CN109346648B - Flame-retardant gel ceramic diaphragm and preparation method thereof - Google Patents
Flame-retardant gel ceramic diaphragm and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- 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
- H01M50/411—Organic material
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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
- H01M50/431—Inorganic material
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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
- H01M50/44—Fibrous material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A flame-retardant gel ceramic diaphragm comprises the following raw materials: the coating comprises a base film, an acrylate monomer, an initiator, a cross-linking agent, a catalyst, a solvent, a leveling agent, a dispersing agent, ceramic powder and a flame retardant. The advantages are that: 1. the liquid absorption rate is improved; 2. the polymerized colloid swells in the electrolyte to firmly bond the anode, the cathode and the diaphragm together, thereby greatly improving the interface of the battery; 3. when the battery is impacted by the outside, the polymerized colloid can absorb the heat generated by the battery, so that the risks of smoke, combustion and explosion of the battery are reduced; 4. the addition of flame retardants can further reduce the risk of battery ignition and explosion.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, relates to a flame-retardant gel ceramic diaphragm and also relates to a preparation method of the flame-retardant gel ceramic diaphragm.
Background
The separator, which is located between the positive and negative electrodes of the battery, is one of the important factors affecting the safety performance of the battery. The diaphragm not only ensures effective isolation of the positive electrode and the negative electrode, but also ensures electronic insulation in the battery and free passage of ions.
Because the conventional Polyethylene (PE) and polypropylene (PP) diaphragms are difficult to meet the requirements of people on the electrochemical performance and the safety performance of the battery, diaphragms coated with ceramics or PVDF are introduced in the market, the liquid absorption rate of the diaphragms is increased, the adhesiveness with electrodes is improved, and the electrochemical performance and the safety performance of the battery are improved; but still cannot meet the requirements of people on safety performance.
Disclosure of Invention
The purpose of the invention is: aiming at the defects, the flame-retardant gel ceramic diaphragm and the preparation method thereof are provided.
In order to achieve the purpose, the invention adopts the technical scheme that:
a flame-retardant gel ceramic diaphragm comprises the following raw materials: the coating comprises a base film, an acrylate monomer, an initiator, a cross-linking agent, a catalyst, a solvent, a leveling agent, a dispersing agent, ceramic powder and a flame retardant, wherein the base film comprises the following raw materials in parts by mass: 5 to 30 portions of acrylate monomer, 0.1 to 0.3 portion of initiator, 1 to 8 portions of cross-linking agent, 0.05 to 1 portion of catalyst, 220 portions of solvent 180, 1 to 5 portions of flatting agent, 1 to 5 portions of dispersing agent, 60 to 90 portions of ceramic powder and 1 to 10 portions of flame retardant,
the base membrane is made of a porous rigid support material, and the porous rigid support material comprises one of non-woven fabrics, ceramic porous diaphragms, glass fiber diaphragms, PP, PE and PP/PE composite diaphragms;
the acrylate monomers comprise conventional acrylate monomers and functionalized acrylate monomers;
the initiator comprises one or more of azobisisobutyronitrile, azobisisoheptonitrile, cumene hydroperoxide, lauroyl peroxide and dibenzoyl peroxide;
the cross-linking agent comprises one or more of diphenylmethane diisocyanate (MDI), Hexamethylene Diisocyanate (HDI), Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI), Lysine Diisocyanate (LDI), an addition product of TDI and trimethylolpropane, IPDI trimer, biuret polyisocyanate, HDI isocyanate, trifunctional aziridine, ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine and trimethylolpropane triglycidyl ether;
the catalyst comprises one or more of stannous octoate, dibutyltin dilaurate, triethylenediamine, triethylamine, N-dimethylbenzylamine, N-dimethylhexadecylamine and N, N-dimethylbutylamine;
the solvent comprises one or more of water, acetone, acetonitrile, N-methylpyrrolidone, N-dimethylformamide, ethylene carbonate, propylene carbonate and methyl ethyl carbonate;
the leveling agent comprises one or more of polydimethylsiloxane and polyether siloxane;
the dispersing agent comprises one or more of polyethylene glycol, sodium metasilicate, polyvinylpyrrolidone, ammonium citrate, tetramethylammonium hydroxide, polyacrylic acid, polypropylene, polyallyl alcohol and sodium polyacrylate;
the ceramic powder contains Li7La3Zr2O12(LLZO)、LixLa2/3-xTiO3(LLTO)、Li1+xAlxTi2-x(PO4)3(LATP)、LiAlO2(LAO)、AlOOH、SiO2、ZrO2、Al2O3、BaTiO3、TiO2One or more of the following;
the flame retardant comprises one or more of tributyl phosphate, tri (2-ethylhexyl) phosphate, tri (2-chloroethyl) phosphate, tri (2, 3-dichloropropyl) phosphate, tri (2, 3-dibromopropyl) phosphate, toluene-diphenyl phosphate, tricresyl phosphate, triphenyl phosphate, 2-ethylhexyl-diphenyl phosphate, and tri (dibromopropyl) phosphate.
The conventional acrylic ester monomer comprises one or more of methyl methacrylate, butyl acrylate, ethoxy ethyl acrylate, styrene and methoxyethyl acrylate.
The functionalized acrylate monomer mainly refers to an acrylate monomer containing carboxyl, hydroxyl, epoxy, ether oxygen or amino; comprises one or more of acrylic acid, hydroxyethyl methacrylate, methoxy polyethylene glycol acrylate, glycidyl methacrylate and acrylamide.
A preparation method of a flame-retardant gel ceramic diaphragm comprises the following preparation steps: the method comprises the following steps: preparation of gel precursor solution A
Adding a conventional acrylate monomer, a functionalized acrylate monomer and a solvent into a reaction kettle, uniformly stirring, introducing inert gas to discharge oxygen in the reaction kettle and materials, keeping a certain pressure, heating while stirring, adding 0.1-0.3 part by mass of an initiator when the temperature of the materials in the reaction kettle is raised to 45-55 ℃, then heating to 60-80 ℃ to start timing reaction for 3-10 hours, cooling to 25-35 ℃ after the reaction is finished, discharging for later use, wherein the viscosity is 1000 plus 10000 cps.
Step two: preparation of gel precursor solution B
Adding 1-8 parts by mass of a cross-linking agent and 0.05-1 part of a catalyst into the prepared gel polymer precursor solution A, uniformly stirring, and storing for 0-6 hours at the temperature of below 25 ℃ for later use;
step three: preparation of gel precursor solution C
Adding 60-90 parts of ceramic powder into a solvent, then adding 1-5 parts of a dispersing agent, uniformly dispersing the ceramic powder into the solvent through stirring, ultrasonic treatment and the like, then adding the dispersed ceramic powder into the gel precursor liquid B, and uniformly stirring to obtain a gel precursor liquid C;
step four: preparation of gel precursor solution D
Adding 1-10 parts of flame retardant and 1-5 parts of flatting agent into the gel precursor liquid C, stirring to uniformly disperse the flame retardant and the flatting agent into the gel precursor liquid C, adding a solvent, adjusting the viscosity of the gel precursor liquid, and keeping the viscosity at 200-1000cps to obtain a gel precursor liquid D;
step five: preparation of flame-retardant gel ceramic diaphragm
And coating the prepared gel precursor solution D on a base film, baking for 2-5 minutes in an oven at 50-70 ℃, rolling, and curing at 30-50 ℃ for 24-72 hours to obtain the flame-retardant gel ceramic diaphragm.
Compared with the prior art, the invention achieves the technical effects that: 1. the liquid absorption rate is improved; 2. the polymerized colloid swells in the electrolyte to firmly bond the anode, the cathode and the diaphragm together, thereby greatly improving the interface of the battery; 3. when the battery is impacted by the outside, the polymerized colloid can absorb the heat generated by the battery, so that the risks of smoke, combustion and explosion of the battery are reduced; 4. the addition of flame retardants can further reduce the risk of battery ignition and explosion.
Detailed Description
The invention is further described below with reference to the following examples:
the first embodiment is as follows:
a flame-retardant gel ceramic diaphragm comprises the following raw materials: the coating comprises a base film, an acrylate monomer, an initiator, a cross-linking agent, a catalyst, a solvent, a leveling agent, a dispersing agent, ceramic powder and a flame retardant, wherein the base film comprises the following raw materials in parts by mass: 15 parts of acrylate monomer, 0.15 part of initiator, 4 parts of cross-linking agent, 0.3 part of catalyst, 220 parts of solvent, 3 parts of flatting agent, 2 parts of dispersing agent, 70 parts of ceramic powder and 5 parts of flame retardant,
wherein, the base film is preferably non-woven fabric;
the acrylate monomers comprise conventional acrylate monomers and functionalized acrylate monomers; wherein, the conventional acrylic ester monomers are preferably oxyethoxy ethyl acrylate and styrene, wherein the oxyethoxy ethyl acrylate is 8 parts, and the styrene is 6 parts; the functionalized acrylate monomer is hydroxyethyl acrylate, and preferably 1 part;
the initiator is preferably lauroyl peroxide;
the crosslinking agent is preferably Toluene Diisocyanate (TDI);
the catalyst is preferably stannous octoate;
the solvent is preferably N-methylpyrrolidone;
the leveling agent is preferably polydimethylsiloxane;
the dispersant is preferably citric acid amine;
the ceramic powder is preferably AlOOH;
the flame retardant is preferably tris (2-ethylhexyl) phosphate.
A preparation method of a flame-retardant gel ceramic diaphragm comprises the following preparation steps: the method comprises the following steps: preparation of gel precursor solution A
Adding 8 parts of oxyethyl acrylate, 6 parts of styrene, 1 part of hydroxyethyl acrylate and 100 parts of N-methyl pyrrolidone into a reaction kettle, uniformly stirring, introducing inert gas to discharge oxygen in the reaction kettle and materials, keeping a certain pressure, heating while stirring, adding 0.15 part by mass of lauroyl peroxide when the temperature of the materials in the reaction kettle is raised to 50 ℃, heating to 75 ℃ to start timing reaction, reacting for 8 hours, cooling to 30 ℃ after the reaction is finished, discharging for later use, wherein the viscosity is 3000 cps.
Step two: preparation of gel precursor solution B
Adding 4 parts of Toluene Diisocyanate (TDI) and 0.3 part of stannous octoate into the prepared gel polymer precursor liquid A, uniformly stirring, storing for 6 hours at the temperature of below 25 ℃ for later use,
step three: preparation of gel precursor solution C
Adding 70 parts of AlOOH into 120 parts of N-methylpyrrolidone, then adding 2 parts of ammonium citrate, uniformly dispersing the AlOOH into a solvent through stirring, ultrasonic treatment and the like, then adding the dispersed AlOOH into the gel precursor liquid B, and uniformly stirring to obtain a gel precursor liquid C;
step four: preparation of gel precursor solution D
Adding 5 parts of tris (2-ethylhexyl) phosphate and 2 parts of polydimethylsiloxane into the gel precursor liquid C, stirring to uniformly disperse tris (2-ethylhexyl) phosphate and polydimethylsiloxane into the gel precursor liquid C, adding a solvent, adjusting the viscosity of the gel precursor liquid, and keeping the viscosity at 500cps to obtain a gel precursor liquid D;
step five: preparation of flame-retardant gel ceramic diaphragm
And coating the prepared gel precursor solution D on non-woven fabrics, baking the non-woven fabrics in an oven at 60 ℃ for 3 minutes, rolling the non-woven fabrics, and curing the non-woven fabrics at 45 ℃ for 30 hours to obtain the flame-retardant gel ceramic diaphragm.
Compared with the prior art, the invention achieves the technical effects that: 1. the liquid absorption rate is improved; 2. the polymerized colloid swells in the electrolyte to firmly bond the anode, the cathode and the diaphragm together, thereby greatly improving the interface of the battery; 3. when the battery is impacted by the outside, the polymerized colloid can absorb the heat generated by the battery, so that the risks of smoke, combustion and explosion of the battery are reduced; 4. the addition of flame retardants can further reduce the risk of battery ignition and explosion.
Example two:
a flame-retardant gel ceramic diaphragm comprises the following raw materials: the coating comprises a base film, an acrylate monomer, an initiator, a cross-linking agent, a catalyst, a solvent, a leveling agent, a dispersing agent, ceramic powder and a flame retardant, wherein the base film comprises the following raw materials in parts by mass: 17 parts of acrylate monomer, 0.1 part of initiator, 2 parts of cross-linking agent, 0.1 part of catalyst, 210 parts of solvent, 3 parts of flatting agent, 1.5 parts of dispersing agent, 60 parts of ceramic powder and 3 parts of flame retardant,
wherein the base membrane is preferably a ceramic porous diaphragm;
the acrylate monomers comprise conventional acrylate monomers and functionalized acrylate monomers; the conventional acrylic ester monomer is preferably butyl acrylate, wherein the butyl acrylate is 5 parts; the functionalized acrylate monomers comprise polyethylene glycol acrylate and acrylamide, wherein the polyethylene glycol acrylate accounts for 10 parts, and the acrylamide accounts for 2 parts;
the initiator is preferably azobisisoheptonitrile;
the cross-linking agent is preferably trimethylolpropane triglycidyl ether;
the catalyst is preferably triethylenediamine;
the solvent is preferably ethylene carbonate;
the leveling agent is preferably polyether siloxane;
the dispersing agent is preferably polyethylene glycol;
the ceramic powder is preferably SiO2；
The flame retardant is preferably tris (dibromopropyl) phosphate.
A preparation method of a flame-retardant gel ceramic diaphragm comprises the following preparation steps: the method comprises the following steps: preparation of gel precursor solution A
Adding 5 parts of butyl acrylate, 10 parts of polyethylene glycol acrylate, 2 parts of acrylamide and 130 parts of ethylene carbonate into a reaction kettle, uniformly stirring, introducing inert gas to discharge oxygen in the reaction kettle and materials, keeping a certain pressure, heating while stirring, adding 0.1 part by mass of azodiisoheptonitrile when the temperature of the materials in the reaction kettle is raised to 45 ℃, then heating to 60 ℃ to start timing reaction for 4 hours, cooling to 30 ℃ after the reaction is finished, discharging for later use, wherein the viscosity is 2000 cps;
step two: preparation of gel precursor solution B
Adding 2 parts of trimethylolpropane triglycidyl ether and 0.1 part of triethylene diamine into the prepared gel polymer precursor solution A, uniformly stirring, storing for 4 hours at the temperature of below 25 ℃ for later use,
step three: preparation of gel precursor solution C
60 parts of SiO2Adding into 80 parts of ethylene carbonate, adding 2 parts of polyethylene glycol, stirring and ultrasonic treating to obtain SiO2Uniformly dispersing into a solvent, and then dispersing the dispersed SiO2Adding the precursor solution B into the gel precursor solution B, and uniformly stirring to obtain a gel precursor solution C;
step four: preparation of gel precursor solution D
Adding 3 parts of tris (dibromopropyl) phosphate and 3 parts of polyether siloxane into the gel precursor solution C, stirring to uniformly disperse the tris (dibromopropyl) phosphate and the polyether siloxane into the gel precursor solution C, adding a solvent, adjusting the viscosity of the gel precursor solution to keep the viscosity at 300cps, and obtaining a gel precursor solution D;
step five: preparation of flame-retardant gel ceramic diaphragm
And coating the prepared gel precursor solution D on a ceramic porous diaphragm, baking the ceramic porous diaphragm in an oven at 50 ℃ for 5 minutes, rolling the ceramic porous diaphragm, and curing the ceramic porous diaphragm at 50 ℃ for 24 hours to obtain the flame-retardant gel ceramic diaphragm.
Compared with the prior art, the invention achieves the technical effects that: 1. the liquid absorption rate is improved; 2. the polymerized colloid swells in the electrolyte to firmly bond the anode, the cathode and the diaphragm together, thereby greatly improving the interface of the battery; 3. when the battery is impacted by the outside, the polymerized colloid can absorb the heat generated by the battery, so that the risks of smoke, combustion and explosion of the battery are reduced; 4. the addition of flame retardants can further reduce the risk of battery ignition and explosion.
Example three:
a flame-retardant gel ceramic diaphragm comprises the following raw materials: the coating comprises a base film, an acrylate monomer, an initiator, a cross-linking agent, a catalyst, a solvent, a leveling agent, a dispersing agent, ceramic powder and a flame retardant, wherein the base film comprises the following raw materials in parts by mass: 15 portions of acrylate monomer, 0.3 portion of initiator, 5 portions of cross-linking agent, 0.05 portion of catalyst, 180 portions of solvent, 2 portions of flatting agent, 2 portions of dispersing agent, 60 portions of ceramic powder and 5 portions of flame retardant,
wherein the base film is preferably a glass fiber separator;
the acrylate monomers comprise conventional acrylate monomers and functionalized acrylate monomers; the conventional acrylate monomers are preferably styrene and methoxyethyl acrylate, wherein the styrene accounts for 3 parts, and the methoxyethyl acrylate accounts for 10 parts; the functionalized acrylate monomer is acrylic acid, wherein the acrylic acid accounts for 2 parts;
the initiator is preferably cumene hydroperoxide and dibenzoyl peroxide, wherein the cumene hydroperoxide is 0.2 part, and the dibenzoyl peroxide is 0.1 part;
the crosslinker is preferably a trifunctional aziridine;
the catalyst is preferably N, N-dimethylbenzylamine;
the solvent is preferably methyl ethyl carbonate;
the leveling agent is preferably polyether siloxane;
the dispersing agent is preferably polyvinylpyrrolidone;
the ceramic powder is preferably LiAlO2(LAO)；
The flame retardant is preferably triphenyl phosphate.
A preparation method of a flame-retardant gel ceramic diaphragm comprises the following preparation steps: the method comprises the following steps: preparation of gel precursor solution A
Adding 3 parts of styrene, 10 parts of methoxyethyl acrylate, 2 parts of acrylic acid and 80 parts of methyl ethyl carbonate into a reaction kettle, uniformly stirring, introducing inert gas to discharge oxygen in the reaction kettle and materials, keeping a certain pressure, heating while stirring, adding 0.2 part by mass of cumene hydroperoxide when the temperature of the materials in the reaction kettle is raised to 55 ℃, then heating to 75 ℃ to start timing reaction for 7 hours, then supplementing 0.1 part of dibenzoyl peroxide, continuing the reaction for 2 hours, cooling to 30 ℃ after the reaction is finished, discharging for later use, wherein the viscosity is 5000 cps;
step two: preparation of gel precursor solution B
Adding 5 parts of trifunctional aziridine and 0.05 part of N, N-dimethylbenzylamine into the prepared gel polymer precursor solution A, uniformly stirring, storing for 5 hours at the temperature of below 25 ℃ for later use,
step three: preparation of gel precursor solution C
60 portions of LiAlO2(LAO) is added to 100 parts of ethyl methyl carbonate, then 2 parts of polyvinylpyrrolidone is added, and LiAlO is added by stirring, sonication, etc2(LAO) is uniformly dispersed in a solvent, and then the dispersed LiAlO is added2(LAO) adding the gel precursor solution B, and uniformly stirring to obtain a gel precursor solution C;
step four: preparation of gel precursor solution D
Adding 5 parts of triphenyl phosphate and 2 parts of polyether siloxane into the gel precursor solution C, stirring to uniformly disperse triphenyl phosphate and polyether siloxane into the gel precursor solution C, adding a solvent, adjusting the viscosity of the gel precursor solution to keep the viscosity at 400cps, and obtaining a gel precursor solution D;
step five: preparation of flame-retardant gel ceramic diaphragm
And coating the prepared gel precursor solution D on a glass fiber diaphragm, baking for 4 minutes in an oven at 60 ℃, rolling, and curing for 48 hours at 60 ℃ to obtain the flame-retardant gel ceramic diaphragm.
Compared with the prior art, the invention achieves the technical effects that: 1. the liquid absorption rate is improved; 2. the polymerized colloid swells in the electrolyte to firmly bond the anode, the cathode and the diaphragm together, thereby greatly improving the interface of the battery; 3. when the battery is impacted by the outside, the polymerized colloid can absorb the heat generated by the battery, so that the risks of smoke, combustion and explosion of the battery are reduced; 4. the addition of flame retardants can further reduce the risk of battery ignition and explosion.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (2)
1. A preparation method of a flame-retardant gel ceramic diaphragm is characterized by comprising the following steps: the preparation method comprises the following preparation steps:
the method comprises the following steps: preparation of gel precursor solution A
Adding 5-30 parts of conventional acrylate monomers, functionalized acrylate monomers and 220 parts of solvent 180-class into a reaction kettle, uniformly stirring, introducing inert gas to discharge oxygen in the reaction kettle and materials, keeping a certain pressure, heating while stirring, adding 0.1-0.3 part by mass of an initiator when the temperature of the materials in the reaction kettle is raised to 45-55 ℃, then heating to 60-80 ℃ to start timing reaction, reacting for 3-10 hours, cooling to 25-35 ℃ after the reaction is finished, adding the solvent, adjusting the viscosity by a viscosity tester to keep the viscosity at 1000-class 10000cps, and discharging for later use;
step two: preparation of gel precursor solution B
Adding 1-8 parts by mass of a cross-linking agent and 0.05-1 part of a catalyst into the prepared gel polymer precursor solution A, uniformly stirring, and storing for 0-6 hours at the temperature of below 25 ℃ for later use;
step three: preparation of gel precursor solution C
Adding 60-90 parts of ceramic powder into a solvent, then adding 1-5 parts of a dispersing agent, uniformly dispersing the ceramic powder into the solvent through stirring, ultrasonic treatment and the like, then adding the dispersed ceramic powder into the gel precursor liquid B, and uniformly stirring to obtain a gel precursor liquid C;
step four: preparation of gel precursor solution D
Adding 1-10 parts of flame retardant and 1-5 parts of flatting agent into the gel precursor liquid C, uniformly dispersing the flame retardant and the flatting agent into the gel precursor liquid C by stirring, simultaneously adding a solvent, and adjusting the viscosity by a viscosity tester to keep the viscosity at 200-1000cps to obtain a gel precursor liquid D;
step five: preparation of flame-retardant gel ceramic diaphragm
Coating the prepared gel precursor solution D on a base film, baking the base film in an oven at 50-70 ℃ for 2-5 minutes, rolling, and curing at 30-50 ℃ for 24-72 hours to obtain the flame-retardant gel ceramic diaphragm;
wherein, the solvent comprises one or more of water, acetone, acetonitrile, N-methyl pyrrolidone, N-dimethylformamide, ethylene carbonate, propylene carbonate and methyl ethyl carbonate;
the initiator comprises one or more of azobisisobutyronitrile, azobisisoheptonitrile, cumene hydroperoxide, lauroyl peroxide and dibenzoyl peroxide;
the cross-linking agent comprises one or more of diphenylmethane diisocyanate (MDI), Hexamethylene Diisocyanate (HDI), Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI), Lysine Diisocyanate (LDI), an addition product of TDI and trimethylolpropane, IPDI trimer, biuret polyisocyanate, HDI isocyanate, trifunctional aziridine, ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine and trimethylolpropane triglycidyl ether;
the catalyst comprises one or more of stannous octoate, dibutyltin dilaurate, triethylenediamine, triethylamine, N-dimethylbenzylamine, N-dimethylhexadecylamine and N, N-dimethylbutylamine;
the ceramic powder contains Li7La3Zr2O12(LLZO)、LixLa2/3-xTiO3(LLTO)、Li1+xAlxTi2-x (PO4)3(LATP)、LiAlO2(LAO)、AlOOH、SiO2、ZrO2、Al2O3、BaTiO3、TiO2One or more of the following;
the dispersing agent comprises one or more of polyethylene glycol, sodium metasilicate, polyvinylpyrrolidone, ammonium citrate, tetramethylammonium hydroxide, polyacrylic acid, polypropylene, polyallyl alcohol and sodium polyacrylate;
the flame retardant comprises one or more of tributyl phosphate, tri (2-ethylhexyl) phosphate, tri (2-chloroethyl) phosphate, tri (2, 3-dichloropropyl) phosphate, tri (2, 3-dibromopropyl) phosphate, toluene-diphenyl phosphate, tricresyl phosphate, triphenyl phosphate, 2-ethylhexyl-diphenyl phosphate, tri (dibromopropyl) phosphate and the like;
the leveling agent comprises one or more of polydimethylsiloxane and polyether siloxane;
the base membrane is made of a porous rigid supporting material, and the porous rigid supporting material comprises one of non-woven fabrics, ceramic porous diaphragms, glass fiber diaphragms, PP, PE and PP/PE composite diaphragms;
the functionalized acrylate monomer mainly refers to an acrylate monomer containing carboxyl, hydroxyl, epoxy, ether oxygen or amino; comprises one or more of acrylic acid, hydroxyethyl methacrylate, methoxy polyethylene glycol acrylate, glycidyl methacrylate and acrylamide.
2. The method of claim 1, wherein the conventional acrylic ester monomer comprises one or more of methyl methacrylate, butyl acrylate, ethoxyethoxyethyl acrylate, styrene, and methoxyethyl acrylate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811194705.6A CN109346648B (en) | 2018-10-15 | 2018-10-15 | Flame-retardant gel ceramic diaphragm and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811194705.6A CN109346648B (en) | 2018-10-15 | 2018-10-15 | Flame-retardant gel ceramic diaphragm and preparation method thereof |
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| Publication Number | Publication Date |
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| CN110124242A (en) * | 2019-05-27 | 2019-08-16 | 中煤科工集团重庆研究院有限公司 | A kind of plasticity sodium silicate gel material and its preparation method and application |
| CN110336069B (en) * | 2019-07-02 | 2020-11-17 | 东莞市创明电池技术有限公司 | Lithium ion battery and preparation method thereof |
| CN112201880B (en) * | 2020-09-28 | 2022-11-11 | 消之源科技技术有限公司 | Preparation method of cooling partition plate for lithium battery |
| CN113937417B (en) * | 2021-10-27 | 2022-08-02 | 长园泽晖新能源材料研究院(珠海)有限公司 | Photocuring modified lithium ion battery diaphragm and preparation method thereof |
| CN116554597B (en) * | 2023-05-29 | 2023-09-29 | 佛山市塑聚新材料科技有限公司 | High glow wire flame-retardant polypropylene material and preparation method thereof |
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