CN109346648A - A kind of fire-retardant gel ceramic diaphragm and preparation method thereof - Google Patents
A kind of fire-retardant gel ceramic diaphragm and preparation method thereof Download PDFInfo
- Publication number
- CN109346648A CN109346648A CN201811194705.6A CN201811194705A CN109346648A CN 109346648 A CN109346648 A CN 109346648A CN 201811194705 A CN201811194705 A CN 201811194705A CN 109346648 A CN109346648 A CN 109346648A
- Authority
- CN
- China
- Prior art keywords
- parts
- precursor liquid
- fire
- retardant
- gel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Cell Separators (AREA)
- Polymerisation Methods In General (AREA)
Abstract
A kind of fire-retardant gel ceramic diaphragm, raw material composition includes: basement membrane, acrylic ester monomer, initiator, crosslinking agent, catalyst, solvent, levelling agent, dispersing agent, ceramic powder and fire retardant.Advantage is: 1, improving imbibition rate；2, it is swollen in the electrolytic solution using the colloid after polymerization and anode, cathode and diaphragm is firmly bonded together, greatly improve the interface of battery；3, when battery is by foreign impacts, the heat of battery generation is can be absorbed in the colloid after polymerization, reduces the risk that battery smolders, burns and explodes；4, the addition of fire retardant can further decrease the risk of cells burst and explosion.
Description
Technical field
The present invention relates to technical field of lithium ion, relate to a kind of fire-retardant gel ceramic diaphragm, have further related to one kind
The preparation method of fire-retardant gel ceramic diaphragm.
Background technique
One of an important factor for diaphragm between battery positive and negative electrode is influence battery safety.Diaphragm is not
Only guarantee that positive and negative electrode is effectively isolated, and guarantees having free passage for inside battery electronic isolation and ion.
Due to conventional polyethylene (PE), polypropylene (PP) diaphragm is difficult to the chemical property and peace that meet people to battery
The demand of full performance, therefore release coated ceramic in the market or coat the diaphragm of PVDF, increase diaphragm imbibition rate, with electricity
The adhesiveness of pole improves the chemical property and security performance of battery；But it is not still able to satisfy people, security performance is wanted
It asks.
Summary of the invention
The purpose of the present invention is: in view of the above deficiencies, provide a kind of fire-retardant gel ceramic diaphragm and preparation method thereof.
In order to achieve the above objectives, the technical solution adopted by the present invention is that:
A kind of fire-retardant gel ceramic diaphragm, raw material composition includes: basement membrane, acrylic ester monomer, initiator, crosslinking
Agent, catalyst, solvent, levelling agent, dispersing agent, ceramic powder and fire retardant, wherein the mass parts of each raw material are respectively as follows: third
Olefin(e) acid esters monomer is 5-30 parts, and initiator is 0.1-0.3 parts, and crosslinking agent is 1-8 parts, and catalyst is 0.05-1 parts, solvent
180-220 parts, levelling agent is 1-5 parts, and dispersing agent is 1-5 parts, and ceramic powder is 60-90 parts, and fire retardant is 1-10 parts,
Wherein, for the basement membrane including being more empty rigid backing materials, the porous rigid backing material includes non-woven fabrics, pottery
One of porcelain porous septum, fibreglass diaphragm, PP, PE and PP/PE composite diaphragm；
The acrylic ester monomer includes the acrylic ester monomer of Conventional acrylic esters monomer and functionalization；
The initiator include azodiisobutyronitrile, azobisisoheptonitrile, isopropyl benzene hydroperoxide, dilauroyl peroxide,
The one or more of dibenzoyl peroxide；
The crosslinking agent includes methyl diphenylene diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene
Diisocyanate (TDI), isophorone diisocyanate (IPDI) dicyclohexyl methyl hydride diisocyanate (HMDI), lysine two
Isocyanates (LDI), the addition product of TDI and trimethylolpropane, IPDI tripolymer, biuret polyisocyanate, HDI isocyanic acid
Ester, trifunctional aziridine, ethylenediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, trimethylolpropane tris glycidol
The one or several kinds of ether；
The catalyst includes stannous octoate, dibutyl tin dilaurate, triethylenediamine, triethylamine, N, N- diformazan
Base benzylamine, N, N- dimethyl cetylamine, N, the one or several kinds of N- dimethyl butylamine；
The solvent include water, acetone, acetonitrile, N-Methyl pyrrolidone, N,N-dimethylformamide, ethylene carbonate,
One of propene carbonate, methyl ethyl carbonate or one or more of any several combinations；
The levelling agent includes one or more of dimethyl silicone polymer, polyether silicone；
The dispersing agent includes polyethylene glycol, sub- sodium metasilicate, polyvinylpyrrolidone, lemon acid amide, tetramethylphosphonihydroxide hydroxide base
One or more of ammonium, polyacrylic acid, polypropylene, POLYPROPYLENE GLYCOL, Sodium Polyacrylate；
The ceramic powder includes Li7La3Zr2O12(LLZO)、LixLa2/3-xTiO3(LLTO)、Li1+xAlxTi2-x(PO4)3
(LATP)、LiAlO2(LAO)、AlOOH、SiO2、ZrO2、Al2O3、BaTiO3、TiO2Etc. one such or several；
The fire retardant includes tributyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate (2- chloroethyl) ester, phosphoric acid
Three (bis- chloropropyl of 2,3-) esters, tricresyl phosphate (2,3- dibromopropyl) ester, tricresyl phosphate-diphenyl ester, tricresyl phosphate, tricresyl phosphate
Phenyl ester, phosphoric acid (2- ethylhexyl)-diphenyl ester, tricresyl phosphate (dibromopropyl) ester etc. are one such or several.
The Conventional acrylic esters monomer includes methyl methacrylate, butyl acrylate, ethoxy ethoxy propylene
One or more of acetoacetic ester, styrene, methoxyethyl acrylate.
The acrylic ester monomer of the functionalization be primarily referred to as containing carboxyl or hydroxyl or epoxy group or ether oxygen base,
Or the acrylic ester monomer of amido；Including acrylic acid, hydroxyethyl methacrylate, methoxy polyethylene glycol acrylate, first
The one or more of base glycidyl acrylate, acrylamide.
A kind of preparation method of fire-retardant gel ceramic diaphragm, including following preparation step: step 1: gel precursor liquid is prepared
A
Conventional acrylic esters monomer, esters monomer containing functionalized acrylic, solvent are added in reaction kettle, stirring is equal
Oxygen that is even, being passed through in inert gas discharge reaction kettle and material, and certain pressure is kept, warming while stirring, wait react
When temperature of charge in kettle is raised to 45 DEG C -55 DEG C, the initiator of 0.1-0.3 mass parts is added, is then warming up to 60 DEG C -80 DEG C and opens
Beginning clock reaction reacts 3-10 hours, is cooled to 25 DEG C -35 DEG C after the reaction was completed, discharges spare, viscosity is in 1000-
10000cps。
Step 2: gel precursor liquid B is prepared
The crosslinking agent of 1-8 mass parts is added into the gelatin polymer precursor liquid A prepared, 0.05-1 parts of catalyst is simultaneously
Stir evenly, 25 DEG C or less preservation 0-6 hours, it is spare；
Step 3: gel precursor liquid C is prepared
60-90 parts of ceramic powder is added in solvent, 1-5 parts of dispersing agent is then added, by stirring ultrasound etc.,
Ceramic powder is evenly spread in solvent, and scattered ceramic powder is then added to gel precursor liquid B, is uniformly mixing to obtain
Gel precursor liquid C；
Step 4: gel precursor liquid D is prepared
By 1-10 parts of fire retardant and 1-5 parts of levelling agent, gel precursor liquid C is added, by stirring make fire retardant and
Levelling agent is evenly spread in gel precursor liquid C, while adding solvent, is adjusted the viscosity of gel precursor liquid, is maintained at viscosity
200-1000cps to get arrive gel precursor liquid D；
Step 5: fire-retardant gel ceramic diaphragm is prepared
Prepared gel precursor liquid D is coated on basement membrane, is wound after 50-70 DEG C of baking oven toasts 2-5 minutes, 30-
It is cured 24-72 hours at 50 DEG C, fire-retardant gel ceramic diaphragm can be obtained.
Compared with prior art, the present invention is achieved has the technical effect that 1, improves imbibition rate；2, after using polymerization
Colloid is swollen in the electrolytic solution to be firmly bonded together anode, cathode and diaphragm, and the interface of battery is greatly improved；3, in electricity
When pond is by foreign impacts, the heat of battery generation is can be absorbed in the colloid after polymerization, is reduced battery and is smoldered, burns and explode
Risk；4, the addition of fire retardant can further decrease the risk of cells burst and explosion.
Specific embodiment
The present invention will be further described below with reference to examples:
Embodiment one:
A kind of fire-retardant gel ceramic diaphragm, raw material composition includes: basement membrane, acrylic ester monomer, initiator, crosslinking
Agent, catalyst, solvent, levelling agent, dispersing agent, ceramic powder and fire retardant, wherein the mass parts of each raw material are respectively as follows: third
Olefin(e) acid esters monomer be 15 parts, initiator be 0.15 part, crosslinking agent be 4 parts, catalyst be 0.3 part, 220 parts of solvent, levelling agent
It is 3 parts, dispersing agent is 2 parts, and ceramic powder is 70 parts, and fire retardant is 5 parts,
Wherein, the basement membrane is preferably non-woven fabrics；
The acrylic ester monomer includes the acrylic ester monomer of Conventional acrylic esters monomer and functionalization；Its
In, Conventional acrylic esters monomer is preferably oxygroup ethoxy ethyl acrylate and styrene, wherein oxygroup ethoxy-c olefin(e) acid
Ethyl ester is 8 parts, and styrene is 6 parts；The acrylic ester monomer of functionalization be hydroxy-ethyl acrylate, preferably 1 part；
The initiator is preferably dilauroyl peroxide；
The crosslinking agent is preferably toluene di-isocyanate(TDI) (TDI)；
The catalyst is preferably stannous octoate；
The solvent is preferably N-Methyl pyrrolidone；
The levelling agent is preferably dimethyl silicone polymer；
The dispersing agent is preferably lemon acid amide；
The ceramic powder is preferably AlOOH；
The fire retardant is preferably tri-2-ethylhexyl phosphate.
A kind of preparation method of fire-retardant gel ceramic diaphragm, including following preparation step: step 1: gel precursor liquid is prepared
A
By 8 parts of oxygroup ethoxy ethyl acrylates, 6 parts of styrene, 1 part of hydroxy-ethyl acrylate, 100 parts of N- crassitudes
Ketone is added in reaction kettle, is stirred evenly, the oxygen being passed through in inert gas discharge reaction kettle and material, and keeps certain pressure
The dilauroyl peroxide of 0.15 mass parts is added when the temperature of charge in reaction kettle is raised to 50 DEG C in power, warming while stirring,
Then 75 DEG C of beginning clock reactions are warming up to, reacts 8 hours, is cooled to after the reaction was completed, 30 DEG C, are discharged spare, viscosity exists
3000cps。
Step 2: gel precursor liquid B is prepared
4 parts of toluene di-isocyanate(TDI) (TDI), 0.3 part of octanoic acid are added into the gelatin polymer precursor liquid A prepared
Stannous simultaneously stirs evenly, and 25 DEG C or less save 6 hours, spare,
Step 3: gel precursor liquid C is prepared
70 parts of AlOOH is added in 120 parts of N-Methyl pyrrolidone, 2 parts of lemon acid amide is then added, passes through
Ultrasound etc. is stirred, AlOOH is evenly spread in solvent, and scattered AlOOH is then added to gel precursor liquid B, and stirring is equal
It is even to obtain gel precursor liquid C；
Step 4: gel precursor liquid D is prepared
By 5 parts of tri-2-ethylhexyl phosphate and 2 parts of dimethyl silicone polymer, gel precursor liquid C, warp is added
Crossing stirring evenly spreads to tri-2-ethylhexyl phosphate and dimethyl silicone polymer in gel precursor liquid C, adds simultaneously
Solvent adjusts the viscosity of gel precursor liquid, and viscosity is made to be maintained at 500cps to get gel precursor liquid D is arrived；
Step 5: fire-retardant gel ceramic diaphragm is prepared
Prepared gel precursor liquid D is coated on non-woven fabrics, is wound after 60 DEG C of baking ovens toast 3 minutes, at 45 DEG C
Curing 30 hours, can be obtained fire-retardant gel ceramic diaphragm.
Compared with prior art, the present invention is achieved has the technical effect that 1, improves imbibition rate；2, after using polymerization
Colloid is swollen in the electrolytic solution to be firmly bonded together anode, cathode and diaphragm, and the interface of battery is greatly improved；3, in electricity
When pond is by foreign impacts, the heat of battery generation is can be absorbed in the colloid after polymerization, is reduced battery and is smoldered, burns and explode
Risk；4, the addition of fire retardant can further decrease the risk of cells burst and explosion.
Embodiment two:
A kind of fire-retardant gel ceramic diaphragm, raw material composition includes: basement membrane, acrylic ester monomer, initiator, crosslinking
Agent, catalyst, solvent, levelling agent, dispersing agent, ceramic powder and fire retardant, wherein the mass parts of each raw material are respectively as follows: third
Olefin(e) acid esters monomer is 17 parts, and initiator is 0.1 part, and crosslinking agent is 2 parts, and catalyst is 0.1 part, and 210 parts of solvent, levelling agent is
3 parts, dispersing agent is 1.5 parts, and ceramic powder is 60 parts, and fire retardant is 3 parts,
Wherein, the basement membrane is preferably ceramic porous diaphragm；
The acrylic ester monomer includes the acrylic ester monomer of Conventional acrylic esters monomer and functionalization；Its
In, Conventional acrylic esters monomer is preferably butyl acrylate, and wherein butyl acrylate is 5 parts；The esters of acrylic acid of functionalization
Monomer is polyethylene glycol acrylate and acrylamide, and wherein polyethylene glycol acrylate is 10 parts, and acrylamide is 2 parts；
The initiator is preferably azobisisoheptonitrile；
The crosslinking agent is preferably trihydroxymethylpropanyltri diglycidyl ether；
The catalyst is preferably triethylenediamine；
The solvent is preferably ethylene carbonate；
The levelling agent is preferably polyether silicone；
The dispersing agent is preferably polyethylene glycol；
The ceramic powder is preferably SiO2；
The fire retardant is preferably tricresyl phosphate (dibromopropyl) ester.
A kind of preparation method of fire-retardant gel ceramic diaphragm, including following preparation step: step 1: gel precursor liquid is prepared
A
By 5 parts of butyl acrylates, 10 parts of polyethylene glycol acrylates, 2 parts of acrylamides, 130 parts of ethylene carbonates are added
It into reaction kettle, stirs evenly, the oxygen being passed through in inert gas discharge reaction kettle and material, and keeps certain pressure, side
Side heating is stirred, when the temperature of charge in reaction kettle is raised to 45 DEG C, the azobisisoheptonitrile of 0.1 mass parts is added, then rises
Temperature is reacted 4 hours, is cooled to after the reaction was completed, 30 DEG C to 60 DEG C of beginning clock reactions, is discharged spare, viscosity is in 2000cps；
Step 2: gel precursor liquid B is prepared
The trihydroxymethylpropanyltri diglycidyl ether of 2 parts of addition into the gelatin polymer precursor liquid A prepared, 0.1 part
Triethylenediamine and stir evenly, 25 DEG C or less save 4 hours, it is spare,
Step 3: gel precursor liquid C is prepared
By 60 parts of SiO2It is added in 80 parts of ethylene carbonate, 2 parts of polyethylene glycol is then added, it is super by stirring
Sound etc., SiO2It evenly spreads in solvent, then by scattered SiO2It is added to gel precursor liquid B, is uniformly mixing to obtain gel
Precursor liquid C；
Step 4: gel precursor liquid D is prepared
By 3 parts of tricresyl phosphates (dibromopropyl) ester and 3 parts of polyether silicone, gel precursor liquid C is added, by stirring
It evenly spreads to tricresyl phosphate (dibromopropyl) ester and polyether silicone in gel precursor liquid C, while adding solvent, adjust gel
The viscosity of precursor liquid makes viscosity be maintained at 300cps to get gel precursor liquid D is arrived；
Step 5: fire-retardant gel ceramic diaphragm is prepared
Prepared gel precursor liquid D is coated on ceramic porous diaphragm, is wound after five minutes through 50 DEG C of baking oven bakings,
It is cured 24 hours at 50 DEG C, fire-retardant gel ceramic diaphragm can be obtained.
Compared with prior art, the present invention is achieved has the technical effect that 1, improves imbibition rate；2, after using polymerization
Colloid is swollen in the electrolytic solution to be firmly bonded together anode, cathode and diaphragm, and the interface of battery is greatly improved；3, in electricity
When pond is by foreign impacts, the heat of battery generation is can be absorbed in the colloid after polymerization, is reduced battery and is smoldered, burns and explode
Risk；4, the addition of fire retardant can further decrease the risk of cells burst and explosion.
Embodiment three:
A kind of fire-retardant gel ceramic diaphragm, raw material composition includes: basement membrane, acrylic ester monomer, initiator, crosslinking
Agent, catalyst, solvent, levelling agent, dispersing agent, ceramic powder and fire retardant, wherein the mass parts of each raw material are respectively as follows: third
Olefin(e) acid esters monomer be 15 parts, initiator be 0.3 part, crosslinking agent be 5 parts, catalyst be 0.05 part, 180 parts of solvent, levelling agent
It is 2 parts, dispersing agent is 2 parts, and ceramic powder is 60 parts, and fire retardant is 5 parts,
Wherein, the basement membrane is preferably fibreglass diaphragm；
The acrylic ester monomer includes the acrylic ester monomer of Conventional acrylic esters monomer and functionalization；Its
In, Conventional acrylic esters monomer is preferably styrene and methoxyethyl acrylate, and wherein styrene is 3 parts, acrylic acid first
Oxygroup ethyl ester is 10 parts；The acrylic ester monomer of functionalization is acrylic acid, and wherein acrylic acid is 2 parts；
The initiator is preferably isopropyl benzene hydroperoxide and dibenzoyl peroxide, and wherein isopropyl benzene hydroperoxide is
0.2 part, dibenzoyl peroxide is 0.1 part；
The crosslinking agent is preferably trifunctional aziridine；
The catalyst is preferably N, N- dimethyl benzylamine；
The solvent is preferably methyl ethyl carbonate；
The levelling agent is preferably polyether silicone；
The dispersing agent is preferably polyvinylpyrrolidone；
The ceramic powder is preferably LiAlO2(LAO)；
The fire retardant is preferably triphenyl phosphate.
A kind of preparation method of fire-retardant gel ceramic diaphragm, including following preparation step: step 1: gel precursor liquid is prepared
A
By 3 parts of styrene, 10 parts of methoxyethyl acrylates, 2 parts of acrylic acid, 80 parts of methyl ethyl carbonates are added to reaction kettle
In, it stirs evenly, the oxygen being passed through in inert gas discharge reaction kettle and material, and keep certain pressure, rises while stirring
Temperature is added the isopropyl benzene hydroperoxide of 0.2 mass parts, is then warming up to 75 when the temperature of charge in reaction kettle is raised to 55 DEG C
DEG C start clock reaction, react 7 hours, add 0.1 part of dibenzoyl peroxide later, the reaction was continued 2 hours, reaction complete
After be cooled to, 30 DEG C, discharge it is spare, viscosity is in 5000cps；
Step 2: gel precursor liquid B is prepared
5 parts of trifunctional aziridine, 0.05 part of N, N- diformazan are added into the gelatin polymer precursor liquid A prepared
Base benzylamine simultaneously stirs evenly, and 25 DEG C or less save 5 hours, spare,
Step 3: gel precursor liquid C is prepared
By 60 parts of LiAlO2(LAO) it is added in 100 parts of methyl ethyl carbonate, 2 parts of polyvinyl pyrrole is then added
Alkanone, by stirring ultrasound etc., LiAlO2(LAO) it evenly spreads in solvent, then by scattered LiAlO2(LAO) it is added
To gel precursor liquid B, it is uniformly mixing to obtain gel precursor liquid C；
Step 4: gel precursor liquid D is prepared
By 5 parts of triphenyl phosphate and 2 parts of polyether silicone, gel precursor liquid C is added, makes tricresyl phosphate by stirring
Phenyl ester and polyether silicone are evenly spread in gel precursor liquid C, while adding solvent, are adjusted the viscosity of gel precursor liquid, are made
Viscosity is maintained at 400cps to get gel precursor liquid D is arrived；
Step 5: fire-retardant gel ceramic diaphragm is prepared
Prepared gel precursor liquid D is coated on fibreglass diaphragm, is wound after 60 DEG C of baking ovens toast 4 minutes,
It is cured 48 hours at 60 DEG C, fire-retardant gel ceramic diaphragm can be obtained.
Compared with prior art, the present invention is achieved has the technical effect that 1, improves imbibition rate；2, after using polymerization
Colloid is swollen in the electrolytic solution to be firmly bonded together anode, cathode and diaphragm, and the interface of battery is greatly improved；3, in electricity
When pond is by foreign impacts, the heat of battery generation is can be absorbed in the colloid after polymerization, is reduced battery and is smoldered, burns and explode
Risk；4, the addition of fire retardant can further decrease the risk of cells burst and explosion.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (4)
1. a kind of fire-retardant gel ceramic diaphragm, it is characterised in that: its raw material composition includes: basement membrane, acrylic ester monomer, draws
Agent, crosslinking agent, catalyst, solvent, levelling agent, dispersing agent, ceramic powder and fire retardant are sent out, wherein the mass parts of each raw material
Being respectively as follows: acrylic ester monomer is 5-30 parts, and initiator is 0.1-0.3 parts, and crosslinking agent is 1-8 parts, catalyst 0.05-1
Part, 180-220 parts of solvent, levelling agent is 1-5 parts, and dispersing agent is 1-5 parts, and ceramic powder is 60-90 parts, fire retardant 1-10
Part,
Wherein, the basement membrane includes for more empty rigid backing materials, and the porous rigid backing material includes that non-woven fabrics, ceramics are more
One of hole diaphragm, fibreglass diaphragm, PP, PE and PP/PE composite diaphragm；
The acrylic ester monomer includes the acrylic ester monomer of Conventional acrylic esters monomer and functionalization；
The initiator includes azodiisobutyronitrile, azobisisoheptonitrile, isopropyl benzene hydroperoxide, dilauroyl peroxide, peroxide
Change the one or more of dibenzoyl；
The crosslinking agent includes that methyl diphenylene diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene two are different
Cyanate (TDI), isophorone diisocyanate (IPDI) dicyclohexyl methyl hydride diisocyanate (HMDI), two isocyanide of lysine
Acid esters (LDI), the addition product of TDI and trimethylolpropane, IPDI tripolymer, biuret polyisocyanate, HDI isocyanates,
Trifunctional aziridine, ethylenediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, trihydroxymethylpropanyltri diglycidyl ether
It is one or several kinds of；
The catalyst includes stannous octoate, dibutyl tin dilaurate, triethylenediamine, triethylamine, N, N- dimethylbenzyl
Amine, N, N- dimethyl cetylamine, N, the one or several kinds of N- dimethyl butylamine；
The solvent includes water, acetone, acetonitrile, N-Methyl pyrrolidone, N,N-dimethylformamide, ethylene carbonate, carbonic acid
One of acrylic ester, methyl ethyl carbonate or one or more of any several combinations；
The levelling agent includes one or more of dimethyl silicone polymer, polyether silicone；
The dispersing agent includes polyethylene glycol, sub- sodium metasilicate, polyvinylpyrrolidone, lemon acid amide, tetramethyl ammonium hydroxide, gathers
One or more of acrylic acid, polypropylene, POLYPROPYLENE GLYCOL, Sodium Polyacrylate；
The ceramic powder includes Li7La3Zr2O12(LLZO)、LixLa2/3-xTiO3(LLTO)、Li1+xAlxTi2-x(PO4)3
(LATP)、LiAlO2(LAO)、AlOOH、SiO2、ZrO2、Al2O3、BaTiO3、TiO2Etc. one such or several；
The fire retardant includes tributyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate (2- chloroethyl) ester, tricresyl phosphate
(bis- chloropropyl of 2,3-) ester, tricresyl phosphate (2,3- dibromopropyl) ester, tricresyl phosphate-diphenyl ester, tricresyl phosphate, phosphoric acid triphen
Ester, phosphoric acid (2- ethylhexyl)-diphenyl ester, tricresyl phosphate (dibromopropyl) ester etc. are one such or several.
2. a kind of fire-retardant gel ceramic diaphragm according to claim 1, it is characterised in that: the Conventional acrylic esters list
Body includes methyl methacrylate, butyl acrylate, ethoxy ethoxy ethyl acrylate, styrene, methoxyethyl second
One or more of ester.
3. a kind of fire-retardant gel ceramic diaphragm according to claim 1, it is characterised in that: the acrylate of the functionalization
Class monomer is primarily referred to as the acrylic ester monomer containing carboxyl or hydroxyl or epoxy group or ether oxygen base or amido；Including third
Olefin(e) acid, hydroxyethyl methacrylate, methoxy polyethylene glycol acrylate, glycidyl methacrylate, acrylamide
It is one or more of.
4. a kind of preparation method of fire-retardant gel ceramic diaphragm, it is characterised in that: including following preparation step:
Step 1: gel precursor liquid A is prepared
Conventional acrylic esters monomer, esters monomer containing functionalized acrylic, solvent are added in reaction kettle, stirred evenly,
The oxygen being passed through in inert gas discharge reaction kettle and material, and certain pressure is kept, warming while stirring, in reaction kettle
Temperature of charge when being raised to 45 DEG C -55 DEG C, the initiator of 0.1-0.3 mass parts is added, is then warming up to 60 DEG C -80 DEG C and starts to count
Shi Fanying reacts 3-10 hours, is cooled to 25 DEG C -35 DEG C after the reaction was completed, adds solvent, is adjusted by viscosity tester glutinous
Degree keeps it in 1000-10000cps, discharges spare.
Step 2: gel precursor liquid B is prepared
The crosslinking agent of 1-8 mass parts, 0.05-1 parts of catalyst and stirring are added into the gelatin polymer precursor liquid A prepared
Uniformly, 25 DEG C or less preservation 0-6 hours, it is spare；
Step 3: gel precursor liquid C is prepared
60-90 parts of ceramic powder is added in solvent, 1-5 parts of dispersing agent is then added, by stirring ultrasound etc., ceramics
Powder is evenly spread in solvent, and scattered ceramic powder is then added to gel precursor liquid B, is uniformly mixing to obtain gel
Precursor liquid C；
Step 4: gel precursor liquid D is prepared
By 1-10 parts of fire retardant and 1-5 parts of levelling agent, gel precursor liquid C is added, makes fire retardant and levelling by stirring
Agent is evenly spread in gel precursor liquid C, while adding solvent, is adjusted viscosity by viscosity tester, is maintained at viscosity
200-1000cps to get arrive gel precursor liquid D；
Step 5: fire-retardant gel ceramic diaphragm is prepared
Prepared gel precursor liquid D is coated on basement membrane, is wound after 50-70 DEG C of baking oven toasts 2-5 minutes, 30-50 DEG C
Fire-retardant gel ceramic diaphragm can be obtained in lower curing 24-72 hours.
Priority Applications (1)
| 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 |
Applications Claiming Priority (1)
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109346648A true CN109346648A (en) | 2019-02-15 |
| CN109346648B CN109346648B (en) | 2021-11-02 |
Family
ID=65309926
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811194705.6A Active CN109346648B (en) | 2018-10-15 | 2018-10-15 | Flame-retardant gel ceramic diaphragm and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109346648B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110336069A (en) * | 2019-07-02 | 2019-10-15 | 东莞市创明电池技术有限公司 | A kind of lithium ion battery and preparation method thereof |
| CN112201880A (en) * | 2020-09-28 | 2021-01-08 | 消之源科技技术有限公司 | Preparation method of automatic intelligent cooling partition plate for new energy lithium battery |
| CN113937417A (en) * | 2021-10-27 | 2022-01-14 | 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 |
| CN116554597A (en) * | 2023-05-29 | 2023-08-08 | 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 |
| CN117801732A (en) * | 2024-02-29 | 2024-04-02 | 深圳好电科技有限公司 | Secondary battery diaphragm binder, slurry composition and battery |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002061872A1 (en) * | 2001-01-31 | 2002-08-08 | Korea Institute Of Science And Technology | A multi-layered polymer electrolyte and lithium secondary battery comprising the same |
| CN1388993A (en) * | 2000-08-12 | 2003-01-01 | Lg化学株式会社 | Multi-component composite film method for preparing the same |
| CN101036247A (en) * | 2004-07-14 | 2007-09-12 | 阿科玛股份有限公司 | Multi-layer polyelectrolyte membrane |
| CN101154750A (en) * | 2006-09-30 | 2008-04-02 | 万向电动汽车有限公司 | High power gel polymer lithium ion power cell and method of producing the same |
| CN102005609A (en) * | 2010-10-20 | 2011-04-06 | 浙江工业大学 | Composite gel polymer electrolyte membrane and application thereof |
| CN102263220A (en) * | 2011-06-22 | 2011-11-30 | 广东博特动力能源有限公司 | Preparation method for battery diaphragm |
| CN102916149A (en) * | 2012-09-26 | 2013-02-06 | 东莞市创明电池技术有限公司 | Micropore membrane of lithium battery and preparation technique for micropore membrane |
| CN103456909A (en) * | 2012-05-31 | 2013-12-18 | 海洋王照明科技股份有限公司 | Preparation method of polyvinylidene fluoride-hexafluoropropene gel electrolyte membrane, polyvinylidene fluoride-hexafluoropropene gel electrolyte and preparation method of the electrolyte |
| CN104088155A (en) * | 2014-06-25 | 2014-10-08 | 江苏华东锂电技术研究院有限公司 | Composite diaphragm, preparation method thereof and lithium ion battery |
| CN107346833A (en) * | 2017-08-30 | 2017-11-14 | 清陶（昆山）能源发展有限公司 | A kind of composite solid polymer electrolyte film and preparation method thereof |
| CN108134036A (en) * | 2014-12-16 | 2018-06-08 | 东莞新能源科技有限公司 | A kind of Organic-inorganic composite dielectric film, preparation method and application |
| CN108598570A (en) * | 2018-06-28 | 2018-09-28 | 清陶（昆山）新能源材料研究院有限公司 | A kind of preparation method of gel polymer electrolyte diaphragm and its application in lithium ion battery |
-
2018
- 2018-10-15 CN CN201811194705.6A patent/CN109346648B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1388993A (en) * | 2000-08-12 | 2003-01-01 | Lg化学株式会社 | Multi-component composite film method for preparing the same |
| WO2002061872A1 (en) * | 2001-01-31 | 2002-08-08 | Korea Institute Of Science And Technology | A multi-layered polymer electrolyte and lithium secondary battery comprising the same |
| CN101036247A (en) * | 2004-07-14 | 2007-09-12 | 阿科玛股份有限公司 | Multi-layer polyelectrolyte membrane |
| CN101154750A (en) * | 2006-09-30 | 2008-04-02 | 万向电动汽车有限公司 | High power gel polymer lithium ion power cell and method of producing the same |
| CN102005609A (en) * | 2010-10-20 | 2011-04-06 | 浙江工业大学 | Composite gel polymer electrolyte membrane and application thereof |
| CN102263220A (en) * | 2011-06-22 | 2011-11-30 | 广东博特动力能源有限公司 | Preparation method for battery diaphragm |
| CN103456909A (en) * | 2012-05-31 | 2013-12-18 | 海洋王照明科技股份有限公司 | Preparation method of polyvinylidene fluoride-hexafluoropropene gel electrolyte membrane, polyvinylidene fluoride-hexafluoropropene gel electrolyte and preparation method of the electrolyte |
| CN102916149A (en) * | 2012-09-26 | 2013-02-06 | 东莞市创明电池技术有限公司 | Micropore membrane of lithium battery and preparation technique for micropore membrane |
| CN104088155A (en) * | 2014-06-25 | 2014-10-08 | 江苏华东锂电技术研究院有限公司 | Composite diaphragm, preparation method thereof and lithium ion battery |
| CN108134036A (en) * | 2014-12-16 | 2018-06-08 | 东莞新能源科技有限公司 | A kind of Organic-inorganic composite dielectric film, preparation method and application |
| CN107346833A (en) * | 2017-08-30 | 2017-11-14 | 清陶（昆山）能源发展有限公司 | A kind of composite solid polymer electrolyte film and preparation method thereof |
| CN108598570A (en) * | 2018-06-28 | 2018-09-28 | 清陶（昆山）新能源材料研究院有限公司 | A kind of preparation method of gel polymer electrolyte diaphragm and its application in lithium ion battery |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110336069A (en) * | 2019-07-02 | 2019-10-15 | 东莞市创明电池技术有限公司 | A kind of lithium ion battery and preparation method thereof |
| 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 |
| CN112201880A (en) * | 2020-09-28 | 2021-01-08 | 消之源科技技术有限公司 | Preparation method of automatic intelligent cooling partition plate for new energy lithium battery |
| 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 |
| CN113937417A (en) * | 2021-10-27 | 2022-01-14 | 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 |
| CN116554597A (en) * | 2023-05-29 | 2023-08-08 | 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 |
| 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 |
| CN117801732A (en) * | 2024-02-29 | 2024-04-02 | 深圳好电科技有限公司 | Secondary battery diaphragm binder, slurry composition and battery |
| CN117801732B (en) * | 2024-02-29 | 2024-06-04 | 深圳好电科技有限公司 | Secondary battery diaphragm binder, slurry composition and battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109346648B (en) | 2021-11-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109346648A (en) | A kind of fire-retardant gel ceramic diaphragm and preparation method thereof | |
| CN103339781B (en) | Electrode assemblie | |
| CN102439769B (en) | Binder composition for non-aqueous secondary battery electrode | |
| CN108598570A (en) | A kind of preparation method of gel polymer electrolyte diaphragm and its application in lithium ion battery | |
| CN103911088B (en) | A kind of acrylate pressure-sensitive adhesive band and preparation method thereof and lithium ion battery | |
| WO2017161974A1 (en) | Isolation membrane for electrochemical apparatus, and preparation method and application thereof | |
| US6632561B1 (en) | Composites bodies used as separators in electrochemical cells | |
| CN103000941A (en) | Formula of gel electrolyte and method for preparing gel electrolyte with formula | |
| CN109935755B (en) | Organic-inorganic composite gel diaphragm and preparation method thereof | |
| CN111668538B (en) | Ceramic matrix composite solid electrolyte and preparation method thereof | |
| CN102306841B (en) | Gel phase polymer lithium ion battery and manufacturing method thereof | |
| KR20120037462A (en) | Resin composition and organic-electrolyte battery | |
| US20220173463A1 (en) | Lithium-ion battery stack | |
| CN110783512B (en) | Soluble type lithium bis (fluorosulfonyl) imide/lithium magnesium silicate coating diaphragm for lithium ion battery and preparation method thereof | |
| CN1458703A (en) | Partition for cell bearing adhesive composition and electrode/partition laminated article produced therefrom | |
| CN107768653A (en) | A kind of lithium ion battery cathode slurry, negative material, lithium ion battery and preparation method thereof | |
| CN115411457A (en) | Lithium ion battery diaphragm and preparation method and application thereof | |
| CN109301316A (en) | A kind of Organic-inorganic composite electrolyte and preparation method thereof and the application in solid lithium-ion secondary cell | |
| CN114014965B (en) | Polymer film, electrolyte, all-solid-state battery, and preparation method and application thereof | |
| CN108023051A (en) | A kind of isolation film and the lithium ion battery containing the isolation film | |
| WO2013011825A1 (en) | Adhesive composition for battery packaging materials | |
| CN109659626A (en) | Battery production method and battery | |
| CN111341975B (en) | Diaphragm for high-efficiency lithium ion secondary battery and preparation method thereof | |
| CN105778804A (en) | Preparation method for double-layer PET protective film for lithium battery pack | |
| CN107611321B (en) | Separator and secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |