CN109037547A - Terpolymer modified ceramic diaphragm and its preparation and application based on catechol - Google Patents
Terpolymer modified ceramic diaphragm and its preparation and application based on catechol Download PDFInfo
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- CN109037547A CN109037547A CN201810686093.6A CN201810686093A CN109037547A CN 109037547 A CN109037547 A CN 109037547A CN 201810686093 A CN201810686093 A CN 201810686093A CN 109037547 A CN109037547 A CN 109037547A
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- catechol
- ceramic diaphragm
- terpolymer
- modified ceramic
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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
-
- 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
- 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
- H01M50/449—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
Abstract
The terpolymer modified ceramic diaphragm and its preparation and application that the invention discloses a kind of based on catechol, preparation method includes: to carry out copolyreaction using the monomer A containing catechol and double bond, the monomer B containing double bond and without catechol and the monomer C containing double bond and without catechol as raw material, obtain terpolymer, terpolymer is dissolved in the mixed liquor of water and ethyl alcohol, obtains polymer solution；Polymer solution is coated in the surface of ceramic diaphragm, the terpolymer modified ceramic diaphragm based on catechol is obtained after drying.Terpolymer modified ceramic diaphragm and its preparation and application proposed by the present invention based on catechol, the preparation method process is simple, rate of polymerization is fast, the obtained terpolymer modified ceramic diaphragm wellability based on catechol is good, percent thermal shrinkage is low, for improving the high rate performance and cycle performance of battery in lithium ion battery.
Description
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of terpolymer based on catechol are modified
Ceramic diaphragm and its preparation and application.
Background technique
The advantages that for lithium ion battery due to voltage height, energy density is big, has extended cycle life, memory-less effect, not only extensively
It applies in consumer electronics field, also in electric car, hybrid electric vehicle yields unusually brilliant results in field.
General lithium ion battery is by anode, cathode, electrolyte and diaphragm composition.Its septation is that physics may be implemented in one kind
The high molecular material for allowing lithium ion to pass through again when positive and negative electrodes in same is isolated.The diaphragm of commercialization is mainly polyalkene diaphragm, in room temperature
Under enough mechanical strengths and chemical stability can be provided, but polyolefin is mainly made of C-H bond, is had hydrophobicity, is caused
Electrolyte wellability is poor；Polyalkene diaphragm ionic conductivity is lower simultaneously, and biggish heat can occur under the high temperature conditions and receive
It contracts (120 DEG C of PE, 150 DEG C of PP), will lead to positive and negative electrode and contact and gather heat rapidly, cause cells burst or explosion, exist
Very big security risk.In order to improve the stability and safety of polyalkene diaphragm, ceramic diaphragm can be used, is existing poly-
On the surface of alkene micropore film base material, single or double is coated with one layer of protective layer that is uniform, being made of ceramic microparticle etc., shape
At porous security functions diaphragm.On the basis of guarantee polyolefin micropore barrier diaphragm original fundamental characteristics, it is high to assign diaphragm
Resistance to heat function reduces the heat-shrinkable of diaphragm, to more effectively reduce inside lithium ion cell short circuit, prevents because of inside battery
Battery thermal runaway caused by short circuit.But there is " picking " phenomenon in current commercial enamel diaphragm, this will greatly affect it is ceramic every
Service performance of the film in lithium ion battery.In nature, contain catechol group in the sufficient albumen of mussel secretion, and it is various
The covalent effect or noncovalent interaction (hydrogen bond, sedimentation power or Van der Waals force etc.) of substrate material are realized in various substrate materials
The Ultrastrength adhesive on surface, but the existing poly-dopamine based on catechol has very low auto polymerization rate, and does not have viscous
Adjustability is spent, will limit its application in actual production.
Summary of the invention
Technical problems based on background technology, the invention proposes a kind of terpolymers based on catechol to change
Property ceramic diaphragm and its preparation and application, the preparation method process are simple, and rate of polymerization is fast, and viscosity is adjustable, obtained base
Good in the terpolymer modified ceramic diaphragm wellability of catechol, percent thermal shrinkage is low, for improving in lithium ion battery
The high rate performance and cycle performance of battery.
A kind of preparation method of terpolymer modified ceramic diaphragm based on catechol proposed by the present invention, including with
Lower step:
S1, with the monomer A containing catechol and double bond, the monomer B containing double bond and without catechol and containing double bond and not
Monomer C containing catechol is that raw material carries out copolyreaction, obtains terpolymer, terpolymer is dissolved in water and ethyl alcohol
Mixed liquor in, obtain polymer solution；
S2, the surface that polymer solution is coated in ceramic diaphragm, obtain the ternary based on catechol after drying
Copolymer-modified ceramic diaphragm.
Preferably, in S1, the monomer A containing catechol and double bond is dopamine Methacrylamide, 3,4- bis-
One of hydroxy benzenes -1- alanine Methacrylamide, 3,4- dihydroxy benzenes methyl ether -1- alanine Methacrylamide.
Preferably, in S1, containing double bond and without catechol monomer B and containing double bond and be free of catechol monomer
C is that 2- acrylic acid -2- methoxy acrylate, styrene, methyl methacrylate, butyl methacrylate, methacrylic acid are different
Butyl ester, hydroxyethyl meth acrylate, polyethylene glycol dimethacrylate, 3- methoxy-methyl acrylate, methyl acrylate,
Any one in ethyl acrylate, glycidyl methacrylate.
Preferably, in S2, during the surface that polymer solution is coated in ceramic diaphragm, used coating side
Formula is one of spin coating, dip-coating, dimple version, spraying.
Preferably, in S2, the ceramic diaphragm includes basement membrane and the ceramic layer for being coated on membrane surface；The ceramic layer
Raw material include one or more of aluminium oxide, boehmite, silica, calcium carbonate, zinc oxide, cerium oxide, magnesia
Mixture.
Preferably, raw material used by the basement membrane is polyethylene, polypropylene, polyimides, polytetrafluoroethylene (PTFE), gathers inclined fluorine
Ethylene, polyvinyl chloride, polyethylene terephthalate, Kynoar-hexafluoropropylene copolymer, poly-methyl methacrylate
The mixture of one or more of ester, polyethylene oxide, polyvinyl alcohol.
A kind of terpolymer modified ceramic diaphragm based on catechol that the present invention also proposes, using described based on neighbour
The preparation method of the terpolymer modified ceramic diaphragm of benzenediol is prepared.
One kind that the present invention also proposes terpolymer modified ceramic diaphragm based on catechol is in lithium-ion electric
Application in pond.
In the present invention, the monomer B containing double bond and without catechol is different from containing double bond and is free of the monomer of catechol
C。
The preparation method of terpolymer modified ceramic diaphragm of the present invention based on catechol, containing adjacent benzene two
Phenol and the monomer of double bond are major ingredient, while joined two different monomers containing double bond and without catechol is raw material, is made
Raolical polymerizable occurs for three, has obtained a kind of terpolymer, has been coated onto the surface of ceramic diaphragm, has obtained base
In the terpolymer modified ceramic diaphragm of catechol, on the one hand, it improves gained because introducing catechol in structure
The wellability and contact angle of diaphragm are conducive to the hydrophily for increasing diaphragm, improve guarantor's liquid rate of diaphragm, ceramic layer is effectively reduced
Picking and leakage, improve the physical property and chemical property of diaphragm, are used in lithium ion battery, improve battery
High rate performance and cycle performance；On the other hand, terpolymer has very strong adhesion strength, can be improved diaphragm and electrode it
Between interface stability, prevent battery flatulence, effectively inhibit the generation of lithium Zhi Jing, be conducive to improve battery capacity keep energy
Power, the application for gained diaphragm in the powerful lithium electrical domain of high-energy provide the foundation, and during preparing diaphragm,
Without separately adding adhesive, cost is reduced, and can choose different monomers and regulate and control feed ratio, regulate and control the adherency of terpolymer
Property；
Compared with prior art, in the present invention, three kinds of different monomers is had chosen and carry out polymerization reaction, and regulate and control different lists
The type and feed ratio of body have obtained the different terpolymers with caking property, are used as improving membrane surface performance
Coating, with mention in the prior art it is single use the monomer containing catechol compared with raw material, terpolymer have more
More adjustability of structure and viscosity adjustability, and polymerization speed is fast.
Detailed description of the invention
Fig. 1 is the terpolymer modified ceramic based on catechol obtained in commercial ceramic diaphragm and the present embodiment 2
Membrane contacts angle comparison diagram, wherein a is the contact angle of commercial ceramic diaphragm, and b is that the ter-polymers based on catechol are modified
The contact angle of ceramic diaphragm；
Fig. 2 be embodiment 1, the terpolymer modified ceramic diaphragm based on catechol prepared in embodiment 2 and
The adhesion strength test result figure of ceramic diaphragm and battery positive/negative plate is commercialized.
Specific embodiment
In the following, technical solution of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of preparation method of terpolymer modified ceramic diaphragm based on catechol proposed by the present invention, including with
Lower step:
S1, by 0.34g dopamine methyl acrylamide monomer (DMA), 1.5g 2- acrylic acid -2- methoxy acrylate
(MEA), 0.08g styrene, 20mg 2,2'- azo bis- (2- methyl propionitrile) (AIBN), 10mL dimethylformamide (DMF) add
Enter in tube sealing, successively carry out a pumping, primary freezing and primary solution and take out, successively carry out later secondary pumping, secondary freezing and
Secondary solution is taken out, then carry out three times pumping, freeze and solve three times pumping three times, react 10h at 60 DEG C after tube sealing, be cooled to room temperature
Afterwards three times with methanol extraction, it is then placed in vacuum oven, dries 10h under room temperature in vacuum conditions and obtain terpolymer,
10g terpolymer is added in the mixed liquor of 10mL water and ethyl alcohol and obtains polymer solution, wherein the volume ratio of water and ethyl alcohol
For 3:1；
S2, the surface that polymer solution is coated in ceramic diaphragm, are then placed in vacuum drying oven, in 60 DEG C of dry 10h
Obtain the terpolymer modified ceramic diaphragm based on catechol.
To the terpolymer modified ceramic diaphragm and commercialization ceramics based on catechol prepared in the present embodiment
Diaphragm tests the guarantor's liquid rate and contact angle of battery, as a result as shown in the table:
| Sample | Imbibition rate (%) | Contact angle (°) |
| Ceramic diaphragm is commercialized | 80 | 68 |
| Diaphragm prepared by embodiment 1 | 150 | 30 |
As seen from the above table, prepared terpolymer modified ceramic diaphragm and quotient based on catechol in the present embodiment
Product ceramic diaphragm is compared, and imbibition rate improves, and contact angle becomes smaller.
Embodiment 2
A kind of preparation method of terpolymer modified ceramic diaphragm based on catechol proposed by the present invention, including with
Lower step:
S1, by 0.34g dopamine methyl acrylamide monomer (DMA), 0.75g 2- acrylic acid -2- methoxy acrylate
(MEA), 0.08g styrene, 20mg 2,2'- azo bis- (2- methyl propionitrile) (AIBN), 20mL dimethylformamide (DMF) add
Enter in tube sealing, tube sealing after pumping-freezing three times-solution is taken out then is repeated, 60 DEG C of reaction 8h are heavy with ether after being cooled to room temperature
It forms sediment three times, is added in vacuum oven, dry 8h under room temperature in vacuum conditions, terpolymer is obtained, by 1g terpolymer
It is added in the mixed liquor of 10mL water and dehydrated alcohol and obtains polymer solution, wherein the volume ratio of water and dehydrated alcohol is 3:1；
S2, the surface that polymer solution is coated in ceramic diaphragm, are put into vacuum drying oven, obtain institute in 60 DEG C of dry 8h
State the terpolymer modified ceramic diaphragm based on catechol.
Fig. 1 is the terpolymer modified ceramic based on catechol obtained in commercial ceramic diaphragm and the present embodiment 2
Membrane contacts angle comparison diagram, wherein a is the contact angle of commercial ceramic diaphragm, and b is that the ter-polymers based on catechol are modified
The contact angle of ceramic diaphragm；As shown in Figure 1, the ter-polymers modified ceramic obtained in the present embodiment 2 based on catechol
The contact angle of diaphragm is substantially reduced compared with commercial ceramic diaphragm.
Fig. 2 be embodiment 1, the terpolymer modified ceramic diaphragm based on catechol prepared in embodiment 2 and
The adhesion strength test result figure of ceramic diaphragm and battery positive/negative plate is commercialized；As shown in Figure 2, embodiment 1, make in embodiment 2
Cohesive force of the standby terpolymer modified ceramic diaphragm based on catechol compared with ceramic diaphragm is commercialized, with positive and negative anodes
Enhance.
Embodiment 3
A kind of preparation method of terpolymer modified ceramic diaphragm based on catechol proposed by the present invention, including with
Lower step:
S1, by 0.34g dopamine methyl acrylamide monomer (DMA), 0.5g 2- acrylic acid -2- methoxy acrylate
(MEA), 0.08g styrene, 20mg 2,2'- azo bis- (2- methyl propionitrile) (AIBN), 10mL dimethylformamide (DMF) add
Enter in tube sealing, tube sealing after pumping-freezing three times-solution is taken out then is repeated, 60 DEG C of reaction 9h after being cooled to room temperature, use methanol
Dissolution precipitating three times, is added in vacuum oven, dries 9h under room temperature in vacuum conditions and obtains terpolymer, 1g ternary is total to
Polymers is added in the mixed liquor of 10mL water and ethyl alcohol, obtains polymer solution；
S2, the surface that polymer solution is coated in ceramic diaphragm, are put into vacuum drying oven, remove in 60 DEG C of dry 10h
Solvent obtains the terpolymer modified ceramic diaphragm based on catechol.
Embodiment 4
A kind of preparation method of terpolymer modified ceramic diaphragm based on catechol proposed by the present invention, including with
Lower step:
S1, by 0.34g dopamine methyl acrylamide monomer (DMA), 0.5g 2- acrylic acid -2- methoxy acrylate
(MEA), 1.5g methyl methacrylate (MA), 20mg 2,2'- azo bis- (2- methyl propionitrile) (AIBN) and 10mL dimethyl methyls
Amide (DMF) is added in tube sealing, and then tube sealing, 60 DEG C of reaction 10h are cooled to room after pumping-freezing three times-solution is taken out repeatedly
Wen Houyong ether dissolution precipitates three times, is added in vacuum oven, dries 9h under room temperature in vacuum conditions, obtains ternary polymerization
1g terpolymer is added in the mixed liquor of 10mL water and ethyl alcohol, obtains polymer solution, wherein the body of water and ethyl alcohol by object
Product is than being 3:1；
S2, the surface that polymer solution is coated in ceramic diaphragm, are put into vacuum drying oven, and dry 10h is obtained at 60 DEG C
The terpolymer modified ceramic diaphragm based on catechol.
Embodiment 5
A kind of preparation method of terpolymer modified ceramic diaphragm based on catechol proposed by the present invention, including with
Lower step:
S1, by 0.34g dopamine methyl acrylamide monomer (DMA), 0.5g 2- acrylic acid -2- methoxy acrylate
(MEA), 1.5g methylol glyceride HEMA, 20mg 2,2'- azo bis- (2- methyl propionitrile) (AIBN), 10mL dimethyl formyl
Amine (DMF) is added in tube sealing, and tube sealing after pumping-freezing three times-solution is taken out then is repeated, reacts 11h at 60 DEG C, is cooled to room
Wen Houyong methanol dissolution precipitating three times, is then added in vacuum oven, dries 11h under room temperature in vacuum conditions, obtain ternary
1g terpolymer is added in the mixed liquor of 10mL water and ethyl alcohol, obtains polymer solution, wherein water and ethyl alcohol by copolymer
Volume ratio be 3:1；
S2, polymer solution is coated on ceramic diaphragm, is put into vacuum drying oven, dry 12h obtains institute at 60 DEG C
State the terpolymer modified ceramic diaphragm based on catechol.
Embodiment 6
A kind of preparation method of terpolymer modified ceramic diaphragm based on catechol proposed by the present invention, including with
Lower step:
S1, with the monomer A containing catechol and double bond, the monomer B containing double bond and without catechol and containing double bond and not
Monomer C containing catechol is that raw material carries out copolyreaction, obtains terpolymer, terpolymer is dissolved in water and ethyl alcohol
Mixed liquor in, obtain polymer solution；
S2, the surface that polymer solution is coated in ceramic diaphragm, obtain the ternary based on catechol after drying
Copolymer-modified ceramic diaphragm.
Embodiment 7
A kind of preparation method of terpolymer modified ceramic diaphragm based on catechol proposed by the present invention, including with
Lower step:
S1, with 3,4- dihydroxy benzenes -1- alanine Methacrylamide, 2- acrylic acid -2- methoxy acrylate and methyl-prop
E pioic acid methyl ester is that raw material carries out copolyreaction, obtains terpolymer, terpolymer is dissolved in the mixed liquor of water and ethyl alcohol
In, obtain polymer solution；
S2, the surface that polymer solution is coated in ceramic diaphragm, obtain the ternary based on catechol after drying
Copolymer-modified ceramic diaphragm；
Wherein, in S2, during the surface that polymer solution is coated in ceramic diaphragm, used coating method
For spin coating；
In S2, the ceramic diaphragm includes basement membrane and the ceramic layer for being coated on membrane surface；The raw material of the ceramic layer
Mixture including silica, zinc oxide, and the weight ratio of silica, zinc oxide is 3:2；Original used by the basement membrane
Material is polyethylene.
A kind of terpolymer modified ceramic diaphragm based on catechol that the present invention also proposes, using described based on neighbour
The preparation method of the terpolymer modified ceramic diaphragm of benzenediol is prepared.
One kind that the present invention also proposes terpolymer modified ceramic diaphragm based on catechol is in lithium-ion electric
Application in pond.
Embodiment 8
A kind of preparation method of terpolymer modified ceramic diaphragm based on catechol proposed by the present invention, including with
Lower step:
S1, it is total to using dopamine Methacrylamide, butyl methacrylate and Isobutyl methacrylate as raw material
Poly- reaction, obtains terpolymer, terpolymer is dissolved in the mixed liquor of water and ethyl alcohol, obtains polymer solution；
S2, the surface that polymer solution is coated in ceramic diaphragm, obtain the ternary based on catechol after drying
Copolymer-modified ceramic diaphragm；
Wherein, in S2, during the surface that polymer solution is coated in ceramic diaphragm, used coating method
For dip-coating；
In S2, the ceramic diaphragm includes basement membrane and the ceramic layer for being coated on membrane surface；The raw material of the ceramic layer
Including aluminium oxide；Raw material used by the basement membrane is the mixture of polyimides, polymethyl methacrylate, and polyamides is sub-
Amine, polymethyl methacrylate weight ratio be 3:4.
A kind of terpolymer modified ceramic diaphragm based on catechol that the present invention also proposes, using described based on neighbour
The preparation method of the terpolymer modified ceramic diaphragm of benzenediol is prepared.
One kind that the present invention also proposes terpolymer modified ceramic diaphragm based on catechol is in lithium-ion electric
Application in pond.
Embodiment 9
A kind of preparation method of terpolymer modified ceramic diaphragm based on catechol proposed by the present invention, including with
Lower step:
S1, with 3,4- dihydroxy benzenes methyl ether -1- alanine Methacrylamide, hydroxyethyl meth acrylate and 3- first
Oxygroup methyl acrylate is that raw material carries out copolyreaction, obtains terpolymer, and terpolymer is dissolved in water and ethyl alcohol
In mixed liquor, polymer solution is obtained；
S2, the surface that polymer solution is coated in ceramic diaphragm, obtain the ternary based on catechol after drying
Copolymer-modified ceramic diaphragm；
Wherein, in S2, during the surface that polymer solution is coated in ceramic diaphragm, used coating method
For spraying；
In S2, the ceramic diaphragm includes basement membrane and the ceramic layer for being coated on membrane surface；The raw material of the ceramic layer
Including boehmite, calcium carbonate, cerium oxide, magnesia mixture, and the weight ratio of boehmite, calcium carbonate, cerium oxide, magnesia
For 2:6:3:1；Raw material used by the basement membrane be polypropylene, polytetrafluoroethylene (PTFE), polyvinyl alcohol mixture, and polypropylene,
Polytetrafluoroethylene (PTFE), polyvinyl alcohol weight ratio be 1:4:2.
A kind of terpolymer modified ceramic diaphragm based on catechol that the present invention also proposes, using described based on neighbour
The preparation method of the terpolymer modified ceramic diaphragm of benzenediol is prepared.
One kind that the present invention also proposes terpolymer modified ceramic diaphragm based on catechol is in lithium-ion electric
Application in pond.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (8)
1. a kind of preparation method of the terpolymer modified ceramic diaphragm based on catechol, which is characterized in that including following
Step:
S1, with containing catechol and double bond monomer A, containing double bond and without catechol monomer B and containing double bond and without neighbour
The monomer C of benzenediol is that raw material carries out copolyreaction, obtains terpolymer, and terpolymer is dissolved in the mixed of water and ethyl alcohol
It closes in liquid, obtains polymer solution；
S2, the surface that polymer solution is coated in ceramic diaphragm, obtain the ternary polymerization based on catechol after drying
Object modified ceramic diaphragm.
2. the preparation method of the terpolymer modified ceramic diaphragm based on catechol according to claim 1, feature
It is, in S1, the monomer A containing catechol and double bond is dopamine Methacrylamide, 3,4- dihydroxy benzenes -1- third
One of propylhomoserin Methacrylamide, 3,4- dihydroxy benzenes methyl ether -1- alanine Methacrylamide.
3. the preparation method of the terpolymer modified ceramic diaphragm according to claim 1 or claim 2 based on catechol, special
Sign is, in S1, the monomer B containing double bond and without catechol and the monomer C containing double bond and without catechol are 2-
Acrylic acid -2- methoxy acrylate, styrene, methyl methacrylate, butyl methacrylate, Isobutyl methacrylate, hydroxyl
Ethylmethyl acrylate, polyethylene glycol dimethacrylate, 3- methoxy-methyl acrylate, methyl acrylate, acrylic acid
Any one in ethyl ester, glycidyl methacrylate.
4. the preparation side of the terpolymer modified ceramic diaphragm described in any one of -3 based on catechol according to claim 1
Method, which is characterized in that in S2, during the surface that polymer solution is coated in ceramic diaphragm, used coating side
Formula is one of spin coating, dip-coating, dimple version, spraying.
5. the preparation side of the terpolymer modified ceramic diaphragm described in any one of -4 based on catechol according to claim 1
Method, which is characterized in that in S2, the ceramic diaphragm includes basement membrane and the ceramic layer for being coated on membrane surface；The ceramic layer
Raw material include one or more of aluminium oxide, boehmite, silica, calcium carbonate, zinc oxide, cerium oxide, magnesia
Mixture.
6. the preparation method of the terpolymer modified ceramic diaphragm based on catechol according to claim 5, feature
It is, raw material used by the basement membrane is polyethylene, polypropylene, polyimides, polytetrafluoroethylene (PTFE), Kynoar, polychlorostyrene
Ethylene, polyethylene terephthalate, Kynoar-hexafluoropropylene copolymer, polymethyl methacrylate, polycyclic oxygen second
The mixture of one or more of alkane, polyvinyl alcohol.
7. a kind of terpolymer modified ceramic diaphragm based on catechol, which is characterized in that using as in claim 1-6
The preparation method of terpolymer modified ceramic diaphragm described in any one based on catechol is prepared.
8. a kind of terpolymer modified ceramic diaphragm based on catechol as claimed in claim 7 is in lithium ion battery
Using.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810686093.6A CN109037547A (en) | 2018-06-28 | 2018-06-28 | Terpolymer modified ceramic diaphragm and its preparation and application based on catechol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810686093.6A CN109037547A (en) | 2018-06-28 | 2018-06-28 | Terpolymer modified ceramic diaphragm and its preparation and application based on catechol |
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| US20180034031A1 (en) * | 2016-07-26 | 2018-02-01 | Massachusetts Institute Of Technology | Lithium-air battery separators and related compositions |
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2018
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| KR20140136807A (en) * | 2013-05-21 | 2014-12-01 | 주식회사 엘지화학 | Polyolefin separator and method for preparing thereof |
| CN105070868A (en) * | 2015-08-26 | 2015-11-18 | 厦门大学 | Dopamine-modifying ceramic composite separator and application thereof |
| US20180034031A1 (en) * | 2016-07-26 | 2018-02-01 | Massachusetts Institute Of Technology | Lithium-air battery separators and related compositions |
| CN106953051A (en) * | 2017-03-10 | 2017-07-14 | 厦门益舟新能源科技有限公司 | A kind of ceramic diaphragm of in-situ preparation compound binding agent and its preparation method and application |
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