CN116565454A - PVDF (polyvinylidene fluoride) coaxial nanotube-based battery diaphragm and preparation method thereof - Google Patents
PVDF (polyvinylidene fluoride) coaxial nanotube-based battery diaphragm and preparation method thereof Download PDFInfo
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- 239000002071 nanotube Substances 0.000 title claims abstract description 104
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 85
- 239000002131 composite material Substances 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 239000011777 magnesium Substances 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 46
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 35
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 26
- 239000012498 ultrapure water Substances 0.000 claims description 26
- 239000006255 coating slurry Substances 0.000 claims description 21
- 239000002070 nanowire Substances 0.000 claims description 21
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 19
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 19
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 17
- 235000012239 silicon dioxide Nutrition 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 14
- 239000002562 thickening agent Substances 0.000 claims description 14
- 239000000080 wetting agent Substances 0.000 claims description 14
- 239000002518 antifoaming agent Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 229920000098 polyolefin Polymers 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 238000005096 rolling process Methods 0.000 claims description 12
- 239000011247 coating layer Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000005253 cladding Methods 0.000 claims description 5
- 239000013530 defoamer Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 150000008431 aliphatic amides Chemical group 0.000 claims description 3
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 3
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 150000008051 alkyl sulfates Chemical group 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 14
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 13
- 239000003063 flame retardant Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 230000014759 maintenance of location Effects 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 238000001291 vacuum drying Methods 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- -1 polyethylene Polymers 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000007761 roller coating Methods 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910019440 Mg(OH) Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000527 sonication Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
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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
-
- 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
-
- 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
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
Abstract
The invention relates to the technical field of battery diaphragms, in particular to a battery diaphragm based on PVDF coaxial nanotubes and a preparation method thereof. The invention provides a battery diaphragm based on PVDF coaxial nanotubes and a preparation method thereof, and PVDF coated Mg (OH) is introduced into the battery diaphragm 2 The coaxial nanotube composite material greatly improves the mechanical strength and the heat shrinkage performance of the diaphragm. In addition, porous PVDF is combined with Mg (OH) having flame retardant properties 2 The nanotubes can cooperate with each other to furtherThe mechanical properties and heat shrinkage properties of the separator are improved. According to the PVDF coaxial nanotube-based battery diaphragm provided by the invention, the modified material integrally presents a hollow porous structure, so that the specific surface area of the material is greatly increased, and the liquid absorption and retention capacity of the diaphragm is greatly enhanced. The composite diaphragm prepared by the invention has excellent flame retardant property, pole piece adhesive property, electrolyte wettability and heat shrinkage property, and has higher mechanical strength.
Description
Technical Field
The invention relates to the technical field of battery diaphragms, in particular to a battery diaphragm based on PVDF coaxial nanotubes and a preparation method thereof.
Background
The lithium battery is used as a novel secondary battery, has high energy density, long cycle life and wider application range, and can be widely applied to energy storage, portable electronic devices and power automobiles. The diaphragm is used as one of important components of the lithium battery, can effectively prevent the contact of the positive electrode and the negative electrode from generating short circuit, and improves the safety performance of the lithium battery, so that the improvement of the performance and the safety of the lithium battery are more and more important.
Polyolefin separators are one of the most widely used lithium battery separators at present, however, there are some disadvantages to the polyolefin separators existing in the market: (1) the bonding performance of the polar plate is poor and the performance of the electrolyte is insufficient, so that a series of problems of poor cycle performance, low thermal stability, unstable interface between the polar plate and the diaphragm, poor hardness of the battery, adverse processing and transportation and the like occur to the battery, and the improvement of the energy density of the battery and the development of a high-performance ultrathin battery are greatly limited; (2) polyolefin materials have very low melting points, and when the battery has thermal runaway, the membrane is easy to break, so that the thermal runaway is more serious, and the battery burns and even explodes. Aiming at the problem that the adhesion of the polyolefin diaphragm to the pole piece and the electrolyte wettability are poor, the main solution is to coat a water-based PVDF adhesive layer on one side or two sides of the polyolefin diaphragm, and the adhesive coating layer can effectively improve the adhesion of the diaphragm and has good wettability with the electrolyte; aiming at the problem of poor heat resistance of a polyolefin diaphragm, the main solution at present is to coat a high-temperature resistant ceramic coating on one side or two sides of the polyolefin diaphragm, so that the diaphragm can be delayed to be closed to 150 ℃, but the closed-pore temperature of 150 ℃ cannot completely avoid the short circuit of a lithium battery at high temperature and spontaneous combustion caused by the short circuit, so that the heat resistance of the diaphragm needs to be further improved, and the rupture risk of the diaphragm is reduced, thereby improving the safety of the battery. Therefore, the development of a lithium ion battery separator with high flame retardance, high adhesion and high electrolyte wettability is a commonly pursued goal in the industry.
In order to solve the problems, the invention provides a battery diaphragm based on PVDF coaxial nanotubes and a preparation method thereof, which are used for improving electrolyte wettability, flame retardance, pole piece bonding performance and heat shrinkage performance of the lithium ion battery diaphragm.
Disclosure of Invention
The invention aims to provide a battery diaphragm based on PVDF coaxial nanotubes and a preparation method thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a battery diaphragm based on PVDF coaxial nanotubes, the battery diaphragm comprises a base film and a coating layer, wherein the coating layer is arranged on any side of the base film; the coating layer comprises the following components: PVDF cladding Mg (OH) 2 Coaxial nanotube composite, dispersant, thickener, binder, wetting agent, defoamer and ultrapure water.
More preferably, the dispersing agent is aliphatic amide, the thickening agent is hydroxymethyl cellulose sodium, the binder is polyacrylic acid, the wetting agent is alkyl sulfate, and the defoaming agent is polyether type defoaming agent.
More preferably, the base film is a polyolefin separator.
More preferably, the coating layer comprises the following components in percentage: 0.6 to 1.9 percent of dispersing agent and 20 to 40 percent of PVDF coated Mg (OH) 2 The coaxial nanotube composite material comprises, by weight, 5% -15% of a thickener, 1% -5% of a binder, 0.1% -0.6% of a wetting agent, 0.05% -0.25% of a defoaming agent, and the balance of ultrapure water.
More optimally, the preparation method of the battery diaphragm comprises the following steps:
step one: dispersing agent and PVDF are used for coating Mg (OH) 2 Adding the coaxial nanotube composite material into ultrapure water, uniformly stirring, adding a thickening agent, a binder, a wetting agent and a defoaming agent, stirring, and filtering to obtain coaxial nanotube coating slurry;
step two: and (3) coating the coaxial nanotube coating slurry on any side of the polyolefin membrane, baking and rolling to obtain the battery membrane based on the PVDF coaxial nanotube.
More preferably, the PVDF is coated with Mg (OH) 2 The preparation method of the coaxial nanotube composite material comprises the following steps: adding polyvinylidene fluoride into N, N-dimethylformamide to obtain a mixed solution, sealing, heating to 70-72 ℃, and uniformly stirring to obtain a PVDF solution; PVDF solution was added to Mg (OH) 2 Uniformly stirring the nano tube dispersion liquid to obtain a mixed liquid; centrifuging, washing and drying the mixed solution to obtain PVDF coated Mg (OH) 2 Coaxial nanotube composites.
Preferably, the Mg (OH) 2 The preparation method of the nanotube dispersion liquid comprises the following steps: dissolving magnesium sulfate powder in ultrapure water, adding hydrophilic treated silica nanowire, stirring uniformly, heating to 70-72 ℃, adding ammonia water, controlling the pH value of the reaction end point to 8-10, filtering precipitate, washing, drying to obtain powder, adding into sodium hydroxide solution, maintaining for 4-5h, filtering, washing, drying to obtain Mg (OH) 2 A nanotube; mg (OH) 2 Adding the nanotubes into ultrapure water, and stirring uniformly to obtain Mg (OH) 2 Nanotube dispersion.
More optimally, the preparation method of the silicon dioxide nanowire after hydrophilic treatment comprises the following steps: adding KH-550 silane coupling agent into absolute ethyl alcohol, stirring uniformly, adding silicon dioxide powder, performing ultrasonic treatment, and drying at 58-62 ℃ to obtain the silicon dioxide nanowire after hydrophilic treatment.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a battery diaphragm based on PVDF coaxial nanotubes and a preparation method thereof, and PVDF coated Mg (OH) is introduced into the battery diaphragm 2 The coaxial nanotube composite material greatly improves the mechanical strength and the heat shrinkage performance of the diaphragm. In addition, porous PVDF is combined with Mg (OH) having flame retardant properties 2 The nanotubes can cooperate to further improve the mechanical properties and heat shrinkage properties of the separator.
(2) According to the PVDF coaxial nanotube-based battery diaphragm provided by the invention, the modified material integrally presents a hollow porous structure, so that the specific surface area of the material is greatly increased, and the liquid absorption and retention capacity of the diaphragm is greatly enhanced.
(3) PVDF particles in the traditional PVDF coating slurry are easy to agglomerate and have small contact area with the base film, so that PVDF attached to the surface is easy to fall off, the cohesiveness of the diaphragm to the pole piece and the electrolyte wettability are greatly reduced, and the performance of the battery is further affected; the PVDF-coaxial nanotube-based battery diaphragm provided by the invention is characterized in that PVDF particles are dissolved and then coated on Mg (OH) 2 On the nanotube, PVDF coats Mg (OH) 2 The coaxial nanotube composite material has larger contact area with the base film, so that the problem of PVDF powder removal is remarkably improved, and on the other hand, due to the larger specific surface area of the composite material, more active sites can be exposed by PVDF, so that the cohesiveness of the diaphragm to the pole piece and the electrolyte wettability are greatly improved.
(4)Mg(OH) 2 The crystal water of (2) is decomposed by heat and absorbs heat to form a charred layer, so Mg (OH) 2 Also has good flame retardant effect. When the temperature rises to the decomposition temperature, mg (OH) 2 The decomposition releases water vapor, absorbs latent heat, dilutes the concentration of oxygen and combustible gas near the surface of the combustion object, and makes surface combustion difficult to carry out; the charring layer formed on the surface prevents oxygen and heat from entering, and magnesium oxide generated by decomposition of the charring layer is also a good refractory material, has good high temperature resistance and heat conduction performance, and can improve the capability of the material for resisting open fire; the invention provides a battery diaphragm based on PVDF coaxial nanotubes, wherein an active material Mg (OH) with flame retardant effect is used 2 The prepared hollow nano tube structure greatly enhances the exposure of flame retardant active sites, compared with the traditional Mg (OH) 2 The particles can play a better flame-retardant role, and the flame retardant property of the diaphragm is improved.
The composite diaphragm prepared by the invention has excellent flame retardant property, pole piece adhesive property, electrolyte wettability and heat shrinkage property, and has higher mechanical strength.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The dispersant used in the invention is an aliphatic amide dispersant: vinyl bis-stearamide 110-30-5, available from Wohan Ji Xinyi, inc. of Biotechnology.
The thickener is sodium hydroxymethyl cellulose, which is provided by He-Fei Hongrui Biotechnology Co.
The binder is polyacrylic acid: ETERSO 1730, provided by chang materials.
The defoamer is polyether defoamer: DF-999, provided by Kelamal.
The wetting agent is sodium dodecyl sulfate: y0000620, provided by sigma aldrich.
The polyvinylidene fluoride model is LBG-8200, supplied by Acomax.
The particle size d50=0.1-1 mm of the magnesium sulfate powder.
The diameter of the silica nanowire is 20-40nm, and the length is 10-20 mu m.
The polyolefin membrane is made by the company, the preparation method refers to patent CN202010339196.2, the polyolefin is polyethylene, and the thickness is 9 mu m.
Example 1:
s1: PVDF cladding Mg (OH) 2 Preparation of coaxial nanotube composite:
step one:
adding 2mL of KH-550 silane coupling agent into 250mL of absolute ethyl alcohol, magnetically stirring for 35min, adding 0.7g of silicon dioxide nanowire powder, carrying out ultrasonic treatment for 60min, and drying at 60 ℃ for 23h to obtain the silicon dioxide nanowire after hydrophilic treatment.
Dissolving magnesium sulfate powder in ultrapure water to prepare 250mL of magnesium sulfate solution with the concentration of 1.91mol/L, then adding 1.6965g of the hydrophilically treated silicon dioxide nanowires into the magnesium sulfate solution under the condition of continuous stirring, magnetically stirring for 80 minutes, and then performing ultrasonic dispersion for 4.5 hours to uniformly disperse the silicon dioxide nanowires in the magnesium sulfate solution; after the temperature of the solution had risen to 70℃2mol were added at a flow rate of 38mL/minAmmonia water of/L, controlling pH value at reaction end point to 9, filtering precipitate, washing precipitate with ultrapure water, drying the precipitate in vacuum drying oven at 80deg.C for 16 hr, controlling vacuum degree of vacuum drying to 0.08Mpa, adding the obtained powder into 5.0mol/L sodium hydroxide solution after vacuum drying, maintaining for 4 hr, filtering, washing, and drying at 80deg.C for 12 hr to obtain Mg (OH) 2 A nanotube.
Step two: at 460rpm, 2.59g of Mg (OH) prepared as described above were added 2 The nanotubes were added to 286mL of ultra-pure water and magnetically stirred at 420rpm for 115 minutes, followed by sonication at 30KHZ and 300w of ultrasonic power for 8 hours to obtain Mg (OH) 2 A nanotube dispersion;
slowly adding 1.04g of polyvinylidene fluoride (PVDF) into 13.37g of N, N-dimethylformamide, sealing the mixed solution, then heating the mixed solution to 70 ℃ in a water bath kettle, stirring the mixed solution for 6 hours at 370rpm to obtain PVDF solution, and adding the PVDF solution into the uniformly dispersed Mg (OH) at a flow rate of 1.4mL/min under the condition of continuous stirring 2 Stirring the nano tube dispersion liquid for 2 hours at a rotating speed of 330rpm, and then treating the nano tube dispersion liquid for 11 hours at ultrasonic power of 35KHZ and 380w to obtain a mixed liquid; centrifuging the mixed solution at 8000rpm for 20 min, washing the precipitate, and vacuum drying at 60deg.C under 0.08Mpa vacuum for 16 hr to obtain PVDF coated Mg (OH) 2 Coaxial nanotube composites.
S2: preparation of coaxial nanotube coating slurry:
1.15% by weight of dispersant, 20% by weight of PVDF-coated Mg (OH) prepared above 2 Premixing the coaxial nanotube composite material in 64.3wt% of ultrapure water for 45min, wherein the rotating speed is 450rpm; adding 9.5wt% of thickener, and stirring for 50min at 650rpm; adding 4.5wt% of binder, and continuously stirring for 80min at 550rpm; adding 0.3wt% of wetting agent, and 0.25wt% of defoaming agent, stirring for 40min at the rotating speed of 300rpm; filtering to remove iron and obtaining the coaxial nanotube coating slurry.
S3: preparation of a battery diaphragm based on PVDF coaxial nanotubes:
and uniformly rolling the prepared coaxial nanotube coating slurry on any side of a polyethylene diaphragm with the thickness of 9 mu m by a coating machine by adopting a micro-gravure roller coating process, baking at 67 ℃ and rolling for standby, thereby obtaining the battery diaphragm based on the PVDF coaxial nanotube.
Example 2:
s1: PVDF cladding Mg (OH) 2 Preparation of coaxial nanotube composite:
step one:
adding 2mL of KH-550 silane coupling agent into 250mL of absolute ethyl alcohol, magnetically stirring for 35min, adding 0.7g of silicon dioxide powder, performing ultrasonic treatment for 60min, and drying at 60 ℃ for 23h to obtain the hydrophilic treated silicon dioxide nanowire.
Dissolving magnesium sulfate powder in ultrapure water to prepare 250mL of magnesium sulfate solution with the concentration of 1.91mol/L, then adding 1.6965g of the hydrophilically treated silicon dioxide nanowires into the magnesium sulfate solution under the condition of continuous stirring, magnetically stirring for 80 minutes, and then performing ultrasonic dispersion for 4.5 hours to uniformly disperse the silicon dioxide nanowires in the magnesium sulfate solution; heating the solution to 70deg.C, adding 2mol/L ammonia water at 38mL/min, controlling pH at reaction end point to 8-10, filtering to obtain precipitate, washing the precipitate with ultrapure water, drying the precipitate in vacuum drying oven at 80deg.C for 16 hr, controlling vacuum degree of vacuum drying to 0.08Mpa, adding the obtained powder into 5.0mol/L sodium hydroxide solution, maintaining for 4 hr, filtering, washing, and drying at 80deg.C for 12 hr to obtain Mg (OH) 2 A nanotube.
Step two: at 460rpm, 2.59g of Mg (OH) prepared as described above were added 2 The nanotubes were added to 286mL of ultra-pure water and magnetically stirred at 420rpm for 115 minutes, followed by sonication at 30KHZ and 300w of ultrasonic power for 8 hours to obtain Mg (OH) 2 A nanotube dispersion;
1.04g of polyvinylidene fluoride (PVDF) was slowly added to 13.37g of N, N-dimethylformamide, the mixture was sealed, and then it was heated in a water bathStirring at 70deg.C for 6 hr at 370rpm to obtain PVDF solution, and adding the obtained PVDF solution into the above uniformly dispersed Mg (OH) at a flow rate of 1.4mL/min under continuous stirring 2 Stirring the nano tube dispersion liquid for 2 hours at a rotating speed of 330rpm, and then treating the nano tube dispersion liquid for 11 hours at ultrasonic power of 35KHZ and 380w to obtain a mixed liquid; centrifuging the mixed solution at 8000rpm for 20 min, washing the precipitate, and vacuum drying at 60deg.C under 0.08Mpa vacuum for 16 hr to obtain PVDF coated Mg (OH) 2 Coaxial nanotube composites.
S2: preparation of coaxial nanotube coating slurry:
1.15% by weight of dispersant, 30% by weight of PVDF-coated Mg (OH) prepared above 2 Premixing the coaxial nanotube composite material in 54.3wt% of ultrapure water for 45min, wherein the rotating speed is 450rpm; adding 9.5wt% of thickener, and stirring for 50min at 650rpm; adding 4.5wt% of binder, and continuously stirring for 80min at 550rpm; adding 0.3wt% of wetting agent, and 0.25wt% of defoaming agent, stirring for 40min at the rotating speed of 300rpm; filtering to remove iron and obtaining the coaxial nanotube coating slurry.
S3: preparation of a battery diaphragm based on PVDF coaxial nanotubes:
and uniformly rolling the prepared coaxial nanotube coating slurry on any side of a polyethylene diaphragm with the thickness of 9 mu m by a coating machine by adopting a micro-gravure roller coating process, baking at 67 ℃ and rolling for standby, thereby obtaining the battery diaphragm based on the PVDF coaxial nanotube.
Example 3:
s1: PVDF cladding Mg (OH) 2 Preparation of coaxial nanotube composite:
step one:
adding 2mL of KH-550 silane coupling agent into 250mL of absolute ethyl alcohol, magnetically stirring for 35min, adding 0.7g of silicon dioxide powder, performing ultrasonic treatment for 60min, and drying at 60 ℃ for 23h to obtain the hydrophilic treated silicon dioxide nanowire.
Dissolving magnesium sulfate powder in ultrapure water to obtain 250mL of magnesium sulfate solution with concentration of 1.91mol/L, and stirring continuously to obtain 1.69Adding 65g of the hydrophilically treated silica nanowires into a magnesium sulfate solution, magnetically stirring for 80 minutes, and then performing ultrasonic dispersion for 4.5 hours to uniformly disperse the silica nanowires in the magnesium sulfate solution; heating the solution to 70deg.C, adding 2mol/L ammonia water at 38mL/min, controlling pH at reaction end point to 8-10, filtering to obtain precipitate, washing the precipitate with ultrapure water, drying the precipitate in vacuum drying oven at 80deg.C for 16 hr, controlling vacuum degree of vacuum drying to 0.08Mpa, adding the obtained powder into 5.0mol/L sodium hydroxide solution, maintaining for 4 hr, filtering, washing, and drying at 80deg.C for 12 hr to obtain Mg (OH) 2 A nanotube.
Step two: at 460rpm, 2.59g of Mg (OH) prepared as described above were added 2 The nanotubes were added to 286mL of ultra-pure water and magnetically stirred at 420rpm for 115 minutes, followed by sonication at 30KHZ and 300w of ultrasonic power for 8 hours to obtain Mg (OH) 2 A nanotube dispersion;
slowly adding 1.04g of polyvinylidene fluoride (PVDF) into 13.37g of N, N-dimethylformamide, sealing the mixed solution, then heating the mixed solution to 70 ℃ in a water bath kettle, stirring the mixed solution for 6 hours at 370rpm to obtain PVDF solution, and adding the PVDF solution into the uniformly dispersed Mg (OH) at a flow rate of 1.4mL/min under the condition of continuous stirring 2 Stirring the nano tube dispersion liquid for 2 hours at a rotating speed of 330rpm, and then treating the nano tube dispersion liquid for 11 hours at ultrasonic power of 35KHZ and 380w to obtain a mixed liquid; centrifuging the mixed solution at 8000rpm for 20 min, washing the precipitate, and vacuum drying at 60deg.C under 0.08Mpa vacuum for 16 hr to obtain PVDF coated Mg (OH) 2 Coaxial nanotube composites.
S2: preparation of coaxial nanotube coating slurry:
1.15% by weight of dispersant, 40% by weight of PVDF-coated Mg (OH) prepared above 2 Premixing the coaxial nanotube composite material in 44.3wt% of ultrapure water for 45min, wherein the rotating speed is 450rpm; adding 9.5wt% of thickener, and stirring for 50min at 650rpm; adding 4.5wt% of binder, stirring for 80min,the rotation speed is 550rpm; adding 0.3wt% of wetting agent, and 0.25wt% of defoaming agent, stirring for 40min at the rotating speed of 300rpm; filtering to remove iron and obtaining the coaxial nanotube coating slurry.
S3: preparation of a battery diaphragm based on PVDF coaxial nanotubes:
and uniformly rolling the prepared coaxial nanotube coating slurry on any side of a polyethylene diaphragm with the thickness of 9 mu m by a coating machine by adopting a micro-gravure roller coating process, baking at 67 ℃ and rolling for standby, thereby obtaining the battery diaphragm based on the PVDF coaxial nanotube.
Comparative example 1: the same polyethylene separator as in example 1 was used, without coating the coating slurry.
Comparative example 2:
S1：Mg(OH) 2 preparation of nanotubes:
adding 2mL of KH-550 silane coupling agent into 250mL of absolute ethyl alcohol, magnetically stirring for 35min, adding 0.7g of silicon dioxide nanowire powder, carrying out ultrasonic treatment for 60min, and drying at 60 ℃ for 23h to obtain the silicon dioxide nanowire after hydrophilic treatment.
Dissolving magnesium sulfate powder in ultrapure water to prepare 250ml of magnesium sulfate solution with the concentration of 1.91mol/L, then adding 1.6965g of the hydrophilically treated silicon dioxide nanowires into the magnesium sulfate solution under the condition of continuous stirring, continuing magnetic stirring for 80 minutes, and then performing ultrasonic dispersion for 4.5 hours to uniformly disperse the silicon dioxide nanowires in the magnesium sulfate solution; heating the solution to 70deg.C, adding 2mol/L ammonia water at a flow rate of 38mL/min, controlling the pH at the end of the reaction at 9, filtering the precipitate, washing the precipitate with ultrapure water, drying the precipitate in a vacuum drying oven at 80deg.C for 16 hr, controlling the vacuum degree of vacuum drying at 0.08Mpa, adding the obtained powder into 5.0mol/L sodium hydroxide solution, maintaining for 4 hr, filtering, washing, and drying at 80deg.C for 12 hr to obtain Mg (OH) 2 A nanotube.
S2：Mg(OH) 2 Preparation of the nanotube coating slurry:
1.15wt% of dispersant, 20wt% of Mg prepared as described above(OH) 2 The nanotubes were premixed in 64.3wt% ultrapure water for 45min at a rotational speed of 450rpm; adding 9.5wt% of thickener, and stirring for 50min at 650rpm; adding 4.5wt% of binder, and continuously stirring for 80min at 550rpm; adding 0.3wt% of wetting agent, and 0.25wt% of defoaming agent, stirring for 40min at the rotating speed of 300rpm; finally, filtering and removing iron to obtain Mg (OH) 2 The nanotubes are coated with the slurry.
S3: mg (OH) 2 Preparation of a nanotube-modified battery separator:
uniformly rolling the prepared coating slurry on any side of a polyethylene diaphragm with the thickness of 9 mu m by a coating machine by adopting a micro-gravure roller coating process, baking by a baking oven at 67 ℃, and rolling for standby to obtain the Mg (OH) to be prepared 2 Nanotube modified battery separator.
Comparative example 3:
s1: preparing PVDF coating slurry:
1.15wt% of dispersant and 20wt% of PVDF powder (model LBG-8200, supplied by Acomat) are premixed in 64.3wt% of ultrapure water for 45min at a rotating speed of 450rpm; adding 9.5wt% of thickener, and stirring for 50min at 650rpm; adding 4.5wt% of binder, and continuously stirring for 80min at 550rpm; adding 0.3wt% of wetting agent, and 0.25wt% of defoaming agent, stirring for 40min at the rotating speed of 300rpm; and finally, filtering to remove iron to obtain the conventional PVDF coating slurry.
S1: preparation of PVDF modified battery separator:
and uniformly rolling the prepared coating slurry on any side of a polyethylene diaphragm with the thickness of 9 mu m by a coating machine by adopting a micro-gravure roller coating process, baking by a baking oven at 67 ℃, and rolling for standby, thus obtaining the conventional PVDF-modified battery diaphragm for the lithium ion battery to be prepared.
Experiment:
the battery separators prepared in examples 1 to 3 and comparative examples 1 to 3 were used for performance test, and the air permeation value, anodic-hot press peeling, needling strength, and heat shrinkage were tested with reference to GB/T36363-2018;
oxygen index measurement: reference IOS4589-2: placing the diaphragm into a transparent combustion cylinder, wherein the temperature of the mixed gas is 24 ℃; when the top surface is ignited, the flame contacts the top surface for 25 seconds, the flame is removed every 5 seconds, whether the membrane burns or not is observed, and the minimum oxygen concentration required by the combustion is just maintained to be the oxygen index;
liquid absorption rate measurement: a 50mm×50mm sample was cut from the prepared membrane, placed in a desiccator for 24 hours, and then taken out, and the sample was weighed and recorded as M (accurate to 0.01 g); immersing the sample in a beaker containing electrolyte, holding for 10min, gently clamping one corner of the sample with plastic forceps, taking out and immediately weighing, and recording as M1 (accurate to 0.01 g); liquid absorption= (M1-M)/M;
and (3) liquid retention rate measurement: a 50mm×50mm sample was cut from the prepared membrane, placed in a desiccator for 24 hours, and then taken out, and the sample was weighed and recorded as M (accurate to 0.01 g); immersing the sample in a beaker filled with electrolyte, slightly clamping one corner of the sample by using plastic forceps after keeping for 10min, taking out and suspending for 3min until part of the electrolyte is naturally dripped off, and weighing, wherein M2 (accurate to 0.01 g) is recorded; retention = (M2-M)/M; the properties of the composite separators prepared in examples 1 to 3 and comparative examples 1 to 3 are shown in the following table:
conclusion: examples 1 to 3 PVDF coated Mg (OH) in the coating slurries 2 The content of the coaxial nanotube composite material is sequentially increased, the ventilation value and the flame retardant property of the diaphragm are continuously increased, and the PVDF is coated with Mg (OH) 2 The coaxial nanotube has a hollow porous structure, so that the specific surface area of the material is greatly increased, and the liquid absorption and retention capacity of the diaphragm is greatly enhanced; meanwhile, porous PVDF and Mg (OH) with flame retardant properties 2 The nanotubes can cooperate to further improve the mechanical properties and heat shrinkage properties of the separator. Comparative example 1 was not coated with the coating and the separator had the worst performance. Comparative example 2 coating slip without PVDF coated Mg (OH) 2 The mechanical strength and heat shrinkage performance of the nano tube and the diaphragm are greatly reduced, and Mg (OH) 2 Nanotube material structureThe number of sex sites is small, and the flame retardant effect is also reduced. Comparative example 3 without Mg (OH) added 2 The PVDF attached to the surface of the diaphragm is easy to fall off, the cohesiveness of the diaphragm to the pole piece and the electrolyte wettability are greatly reduced, the active site is reduced, the cohesiveness of the diaphragm to the pole piece and the electrolyte wettability are poor, and meanwhile, no Mg (OH) is added 2 The flame retardant properties of the particles and the diaphragm are greatly reduced.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A battery separator based on PVDF coaxial nanotubes, characterized by: the battery diaphragm comprises a base film and a coating layer, wherein the coating layer is arranged on any side of the base film; the coating layer comprises the following components: PVDF cladding Mg (OH) 2 Coaxial nanotube composite, dispersant, thickener, binder, wetting agent, defoamer and ultrapure water.
2. The PVDF coaxial nanotube based battery separator of claim 1, wherein: the dispersing agent is aliphatic amide, the thickening agent is hydroxymethyl cellulose sodium, the binder is polyacrylic acid, the wetting agent is alkyl sulfate, and the defoaming agent is polyether type defoaming agent.
3. The PVDF coaxial nanotube based battery separator of claim 1, wherein: the base film is a polyolefin separator.
4. The PVDF-based coaxial nanotube cell separator of claim 1, wherein: the coating layer comprises the following components in percentage: 0.6 to 1.9 percent of dispersing agent and 20 to 40 percent of PVDF coated Mg (OH) 2 The coaxial nanotube composite material comprises, by weight, 5% -15% of a thickener, 1% -5% of a binder, 0.1% -0.6% of a wetting agent, 0.05% -0.25% of a defoaming agent, and the balance of ultrapure water.
5. A preparation method of a battery diaphragm based on PVDF coaxial nanotubes is characterized by comprising the following steps: the preparation method of the battery diaphragm comprises the following steps:
step one: dispersing agent and PVDF are used for coating Mg (OH) 2 Adding the coaxial nanotube composite material into ultrapure water, uniformly stirring, adding a thickening agent, a binder, a wetting agent and a defoaming agent, stirring, and filtering to obtain coaxial nanotube coating slurry;
step two: and (3) coating the coaxial nanotube coating slurry on any side of the polyolefin membrane, baking and rolling to obtain the battery membrane based on the PVDF coaxial nanotube.
6. The method for preparing the battery diaphragm based on the PVDF coaxial nanotube, which is characterized in that: the PVDF is coated with Mg (OH) 2 The preparation method of the coaxial nanotube composite material comprises the following steps: adding polyvinylidene fluoride into N, N-dimethylformamide to obtain a mixed solution, sealing, heating to 70-72 ℃, and uniformly stirring to obtain a PVDF solution; PVDF solution was added to Mg (OH) 2 Uniformly stirring the nano tube dispersion liquid to obtain a mixed liquid; centrifuging, washing and drying the mixed solution to obtain PVDF coated Mg (OH) 2 Coaxial nanotube composites.
7. The method for preparing the battery diaphragm based on the PVDF coaxial nanotube, which is characterized in that: said Mg (OH) 2 The preparation method of the nanotube dispersion liquid comprises the following steps: dissolving magnesium sulfate powder in ultrapure water, adding hydrophilic treated silica nanowire, stirring, heating to 70-72deg.C, adding ammonia water, controlling pH at reaction end point to 8-10, filtering precipitate, and washingWashing, drying to obtain powder, adding into sodium hydroxide solution, maintaining for 4-5 hr, filtering, washing, and drying to obtain Mg (OH) 2 A nanotube; mg (OH) 2 Adding the nanotubes into ultrapure water, and stirring uniformly to obtain Mg (OH) 2 Nanotube dispersion.
8. The method for preparing the battery diaphragm based on the PVDF coaxial nanotube, which is characterized in that: the preparation method of the silicon dioxide nanowire after hydrophilic treatment comprises the following steps: adding KH-550 silane coupling agent into absolute ethyl alcohol, stirring uniformly, adding silicon dioxide powder, performing ultrasonic treatment, and drying at 58-62 ℃ to obtain the silicon dioxide nanowire after hydrophilic treatment.
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