CN118399020B - Battery diaphragm, preparation method thereof, secondary battery and power utilization device - Google Patents
Battery diaphragm, preparation method thereof, secondary battery and power utilization device Download PDFInfo
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- CN118399020B CN118399020B CN202410869329.5A CN202410869329A CN118399020B CN 118399020 B CN118399020 B CN 118399020B CN 202410869329 A CN202410869329 A CN 202410869329A CN 118399020 B CN118399020 B CN 118399020B
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- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 119
- 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 class 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 claims abstract description 91
- 239000011248 coating agent Substances 0.000 claims abstract description 58
- 238000000576 coating method Methods 0.000 claims abstract description 58
- 239000000919 ceramic Substances 0.000 claims abstract description 37
- 239000003063 flame retardant Substances 0.000 claims description 54
- 239000002562 thickening agent Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000002270 dispersing agent Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 26
- 229920000098 polyolefin Polymers 0.000 claims description 25
- DWHIUNMOTRUVPG-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-(2-dodecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCO DWHIUNMOTRUVPG-UHFFFAOYSA-N 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 22
- 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 22
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims description 22
- 229940031674 laureth-7 Drugs 0.000 claims description 22
- 229910052708 sodium Inorganic materials 0.000 claims description 22
- 239000011734 sodium Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 19
- 239000003607 modifier Substances 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 15
- 239000000853 adhesive Substances 0.000 claims description 14
- 230000001070 adhesive effect Effects 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 10
- 239000000347 magnesium hydroxide Substances 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 7
- 239000011343 solid material Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims 1
- 230000002159 abnormal effect Effects 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- 239000004698 Polyethylene Substances 0.000 description 9
- 229920000573 polyethylene Polymers 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- -1 Polyethylene Polymers 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000005524 ceramic coating Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62C—FIRE-FIGHTING
- A62C3/00—Fire prevention, containment or extinguishing specially adapted for particular objects or places
- A62C3/16—Fire prevention, containment or extinguishing specially adapted for particular objects or places in electrical installations, e.g. cableways
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- 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)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Emergency Management (AREA)
- Business, Economics & Management (AREA)
- Public Health (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a battery diaphragm, a preparation method thereof, a secondary battery and an electric device, and relates to the technical field of battery diaphragms. According to the invention, the modified flame retardant particles and the ceramic particles are added into the coating of the diaphragm, and the high-temperature resistant ceramic and the modified flame retardant particles in the coating can improve the heat resistance of the diaphragm, so that the heat shrinkage resistance of the diaphragm is improved, and the safety of the diaphragm in a high-temperature environment is ensured. In addition, after the battery catches fire out of control, the modified flame retardant particles in the coating can absorb heat rapidly again, so that the risk of battery catching fire is reduced. According to the invention, the modified flame-retardant particles can be more uniformly dispersed by matching with the adjustment of the dosage of other components, so that abnormal heat resistance caused by local powder falling of the coating is avoided.
Description
Technical Field
The invention relates to the technical field of battery diaphragms, in particular to a battery diaphragm, a preparation method thereof, a secondary battery and an electric device.
Background
Lithium ion batteries have been widely used at present, which mainly rely on Li + to and fro intercalation and deintercalation between two electrodes to operate, and mainly consist of four parts: cathode (positive electrode), electrolyte, separator, anode (negative electrode). In the structure of a lithium battery, a separator is one of the key inner layer components of the lithium battery. The separator is mainly used for separating cathode and anode materials of the battery to prevent short circuit of two-stage contact, and can maintain necessary electrolyte during electrochemical reaction to form ion moving channels (Li + can move in the electrolyte through the separator). The performance of the diaphragm determines the interface structure, internal resistance and the like of the battery, directly influences the capacity, circulation, safety performance and other characteristics of the battery, and the diaphragm with excellent performance plays an important role in improving the comprehensive performance of the battery. The lithium ion battery diaphragm with excellent performance has a porous structure, and has the advantages of high liquid absorption rate, high mechanical strength, thinner thickness, stable electrochemical performance and the like.
Most microporous membranes in the market today are mainly Polyethylene (PE), polypropylene (PP) and composite membranes of these two membranes (e.g. PE/PP and PP/PE/PP etc.). However, the conventional polyolefin separator has a thermal shrinkage at high temperature, which greatly affects the safety of the battery. In order to solve the defect of poor thermal stability of polyolefin membranes at high temperature, surface coating modification is one of the viable schemes. For example, a polyolefin separator is coated with an inorganic ceramic coating, and the prepared ceramic separator has good heat shrinkage resistance and has been applied commercially on a large scale.
Although the ceramic coating diaphragm with high temperature resistance in the market is better than the common diaphragm in heat resistance, the ceramic coating diaphragm has no great help to spontaneous combustion caused by short circuit of a lithium battery at high temperature, so that the diaphragm with high heat resistance and flame retardance is needed to reduce the risks of diaphragm rupture and battery spontaneous combustion, thereby improving the safety of the battery. In the prior art, organic or inorganic flame retardants are often added into coating paint, and although the flame retardants have a certain flame retardant effect, the compatibility with adhesives and other ceramic particles is poor, the dispersion of the ceramic particles is not facilitated, the problems of uneven distribution and easy precipitation of the inorganic particles exist, and the local heat resistance can be influenced to a certain extent.
Therefore, the separator in the prior art cannot achieve both heat resistance and flame retardance, and development of a separator with lower heat shrinkage and higher flame retardance is needed to improve the safety of the lithium ion battery in the use process.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a battery diaphragm, a preparation method thereof, a secondary battery and an electric device, and aims to improve the heat shrinkage rate of the diaphragm and the flame retardance of the diaphragm.
The invention is realized in the following way:
In a first aspect, the present invention provides a battery separator comprising a polyolefin-based film and a heat-resistant flame-retardant coating supported on the polyolefin-based film;
The raw materials for forming the heat-resistant flame-retardant coating comprise the following components in parts by mass: 20-35 parts of ceramic particles, 5-15 parts of modified flame retardant particles, 1-5 parts of adhesive, 0.1-3 parts of thickener and 50-75 parts of water;
The raw materials also comprise a dispersing agent, and the ratio of the dispersing agent to the total mass of the ceramic particles and the modified flame-retardant particles is (0.5-3.0): 100;
the modified flame-retardant particles are obtained by modifying flame-retardant particles by a modifier, and the flame-retardant particles are at least one selected from magnesium hydroxide, aluminum hydroxide and magnesium aluminum double hydroxide particles; the modifier comprises sodium lignin sulfonate and sodium bis (laureth-7) citrate.
In an alternative embodiment, the mass ratio of sodium lignin sulfonate to sodium bis (laureth-7) citrate is 1: (1-3);
And/or the ceramic particles are selected from at least one of alumina and boehmite;
and/or the ceramic particles have a particle size of 0.2 μm to 2.0 μm.
In an alternative embodiment, the binder is selected from at least one of aqueous polyacrylates and styrene-butadiene rubbers;
and/or the thickener is carboxymethyl cellulose thickener;
And/or the dispersant is an aqueous polymeric dispersant.
In an alternative embodiment, the polyolefin-based film is selected from at least one of a PP separator and a PE separator;
and/or the polyolefin-based film has a thickness of 5 μm to 30 μm and the heat-resistant flame-retardant coating has a thickness of 1 μm to 10 μm.
In a second aspect, the present invention provides a method for preparing a battery separator according to any one of the preceding embodiments, comprising: according to the raw material formula of the heat-resistant flame-retardant coating, ceramic particles, modified flame-retardant particles, an adhesive, a thickener, a dispersing agent and water are mixed to prepare the coating, and the coating is coated on a polyolefin-based film and dried.
In an alternative embodiment, the modified flame retardant particles are prepared by a process comprising: mixing flame-retardant particles, water and a modifier, performing hydrothermal reaction for 2-8 hours at 160-200 ℃, cooling, performing solid-liquid separation, and drying the obtained solid material;
wherein, the mass ratio of the flame retardant particles to the modifier is 10: (0.2-0.8);
And/or the mass ratio of the flame retardant particles to the water is 10 (180-200);
And/or the flame retardant particles have a particle size of 0.05 μm to 0.50 μm;
And/or controlling the drying temperature of the solid material to be 100-120 ℃ and the drying time to be 10-24 h.
In an alternative embodiment, the process for preparing the coating comprises: mixing a thickener with water to obtain a thickener solution, mixing a dispersant with water to obtain a first premix, mixing the first premix with the thickener solution to obtain a second premix, mixing the second premix with ceramic particles and modified flame retardant particles to obtain a third premix, and mixing the third premix with an adhesive;
In the mixing process, a high-speed disperser is used for mixing.
In an alternative embodiment, the coating is applied to one or both sides of the polyolefin-based film and dried using hot air;
the temperature of the hot air is controlled to be 70-90 ℃ and the drying time is controlled to be 2-5 min.
In a third aspect, the present invention provides a secondary battery comprising a battery separator according to any one of the preceding embodiments or a battery separator prepared by a method according to any one of the preceding embodiments.
In a fourth aspect, the present invention provides an electric device comprising the secondary battery of the foregoing embodiment.
The invention has the following beneficial effects: according to the invention, the modified flame retardant particles and the ceramic particles are added into the coating of the diaphragm, and the high-temperature resistant ceramic and the modified flame retardant particles in the coating can improve the heat resistance of the diaphragm, so that the heat shrinkage resistance of the diaphragm is improved, and the safety of the diaphragm in a high-temperature environment is ensured. In addition, after the battery catches fire out of control, the modified flame retardant particles in the coating can absorb heat rapidly again, so that the risk of battery catching fire is reduced. According to the invention, the modified flame-retardant particles can be more uniformly dispersed by matching with the adjustment of the dosage of other components, so that abnormal heat resistance caused by local powder falling of the coating is avoided.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a structural diagram of a battery separator according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The embodiment of the invention provides a battery diaphragm, as shown in figure 1, which comprises a polyolefin-based film and a heat-resistant flame-retardant coating supported on the polyolefin-based film, wherein the heat-resistant flame-retardant coating contains ceramic particles and flame-retardant particles.
In some embodiments, the polyolefin-based film is selected from at least one of a PP separator and a PE separator, and the polyolefin-based film may be any one or several of the above, not limited to the PE separator in fig. 1.
The raw materials for forming the heat-resistant flame-retardant coating comprise the following components in parts by mass: 20-35 parts of ceramic particles, 5-15 parts of modified flame retardant particles, 1-5 parts of adhesive, 0.1-3 parts of thickener and 50-75 parts of water; the raw materials also comprise a dispersing agent, and the ratio of the dispersing agent to the total mass of the ceramic particles and the modified flame-retardant particles is (0.5-3.0): 100. the dosage of each component is controlled in the above range, so that the modified flame-retardant particles can be better dispersed, and the prepared diaphragm has lower heat shrinkage and better flame-retardant effect.
Specifically, in the raw materials for forming the heat-resistant flame-retardant coating layer, the ceramic particles may be used in an amount of 20 parts, 23 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, etc.; the amount of the modified flame retardant particles may be 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, etc.; the amount of the adhesive may be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, etc.; the thickener may be used in an amount of 0.1 part, 0.3 part, 0.5 part, 0.8 part, 1.0 part, 1.5 part, 2.0 parts, 2.5 parts, 3.0 parts, etc.; the water may be used in an amount of 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, etc. The ratio of the amount of dispersant to the total mass of ceramic particles and modified flame retardant particles may be 0.5:100, 1.0:100, 1.5:100, 2.0:100, 2.5:100, 3.0:100, etc.
In some embodiments, the ceramic particles are selected from at least one of alumina and boehmite, and the ceramic particles may be any one or more of the above. The particle diameter of the ceramic particles is 0.2 μm to 2.0. Mu.m, for example, 0.2 μm, 0.5 μm, 0.8 μm, 1.0 μm, 1.2 μm, 1.5 μm, 1.8 μm, 2.0 μm, etc. The particle size of the ceramic particles should not be too large to ensure that the ceramic particles are uniformly dispersed in the coating.
The modified flame-retardant particles are obtained by modifying flame-retardant particles by a modifier, the flame-retardant particles are at least one selected from magnesium hydroxide, aluminum hydroxide and magnesium aluminum double hydroxide particles, and the flame-retardant particles can be any one or more of the above; the modifier comprises sodium lignin sulfonate and sodium bis (laureth-7) citrate, and the mass ratio of the sodium lignin sulfonate to the sodium bis (laureth-7) citrate is 1: (1-3), such as 1:1, 1:2, 1:3, etc. The auxiliary agent has carboxylate radical as hydrophilic radical and metal ion in the flame retardant particle, and through chemical adsorption or ion exchange reaction between carboxylate radical ion and magnesium ion, the auxiliary agent may be grafted onto the surface of magnesium hydroxide to result in great steric hindrance effect. In addition, the anionic auxiliary agent and the carboxymethyl cellulose thickener are both anionic polymers, and under the condition that the anionic auxiliary agent and the carboxymethyl cellulose thickener have the same charge, the steric hindrance effect of magnesium hydroxide is further increased, so that the dispersibility and the stability of the coating are further improved. Therefore, the inorganic particles can be adhered in the coating more uniformly after film formation, so that abnormal heat resistance caused by local powder falling of the coating is avoided, and the safety of the battery is further threatened.
It should be noted that, sodium lignin sulfonate has a benzene ring structure, has larger steric hindrance, and sodium di (laureth-7) citrate has long-chain carbon chains, so that sodium di (laureth-7) citrate with long-chain carbon chains can be inserted into sodium lignin sulfonate, and the two can reduce interfacial free energy by compounding, and can form micelle at lower concentration, thereby generating synergistic effect.
In some embodiments, the binder is at least one of aqueous polyacrylate and styrene-butadiene rubber, the binder can be any one or more of the above, and can be specifically polyacrylate emulsion, styrene-butadiene rubber emulsion or a mixture of the polyacrylate emulsion, the styrene-butadiene rubber emulsion and the styrene-butadiene rubber emulsion in any proportion, the binder is an emulsion type solution, and the particle size of the particles is 0.05-0.5 mu m. The thickener is carboxymethyl cellulose thickener, specifically carboxymethyl cellulose.
In some embodiments, the dispersant is an aqueous polymeric dispersant, such as BYK2010, BYK9151, and the like.
In some embodiments, the heat-resistant flame-retardant coating layer may be located on the upper layer or the upper and lower layers of the polyolefin-based film, the thickness of the polyolefin-based film is 5 μm to 30 μm, the thickness of the heat-resistant flame-retardant coating layer is 1 μm to 10 μm, and the thicknesses of the polyolefin-based film and the heat-resistant flame-retardant coating layer are preferably within the above-mentioned range, in which the heat shrinkage rate of the separator is low and the flame retardancy is also good.
Specifically, the thickness of the polyolefin-based film may be 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, etc., and the thickness of the heat-resistant flame-retardant coating layer may be 1 μm, 3 μm, 5 μm, 8 μm, 10 μm, etc.
The embodiment of the invention provides a preparation method of a battery diaphragm, which comprises the following steps:
S1, preparing modified flame-retardant particles
The flame retardant particles are modified with a modifier selected from at least one of magnesium hydroxide, aluminum hydroxide and magnesium aluminum double hydroxide particles, and the modifier is selected from at least one of sodium lignin sulfonate and sodium bis (laureth-7) citrate. The flame retardant particles preferably have a particle diameter of 0.05 μm to 0.50 μm (e.g., 0.05 μm, 0.10 μm, 0.20 μm, 0.30 μm, 0.40 μm, 0.50 μm, etc.) so as to disperse the flame retardant particles uniformly.
In some embodiments, the modification may be performed using a one-step hydrothermal process, the preparation of the modified flame retardant particles comprising: mixing the flame-retardant particles, water and a modifier, performing hydrothermal reaction for 2-8 hours at 160-200 ℃, cooling, performing solid-liquid separation, and drying the obtained solid material. The modified flame-retardant particles are prepared by a hydrothermal method, and the operation is convenient. In the reaction process, the modifier contains hydrophilic carboxylate, metal ions exist in flame retardant particles such as magnesium hydroxide and the like, and the auxiliary agents can be grafted to the surface of the magnesium hydroxide through chemical adsorption or ion exchange reaction between the carboxylate ions and the magnesium ions, so that the magnesium hydroxide has a larger steric hindrance effect, and the dispersibility and the stability of the coating are further improved.
Specifically, the temperature of the hydrothermal reaction may be 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, etc., and the hydrothermal reaction time may be 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, etc. After the reaction is completed, solid-liquid separation can be performed by filtration.
In some embodiments, the mass ratio of flame retardant particles to modifier is 10: (0.2-0.8), the mass ratio of the flame-retardant particles to the water is 10 (180-200), and the raw materials are further controlled to fully react, and the introduction amount of the modifier is controlled to ensure better dispersibility and stability of the coating. Specifically, the mass ratio of the flame retardant particles to the modifier may be 10:0.2, 10:0.3, 10:0.4, 10:0.5, 10:0.6, 10:0.7, 10:0.8, etc., and the mass ratio of the flame retardant particles to the water may be 10:180, 10:190, 10:200, etc.
In some embodiments, the drying temperature of the solid material is controlled to be 100 ℃ to 120 ℃ and the drying time is controlled to be 10 hours to 24 hours, so that the moisture on the surface of the solid material is sufficiently removed. Specifically, the drying temperature may be 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, etc., and the drying time may be 10 hours, 15 hours, 20 hours, 24 hours, etc.
S2, preparing a coating
According to the raw material formula of the heat-resistant flame-retardant coating, ceramic particles, modified flame-retardant particles, an adhesive, a thickener, a dispersing agent and water are mixed to prepare the coating. The formula is as follows: the raw materials for forming the heat-resistant flame-retardant coating comprise the following components in parts by mass: 20-35 parts of ceramic particles, 5-15 parts of modified flame retardant particles, 1-5 parts of adhesive, 0.1-3 parts of thickener and 50-75 parts of water; the raw materials also comprise a dispersing agent, and the ratio of the dispersing agent to the total mass of the ceramic particles and the modified flame-retardant particles is (0.5-3.0): 100.
In some embodiments, the process for preparing the coating includes: mixing a thickener with water to obtain a thickener solution, mixing a dispersant with water to obtain a first premix, mixing the first premix with the thickener solution to obtain a second premix, mixing the second premix with ceramic particles and modified flame retardant particles to obtain a third premix, and mixing the third premix with a binder. In the mixing process, the thickener and the dispersant are mixed respectively, then the thickener and the dispersant are mixed, and finally the adhesive is added, so that the raw materials such as the thickener, the dispersant and the like can be better dispersed.
In some embodiments, a high speed disperser is used to mix the materials during the mixing process to achieve rapid and uniform mixing of the materials.
S3, coating film
The coating is coated on a polyolefin-based film, and then dried to remove water, forming a uniform heat-resistant flame-retardant coating.
In the actual operation process, the coating can be coated on one side or two sides of the polyolefin-based film, and then the coating is dried by hot air, so that the moisture can be removed more rapidly, and the drying rate is improved. The temperature of the hot air is controlled to be 70-90 ℃, the drying time is controlled to be 2-5 min, and the moisture can be removed through short-time hot air drying. Specifically, the hot air temperature may be 70deg.C, 80deg.C, 90deg.C, etc., and the drying time may be 2min, 3min, 4min, 5min, etc.
The embodiment of the invention also provides a secondary battery, which comprises the battery diaphragm, and can also comprise a positive plate, a negative plate, electrolyte and the like, so as to form a complete battery structure. By improving the battery separator, the thermal stability of the secondary battery can be remarkably improved, and the risk of ignition of the battery can be reduced.
The embodiment of the invention also provides an electric device which comprises the secondary battery, and the secondary battery is used for supplying power, so that the specific type of the electric device is not limited, and the electric device can be an electric vehicle, an electronic device and the like.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides a preparation method of a battery diaphragm, which comprises the following steps:
(1) Preparation of modified flame-retardant particles by hydrothermal method
100G of magnesium hydroxide particles (particle size 1.0 μm), 1900 g of deionized water and 6g of surfactant are weighed in sequence, wherein the surfactant comprises sodium lignin sulfonate and sodium bis (laureth-7) citrate, and the mass ratio of the sodium lignin sulfonate to the sodium bis (laureth-7) citrate is 1:3. The raw materials are placed in a reaction kettle, the reaction kettle is placed at 200 ℃, and the sample is subjected to hydrothermal modification treatment for 8 hours. And after the reaction kettle is cooled to room temperature, filtering, and drying the solid component obtained by filtering at 110 ℃ for 24 hours to finally obtain the modified magnesium hydroxide flame-retardant particles.
(2) Coating for configuration
97G of deionized water and 3g of carboxymethyl cellulose thickener are weighed and added into a charging bucket, and are dispersed by using an electric high-speed dispersing machine at the rotating speed of 600rpm/min for 12 hours, so that the thickener can be uniformly dissolved in the deionized water, and a thickener aqueous solution with 3% of solid content is obtained.
1.5G of BYK2010 dispersing agent and 300g of deionized water are weighed and added into a charging bucket, and the mixture is dispersed at a high speed by using an electric high-speed dispersing machine at a rotating speed of 1000rpm/min for 5min, so that the dispersing agent is uniformly dispersed in a deionized water medium, and a premix liquid 1 is obtained.
33G of thickener aqueous solution with 3% solid content is added into the premix liquid 1, and the high-speed dispersion is continued, wherein the rotating speed is 1000rpm/min, and the dispersion is carried out for 10min, so that the thickener is fully dissolved in the premix liquid 1 to obtain a premix liquid 2.
150G of boehmite ceramic particles (particle size 1.0 μm) and 50g of modified magnesium hydroxide flame retardant particles (particle size 1.0 μm) were added to the premix liquid 2 to conduct high-speed dispersion at a rotation speed of 1000rpm/min for 10min, so that the ceramic particles and the modified flame retardant particles were uniformly dispersed in the premix liquid 1. And finally adding 9g of the aqueous polyacrylate emulsion, continuing to disperse at a high speed, and dispersing at a rotating speed of 1000rpm/min for 10min to obtain the final coating.
(3) Coating film
The coating is coated on the upper layer of a PE diaphragm (9 mu m) by using an RSD wire rod coater, the moisture of the coating is removed by using a hot air drying mode (the condition is 80 ℃ for 3 min), and the thickness of the coating after drying is 3 mu m, so that a single-layer coating diaphragm with the thickness of 9+3 mu m is finally obtained.
Example 2
The only difference from example 1 is that: the coating has different dosages of each component, and the specific steps are as follows: 160g of ceramic particles; 40g of modified flame retardant particles; 1.2g of thickener; 300g of water; 12g of adhesive; 3g of dispersing agent.
Example 3
The only difference from example 1 is that: the coating has different dosages of each component, and the specific steps are as follows: 140g of ceramic particles; 60g of modified flame retardant particles; 1.5g of thickener; 350g of water; 15g of adhesive; 4.5g of dispersant.
Example 4
The only difference from example 1 is that: the surfactant was sodium lignin sulfonate alone in the same amount as the total amount of example 1.
Example 5
The only difference from example 1 is that: the surfactant used was sodium bis (laureth-7) citrate alone, in the same amount as the total amount of example 1.
Example 6
The only difference from example 1 is that: the mass ratio of sodium lignin sulfonate to sodium di (laureth-7) citrate is 1:1.
Example 7
The only difference from example 1 is that: the mass ratio of sodium lignin sulfonate to sodium di (laureth-7) citrate is 1:2.
Example 8
The only difference from example 1 is that: the mass ratio of sodium lignin sulfonate to sodium di (laureth-7) citrate is 1:4.
Example 9
The only difference from example 1 is that: the mass ratio of sodium lignin sulfonate to sodium di (laureth-7) citrate is 1:5.
Example 10
The only difference from example 1 is that: the mass ratio of sodium lignin sulfonate to sodium di (laureth-7) citrate is 2:1.
Example 11
The only difference from example 1 is that: the mass ratio of sodium lignin sulfonate to sodium di (laureth-7) citrate is 3:1.
Example 12
The only difference from example 1 is that: the total amount of sodium lignin sulfonate and sodium bis (laureth-7) citrate was different and was 4g.
Example 13
The only difference from example 1 is that: the total amount of sodium lignin sulfonate and sodium bis (laureth-7) citrate was varied, 8g.
Comparative example 1
Uncoated plain PE separator.
Comparative example 2
The only difference from example 1 is that: no modified flame retardant particles are added to the coating.
Comparative example 3
The only difference from example 1 is that: the modifier in step (1) is replaced by an equivalent amount of silane coupling agent KH550.
Testing performance
The particle size distribution of the coating materials and the heat shrinkage performance and flame retardant performance of the separator prepared in examples and comparative examples were tested, and the results are shown in table 1 below.
The testing method comprises the following steps: 130 ℃ and 1 hour of heat shrinkage performance and flame retardance. The particle size distribution of the coating was tested using the GB/T19077-2016 standard, the heat shrinkage test was tested using the GB/T-36363-2018 standard, and the flame retardant test was tested using the GB/T2406.2-2009 standard.
Table 1 heat shrinkage and flame retardant properties of the separator prepared in examples and comparative examples
From table 1, it can be seen that the modification effect of modifying sodium lignin sulfonate and sodium bis (laureth-7) citrate serving as surfactants is optimal, and the flame retardant property of the product can be further improved and the heat shrinkage rate of the diaphragm can be reduced by optimizing the dosage ratio of the sodium lignin sulfonate and the sodium bis (laureth-7) citrate and the total dosage of the surfactants.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. 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 (10)
1. A battery separator comprising a polyolefin-based film and a heat-resistant flame-retardant coating supported on the polyolefin-based film;
the raw materials for forming the heat-resistant flame-retardant coating comprise the following components in parts by mass: 20-35 parts of ceramic particles, 5-15 parts of modified flame retardant particles, 1-5 parts of adhesive, 0.1-3 parts of thickener and 50-75 parts of water;
The raw materials further comprise a dispersing agent, and the ratio of the dispersing agent to the total mass of the ceramic particles and the modified flame-retardant particles is (0.5-3.0): 100;
The modified flame-retardant particles are obtained by modifying flame-retardant particles by a modifier, wherein the flame-retardant particles are selected from at least one of magnesium hydroxide, aluminum hydroxide and magnesium aluminum double hydroxide particles; the modifier comprises sodium lignin sulfonate and sodium bis (laureth-7) citrate;
The mass ratio of sodium lignin sulfonate to sodium di (laureth-7) citrate is 1: (1-3).
2. The battery separator according to claim 1, wherein the ceramic particles are selected from at least one of alumina and boehmite;
and/or the ceramic particles have a particle size of 0.2 μm to 2.0 μm.
3. The battery separator according to claim 1 or 2, wherein the binder is selected from at least one of aqueous polyacrylates and styrene-butadiene rubbers;
And/or the thickener is carboxymethyl cellulose thickener;
and/or the dispersing agent is an aqueous polymer dispersing agent.
4. The battery separator according to claim 1, wherein the polyolefin-based film is selected from at least one of a PP separator and a PE separator;
And/or the polyolefin-based film has a thickness of 5 μm to 30 μm and the heat-resistant flame-retardant coating has a thickness of 1 μm to 10 μm.
5. A method of making a battery separator according to any one of claims 1-4, comprising: and mixing the ceramic particles, the modified flame-retardant particles, the adhesive, the thickener, the dispersing agent and water according to the raw material formula of the heat-resistant flame-retardant coating to prepare a coating, coating the coating on the polyolefin-based film, and drying.
6. The method of claim 5, wherein the modified flame retardant particles are prepared by a process comprising: mixing the flame-retardant particles, water and the modifier, performing hydrothermal reaction for 2-8 hours at 160-200 ℃, cooling, performing solid-liquid separation, and drying the obtained solid material;
Wherein the mass ratio of the flame retardant particles to the modifier is 10: (0.2-0.8);
and/or the mass ratio of the flame retardant particles to the water is 10 (180-200);
And/or the flame retardant particles have a particle size of 0.05 μm to 0.50 μm;
and/or controlling the drying temperature of the solid material to be 100-120 ℃ and the drying time to be 10-24 hours.
7. The method according to claim 5 or 6, wherein the process for preparing the coating comprises: mixing the thickener and water to obtain a thickener solution, mixing the dispersant and water to obtain a first premix, mixing the first premix and the thickener solution to obtain a second premix, mixing the second premix with the ceramic particles and the modified flame retardant particles to obtain a third premix, and mixing the third premix with the adhesive;
In the mixing process, a high-speed disperser is used for mixing.
8. The method according to claim 5, wherein the coating material is applied to one side or both sides of the polyolefin-based film, and dried with hot air;
the temperature of the hot air is controlled to be 70-90 ℃ and the drying time is controlled to be 2-5 min.
9. A secondary battery comprising the battery separator according to any one of claims 1 to 4 or the battery separator produced by the production method according to any one of claims 5 to 8.
10. An electric device comprising the secondary battery according to claim 9.
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| CN115939665A (en) * | 2022-11-29 | 2023-04-07 | 江苏厚生新能源科技有限公司 | Flame-retardant high-temperature-resistant slurry, preparation method and diaphragm coated by flame-retardant high-temperature-resistant slurry |
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| EP3154528B1 (en) * | 2014-06-11 | 2023-04-05 | SpecGx LLC | Spray dried compositions having different dissolution profiles and processes for their preparation |
| JP2016155885A (en) * | 2015-02-23 | 2016-09-01 | 国立大学法人 奈良先端科学技術大学院大学 | Complex comprising coordination polymer |
| JP2016199460A (en) * | 2015-04-10 | 2016-12-01 | 協和化学工業株式会社 | Separation agent for annealing for grain oriented silicon steel sheet |
| CN114276159A (en) * | 2021-12-16 | 2022-04-05 | 惠州锂威新能源科技有限公司 | Preparation method of porous alumina ceramic and preparation method of lithium ion battery diaphragm |
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| CN104371374A (en) * | 2014-10-15 | 2015-02-25 | 上海应用技术学院 | Method for surface modification of magnesium hydroxide flame retardant |
| CN108206258A (en) * | 2017-12-26 | 2018-06-26 | 上海恩捷新材料科技股份有限公司 | A kind of high security self-gravitation lithium ion battery separator |
| CN114243215A (en) * | 2021-12-17 | 2022-03-25 | 蜂巢能源科技股份有限公司 | Coating slurry, preparation method thereof, composite diaphragm and lithium ion battery |
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