weighed, 150g of PAN and 150g of DBP are added, and the mixture is heated to 350 ℃ to obtain a melt; extruding and casting the melt from a die head, cooling the cast sheet on a cooling roller, taking the cooled cast sheet, biaxially stretching the cast sheet at 135 ℃, and finally performing heat setting at 80 ℃ to prepare the lithium ion battery high-safety diaphragm, wherein the load ratio of the nano elastomer is 4.83%.
Comparative example 1
The difference from example 1 is that no nanoelastomer is added in step (2); the loading rate of the nano elastomer is 0.
Comparative example 2
The difference from example 2 is that no nanoelastomer is added in step (2); the loading rate of the nano elastomer is 0.
Comparative example 3
The difference from example 3 is that no nanoelastomer is added in step (2); the loading rate of the nano elastomer is 0.
Comparative example 4
The difference from example 4 is that no nanoelastomer is added in step (2); the loading rate of the nano elastomer is 0.
Comparative example 5
The difference from example 5 is that no nanoelastomer is added in step (2); the loading rate of the nano elastomer is 0.
Comparative example 6
As in example 1, the difference is that B in step (1) 2 O 3 The nanoparticles are replaced with CaO nanoparticles;the loading rate of the nano elastomer is 3.81%.
Effect example 1
The separator materials prepared in examples 1 to 5 and comparative examples 1 to 6 were subjected to performance test, and the test results are shown in Table 1.
TABLE 1
Effect example 2
The volume expansion and contraction times of the nano-elastomer were measured by heating the nano-elastomer sample and then cooling to 25℃and the results are shown in Table 2.
TABLE 2 volume changes of nanoelastomers at different temperatures
Effect example 3
The porosity of the prepared high-safety diaphragm of the lithium ion battery changes along with the temperature in the application process, and the result is shown in Table 3.
Table 3 porosity of high safety separator for lithium ion battery at different temperatures
| Group of | Temperature (. Degree. C.) | Porosity of the porous material | Temperature (. Degree. C.) | Porosity of the porous material |
| Example 1 | 100 | 9.1 | 25 | 38.6 |
| Example 2 | 100 | 10.5 | 25 | 40.3 |
| Example 3 | 100 | 7.1 | 25 | 41.8 |
| Example 4 | 100 | 7.7 | 25 | 41.4 |
| Example 5 | 100 | 10.9 | 25 | 35.6 |
| Comparative example 1 | 100 | 22.8 | 25 | 35.1 |
| Comparative example 2 | 100 | 25.1 | 25 | 17.6 |
| Comparative example 3 | 100 | 23.9 | 25 | 15.9 |
| Comparative example 4 | 100 | 24.3 | 25 | 16.2 |
| Comparative example 5 | 100 | 23.6 | 25 | 15.7 |
| Comparative example 6 | 100 | 17.7 | 25 | 13.2 |
As can be seen from fig. 1-3 and table 1, the lithium ion battery diaphragm material with the "switching effect" prepared by the nano elastomer has uniform pore size distribution, good air permeability and strong tearing resistance, and can effectively improve the safety and reliability of the lithium ion battery in the charging and discharging processes.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (6)
1. The high-safety diaphragm of the lithium ion battery is characterized by comprising a nano elastomer and a high polymer film, wherein the nano elastomer is dispersed in the high polymer film;
the nano elastomer takes inorganic nano particles as an inner core and elastic high polymer material as an outer shell; the polymer film has a porous structure, and the porosity is 44.4% -48.6%;
the inorganic nano particles are B 2 O 3 A nanoparticle; the elastic high polymer material is rubber;
the preparation of the nano elastomer specifically comprises the following steps: uniformly mixing inorganic nano particles and an elastic polymer material, adding a stabilizer, a solvent and a dispersing agent, and uniformly heating and dispersing to obtain the nano elastomer; the mass ratio of the elastic polymer material to the inorganic nano particles is 1.25:1, a step of;
the temperature of the heating was 160 ℃.
2. A method for preparing the high safety diaphragm of the lithium ion battery according to claim 1, which comprises the following steps: and uniformly mixing the nano elastomer and the high polymer material, adding a pore-forming agent and a plasticizer, heating to obtain a mixture melt, and sequentially carrying out extrusion casting, biaxial stretching and heat setting to obtain the lithium ion battery high safety diaphragm.
3. The method for preparing a high safety diaphragm of a lithium ion battery according to claim 2, wherein the polymer material comprises one of polytetrafluoroethylene or polypropylene; the mass ratio of the high polymer material to the nano elastomer is 1:0.01 to 0.1.
4. The method for preparing the lithium ion battery high safety diaphragm according to claim 2, wherein the mass ratio of the high polymer material to the nano elastomer is 1:0.02 to 0.07.
5. The method for preparing the lithium ion battery high safety diaphragm according to claim 2, wherein the heating temperature of the mixture melt obtained by heating is 160-350 ℃; the pore-forming agent is peroxyacetyl nitrate; the plasticizer is dibutyl phthalate.
6. Use of the lithium ion battery high safety separator according to claim 1 in the preparation of lithium ion batteries.
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| CN110911617A (en) * | 2019-12-10 | 2020-03-24 | 安徽新衡新材料科技有限公司 | High-toughness polyolefin lithium ion battery diaphragm and preparation method thereof |
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| JP2019511103A (en) * | 2016-04-07 | 2019-04-18 | ストアドット リミテッド | Lithium ion cell and anode therefor |
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