CN110061174A - A kind of method and ceramic diaphragm preparing gluing ceramic diaphragm based on sol-gel technique - Google Patents
A kind of method and ceramic diaphragm preparing gluing ceramic diaphragm based on sol-gel technique Download PDFInfo
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- CN110061174A CN110061174A CN201910264679.8A CN201910264679A CN110061174A CN 110061174 A CN110061174 A CN 110061174A CN 201910264679 A CN201910264679 A CN 201910264679A CN 110061174 A CN110061174 A CN 110061174A
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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
- 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
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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
The invention discloses a kind of methods and product that gluing ceramic diaphragm is prepared based on sol-gel technique, comprising the following steps: prepares modified Nano-meter SiO_22Colloidal sol and alumina sol, epoxy analog derivative isogel auxiliary agent is added after the two is mixed according to a certain percentage and prepares mixed sols gel, by non-woven polyolefin basement membrane in mixed sols gel after second dipping and rolling, carry out drying and processing, and film surface two sides after the drying coat organic matter coating micelle, are prepared into ceramic diaphragm.Gluing ceramic diaphragm is prepared using mixed gel in the application, after triazines nitrogen-containing group is added, reaction forms amido bond, with very strong adhesive force, not only increase the bonding force of diaphragm and positive/negative plate, make the consistent of cell thickness, and there is better imbibition ability and thermal stability, greatly increases the security performance of battery.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to one kind prepares gluing ceramics based on sol-gel technique
The method and ceramic diaphragm of diaphragm.
Background technique
With flourishing for China's new energy cause, lithium ion battery is due to its high-energy density and longer circulation longevity
The advantages that life, has become electric car and the battery system of large-scale energy storage device is preferred.In recent years, with lithium battery applications market
Continuous development, requirement of the client to performance of lithium ion battery also constantly promoting, especially combo class battery, it is desirable that battery core
Necessary consistency and stability with higher have high consistency to meet each battery core during being recycled for a long time,
The deterioration because of Individual cells is avoided to lead to the decaying of whole group battery performance.
Lithium ion battery there is also some problems that wherein the important point is exactly safety issue, and diaphragm plays very
Crucial effect.The working principle of diaphragm is barrier positive and negative pole material, and the two directly contact is avoided to lead to short circuit, so as to avoid
Safety accident.So the performance of diaphragm directly affects the safety of lithium ion battery.Monolayer polyethylene (PE), single-layer polypropylene
(PP), the polyolefins such as PP/PE/PP three-layer membrane diaphragm liquid retention is low, thermal stability is poor and there are biggish safety is hidden
Suffer from.The bonding force of the pore-size distribution of diaphragm also extreme influence battery core electrical property consistency, diaphragm and pole piece also influence battery core into
The battery core thickness of row high rate charge-discharge, in the case where high current intensity, high temperature or lithium dendrite growth, be easy to happen contraction or
Perforation, so as to cause positive and negative anodes short circuit.Such diaphragm has been unable to meet application demand, coated ceramic on the substrates such as polyolefin at present
The method that composite diaphragm is made in layer is widely adopted.Common ceramic material includes silica, zirconium dioxide, aluminium oxide
Deng.
PET basement membrane has greater advantage in terms of thermodynamics, is heat-shrinked≤1% in 200 DEG C of lower diaphragm plates；Gel coat makes
PET membrane pore size is reduced and is evenly distributed, and rate of liquid aspiration is accelerated, and is effectively improved the thermodynamic property of diaphragm；Rubberised layer can have
Effect improve battery core comprehensive performance, such as improve battery core surface smoothness, reduce battery core thickness, improve battery core interface, increase diaphragm with
The cohesive force of pole piece so that battery core is in energy density, fast charging and discharging is horizontal, cycle specificity and in terms of mentioned
It rises, all largely improves in security feature, anode ring forming level, this develops Lithium Battery Industryization highly beneficial.
108063209 A of patent of invention CN discloses a kind of lithium ion battery ceramic diaphragm and preparation method thereof, specially
The ceramic layer that a layer thickness is 1-4um is applied on the surface in lithium ion battery substrate diaphragm, binder is epoxy resin, is led to
Ultraviolet light is crossed, so that epoxy resin of binder crosslinks solidification, improves ceramic layer heat resisting temperature and and ceramic layer
With the adhesion strength of basement membrane.
Patent of invention CN104538573A is using using graphite, LANO base graphene or graphene coated inorganic matter as painting
The inorganic filler of layer diaphragm is prepared into after uniform slurry using churned mechanically mode coated on diaphragm etc..The technique stream
Journey is simple, but not ideal enough to the dispersion effect of ceramic powder, and there are the soft-agglomerated phenomenons in part, is easy to cause Stability of Slurry poor,
The problems such as ceramic diaphragm rough surface, uneven thickness.These problems will bring hidden danger to the security performance of lithium ion battery.
Summary of the invention
In order to overcome the problems of the prior art, battery core surface smoothness is improved, battery core thickness is reduced, improves battery core circle
Face, increases the cohesive force of diaphragm and pole piece, and the present invention provides a kind of side that gluing ceramic diaphragm is prepared based on sol-gel technique
Method and ceramic diaphragm, by that will include Nano-meter SiO_22Mixed sols immersing hydrogels with aluminium oxide are organic coating after diaphragm
Object coating micelle, is prepared into ceramic diaphragm, improves the imbibition ability and thermal stability of diaphragm, increases the security performance of battery.
To achieve the goals above, the invention is realized by the following technical scheme:
A method of gluing ceramic diaphragm is prepared based on sol-gel technique, comprising the following steps:
S1, Nano-meter SiO_22The modification of colloidal sol: by positive silicate class, Organic Alcohol, halogen acids mixes simultaneously with water, wherein positive silicon
Esters of gallic acid, water, Organic Alcohol and halogen acids the ratio of amount of substance be (1-2): (3-5): (5-7): 8 × 10-3, at a temperature of 60 DEG C
20-40min is stirred, pH value is adjusted between 2-3, nitrogen-containing group compound is added, continues to stir 5-8h, prepares SiO2It is molten
Glue；SiO will be added to after stearic acid heating and melting2In colloidal sol, it is stirred acceleration polycondensation while ammonium hydroxide is added, works as pH=7
When stop be added ammonium hydroxide, prepare modified SiO2Colloidal sol.
The preparation of S2, alumina sol: organo-aluminum compound and Organic Alcohol are mixed simultaneously, are stirred at a temperature of 50-70 DEG C
30min is mixed, alumina sol is prepared.
The preparation of S3, mixed sols gel: modification SiO prepared by S12After alumina sol prepared by colloidal sol, S2 is stablized
Mixed with epoxy analog derivative, wherein epoxy analog derivative, the mass ratio of the material of silicon is 1:(8-12 in aluminium and solution in solution):
(2-4) generates stable mixed sols gel after reaction.
S4, immersion and mangle: non-woven polyolefin is impregnated in 3h in the mixed sols gel of S3 preparation, then uses padding machine
It to non-woven polyolefin mangle under 0.4-0.6GP pressure, is placed in colloidal sol again after removing and impregnates 10min, then mangle is primary,
Non-woven polyolefin after mangle is dried into postposition and bakes 8-12h, pressure 0.1Pa for 90-140 DEG C in a vacuum drying oven.
S5, coating micelle: it is applied using dotted spraying method in the film surface two sides of the S4 diaphragm basement membrane prepared coating organic matter
Layer micelle, is prepared into ceramic diaphragm.
Further, nitrogen-containing group compound is triazines nitrogen-containing group compound in the step S1, wherein triazines
The crosslinking alkyds that nitrogen-containing group compound generates after reacting with step S1 occur ammonia -ester exchange reaction and form amido bond, tool
There is very strong adhesive force, reaction skeleton symbol is as follows: R1NH2+RCOOR2 → RCONH-R1.
Further, one or both of the triazines nitrogen-containing group compound is as follows formula 1 or formula 2,
Wherein formula 1 is triazines nitrogen-containing group -1, and formula 2 is triazines nitrogen-containing group -2,
Further, halogen acids is one of HCl or HF in step S1.
Further, the organo-aluminum compound in the step S2 is one of aluminium isopropoxide or aluminium secondary butylate.
Further, epoxy analog derivative is one of 1,2- propylene oxide and propylene oxide in the step S3.
Further, Organic Alcohol is ethyl alcohol, isopropanol, one or more of tert-butyl alcohol in the step S1 and step S2
Mixing.
Further, non-woven polyolefin is cellulose basement membrane, polyimide basement membrane, PET basement membrane in the step S4
One of.
Further, the organic matter coating micelle in the step S5 be one of PMMA micelle or PVDF micelle,
Middle PMMA is the abbreviation of Poly (methyl methacrylate), and its chemical name is polymethyl methacrylate, PVDF is
The abbreviation of Poly (vinylidene fluoride), its chemical name is polyvinylidene fluoride.
According to the ceramic diaphragm of the above-mentioned method preparation for preparing gluing ceramic diaphragm based on sol-gel technique, the ceramics
Diaphragm includes diaphragm basement membrane, and the first mixed gel composite coating, the second mixed gel that diaphragm basement membrane two sides are arranged in are compound
Coating, and the first organic coating on the outside of the first mixed gel composite coating is set and is arranged compound in the second mixed gel
The second organic coating on the outside of coating.
Main process of the invention is the positive silicate class that will prepare gel and organo-aluminum compound as presoma, will just
Silicate class is modified hydrolyzed in acid condition to be made collosol substance, by organo-aluminum compound directly and Organic Alcohol mix generation it is molten
Finally gel auxiliary agent is added in silicon source colloidal sol and silicon source colloidal sol by gelatin substance, i.e. epoxy analog derivative generates gel.
Beneficial effects of the present invention are as follows:
(1) the mixed sols gel based on sol-gel technique preparation in the present invention introduces silicon member in alumina aerogels
Element not only concentrates pore-size distribution more, and specific surface area is bigger, while also improving structural strength and networking degree, furthermore
The silica sections being introduced into are present in skeleton structure in the form of low polymer, have played certain supporting role, favorably
In the cracking and shrinkage phenomenon of reduction sample during the preparation process.
(2) mixed sols gel itself prepared by the present invention has certain aperture, can block polyolefin fibrous non-woven after dry
The large aperture of cloth just improves the macrovoid problem of non-woven polyolefin, solves polyolefin fibrous non-woven cloth diaphragm due to aperture
The excessive problem of self-discharge of battery caused by excessive defect, and there is better imbibition ability and thermal stability.
(3) triazines nitrogen-containing group is added in the present invention, after wherein triazines nitrogen-containing group compound is reacted with step S1
The crosslinking alkyds of generation occur ammonia -ester exchange reaction and form amido bond, have very strong adhesive force, so that the gluing of preparation
Ceramic diaphragm and positive/negative plate have certain bonding force, also improve battery while improving the consistency of cell thickness
Security performance.
Detailed description of the invention
Fig. 1 is the schematic diagram of gluing ceramic diaphragm prepared by embodiment 1；
Appended drawing reference is as follows:
1, diaphragm basement membrane；2, the first mixed gel composite coating；3, the second mixed gel composite coating；4, first organic painting
Layer；5, the second organic coating.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with attached drawing and specific implementation
Example, the present invention will be described in further detail.
Embodiment 1
A method of gluing ceramic diaphragm is prepared based on sol-gel technique, comprising the following steps:
Step S1: Nano-meter SiO_22The modification of colloidal sol
By ethyl orthosilicate, ethyl alcohol, water mixes simultaneously with hydrochloric acid, and mixed proportion is n (ethyl orthosilicate): n (water): n
(ethyl alcohol): n (hydrochloric acid)=1:4:6:8 × 10-3, 30min is stirred at a temperature of 60 DEG C, adjusts pH value between 2-3, triazine is added
Class nitrogen-containing group -1 continues to stir 6h, prepares SiO2Colloidal sol.
By stearic acid heating and melting, the stearic acid of melting is added to SiO2In colloidal sol, stirred while ammonium hydroxide is added
Acceleration polycondensation is mixed, stops that ammonium hydroxide is added as pH=7, prepares modified SiO2Colloidal sol.
Step S2: the preparation of alumina sol
Aluminium isopropoxide and dehydrated alcohol are mixed, 30min is stirred at a temperature of 60 DEG C, prepares alumina sol.
Step S3: the preparation of mixed sols gel
Modification SiO prepared by S12Colloidal sol, S2 preparation alumina sol stablize after and 1,2- propylene oxide mixing,
In 1,2- propylene oxide, the mass ratio of the material of silicon is 1:10:3 in aluminium and solution in solution, it is molten that stable mixing is generated after reaction
Glue gel.
Step S4: immersing and mangle
PET basement membrane is impregnated in 3h in the mixed sols gel of S3 preparation, it is then right under 0.4-0.6GP pressure with padding machine
Non-woven polyolefin mangle, is placed in colloidal sol again after removing and impregnates 10min, then mangle is primary, second dipping and rolling, after mangle
PET basement membrane dries, and then puts PET basement membrane and bakes 12h in a vacuum drying oven, prepares diaphragm basement membrane, wherein vacuum oven
Operating condition be 90 DEG C of stoving temperature, pressure be 0.1Pa high vacuum environment.
Step S5: coating micelle
PVDF micelle is coated in the film surface two sides of the S4 diaphragm basement membrane prepared using dotted spraying method, is made based on colloidal sol
Gel technique prepares gluing ceramic diaphragm.
Embodiment 2
Step S1: Nano-meter SiO_22The modification of colloidal sol
By ethyl orthosilicate, ethyl alcohol, water mixes simultaneously with hydrochloric acid, and mixed proportion is n (ethyl orthosilicate): n (water): n
(ethyl alcohol): n (hydrochloric acid)=1:4:6:8 × 10-3, 30min is stirred at a temperature of 60 DEG C, adjusts pH value between 2-3, triazine is added
- 2 additive of class nitrogen-containing group continues to stir 6h, prepares SiO2Colloidal sol.
By stearic acid heating and melting, the stearic acid of melting is added to SiO2In colloidal sol, stirred while ammonium hydroxide is added
Acceleration polycondensation is mixed, stops that ammonium hydroxide is added as pH=7, prepares modified SiO2Colloidal sol.
Step S2: the preparation of alumina sol
Aluminium isopropoxide and dehydrated alcohol are mixed, 30min is stirred at a temperature of 60 DEG C, prepares alumina sol.
Step S3: the preparation of mixed sols gel
Modification SiO prepared by S12Colloidal sol, S2 preparation alumina sol stablize after and 1,2- propylene oxide mixing,
In 1,2- propylene oxide, the mass ratio of the material of silicon is 1:12:4 in aluminium and solution in solution, it is molten that stable mixing is generated after reaction
Glue gel.
Step S4: immersing and mangle
PET basement membrane is impregnated in 3h in the mixed sols gel of S3 preparation, it is then right under 0.4-0.6GP pressure with padding machine
Non-woven polyolefin mangle, is placed in colloidal sol again after removing and impregnates 10min, then mangle is primary, second dipping and rolling, after mangle
PET basement membrane dries, and then puts PET basement membrane and bakes 8h in a vacuum drying oven, prepare diaphragm basement membrane, wherein vacuum oven
Operating condition is 140 DEG C of stoving temperature, and pressure is the high vacuum environment of 0.1Pa.
Step S5: coating micelle
PVDF micelle is coated in the film surface two sides of the S4 diaphragm basement membrane prepared using dotted spraying method, is made based on colloidal sol
Gel technique prepares gluing ceramic diaphragm.Ceramic diaphragm as shown in Figure 1 includes diaphragm basement membrane 1, is arranged in diaphragm basement membrane two sides
The first mixed gel composite coating 2, the second mixed gel composite coating 3, and be arranged in the first mixed gel composite coating 2
First organic coating 4 in outside and the second organic coating 5 that 3 outside of the second mixed gel composite coating is set, wherein first
Organic coating 4 and the second organic coating 5 are PVDF glue granular layer.
Embodiment 3
Step S1: Nano-meter SiO_22The modification of colloidal sol
By ethyl orthosilicate, ethyl alcohol, water mixes simultaneously with hydrochloric acid, and mixed proportion is n (ethyl orthosilicate): n (water): n
(ethyl alcohol): n (hydrochloric acid)=1:4:6:8 × 10-3, 30min is stirred at a temperature of 60 DEG C, adjusts pH value between 2-3, triazine is added
- 2 additive of class nitrogen-containing group continues to stir 6h, prepares SiO2Colloidal sol.
By stearic acid heating and melting, the stearic acid of melting is added to SiO2In colloidal sol, stirred while ammonium hydroxide is added
Acceleration polycondensation is mixed, stops that ammonium hydroxide is added as pH=7, prepares modified SiO2Colloidal sol.
Step S2: the preparation of alumina sol
Aluminium isopropoxide and dehydrated alcohol are mixed, 30min is stirred at a temperature of 60 DEG C, prepares alumina sol.
Step S3: the preparation of mixed sols gel
Modification SiO prepared by S12It is mixed after alumina sol prepared by colloidal sol, S2 is stablized with propylene oxide, middle ring
The mass ratio of the material of silicon is 1:10:3 in aluminium and solution in oxypropylene, solution.
Step S4: immersing and mangle
PE/PET MULTILAYER COMPOSITE basement membrane is impregnated in 3h in the mixed sols gel of S3 preparation, then with padding machine in 0.4-
It to non-woven polyolefin mangle under 0.6GP pressure, is placed in colloidal sol again after removing and impregnates 10min, then mangle is primary, two leachings two
It rolls, the PET basement membrane after mangle is dried, then PET basement membrane is put and bakes 8h in a vacuum drying oven, prepares diaphragm basement membrane,
The operating condition of middle vacuum oven is 140 DEG C of stoving temperature, and pressure is the high vacuum environment of 0.1Pa.
Step S5: coating micelle
PVDF micelle is coated in the film surface two sides of the S4 diaphragm basement membrane prepared using dotted spraying method, is made based on colloidal sol
Gel technique prepares gluing ceramic diaphragm.
A kind of method that gluing ceramic diaphragm is prepared based on sol-gel technique that the present invention announces, by by Nano-meter SiO_22
1,2- propylene oxide is added after being mixed after sol-gel modified with alumina sol and prepares mixed sols gel, wherein 1,2- epoxy
Propane is a kind of very effective proton capture agent, and being typically due to lewis acid attack epoxy analog derivative makes its generation can not
Inverse ring-opening reaction, forming free radical has very high activity, can accelerate the reaction rate between hydrated metal ion, polymerization reaction
To form the network structure of long-chain.Polyolefin fibrous non-woven is distributed in after carrying out second dipping and rolling in mixed sols gel and is dried, at it
It is made after surface spraying organic matter coating micelle, gluing ceramic diaphragm prepared by the present invention not only increases diaphragm and positive/negative plate
Bonding force makes the consistent of cell thickness, and has better imbibition ability and thermal stability, makes the security performance of battery significantly
Increase.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these explanations.For those skilled in the art, do not departing from
Under the premise of present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to protection model of the invention
It encloses.
Claims (10)
1. a kind of method for preparing gluing ceramic diaphragm based on sol-gel technique, which comprises the following steps:
S1, Nano-meter SiO_22The modification of colloidal sol: by positive silicate class, Organic Alcohol, halogen acids mixes simultaneously with water, wherein positive esters of silicon acis
Class, water, Organic Alcohol and halogen acids the ratio of amount of substance be (1-2): (3-5): (5-7): 8 × 10-3, stirred at a temperature of 60 DEG C
20-40min adjusts pH value between 2-3, nitrogen-containing group compound is added, and continues to stir 5-8h, prepares SiO2Colloidal sol；It will
SiO is added to after stearic acid heating and melting2In colloidal sol, it is stirred acceleration polycondensation while ammonium hydroxide is added, is stopped as pH=7
Ammonium hydroxide is added, prepares modified SiO2Colloidal sol；
The preparation of S2, alumina sol: organo-aluminum compound and Organic Alcohol are mixed simultaneously, are stirred at a temperature of 50-70 DEG C
30min prepares alumina sol；
The preparation of S3, mixed sols gel: modification SiO prepared by S12Colloidal sol, S2 preparation alumina sol stablize after and ring
The mixing of oxygen analog derivative, wherein epoxy analog derivative, the mass ratio of the material of silicon is 1:(8-12 in aluminium and solution in solution): (2-
4) stable mixed sols gel, is generated after reaction；
S4, immersion and mangle: non-woven polyolefin is impregnated in 3h in the mixed sols gel of S3 preparation, is then existed with padding machine
It to non-woven polyolefin mangle under 0.4-0.6GP pressure, is placed in colloidal sol again after removing and impregnates 10min, then mangle is primary, it will
Non-woven polyolefin after mangle dries postposition and bakes 8-12h, pressure 0.1Pa for 90-140 DEG C in a vacuum drying oven；
S5, coating micelle: organic matter coating adhesive is coated in the film surface two sides of the S4 diaphragm basement membrane prepared using dotted spraying method
Grain, is prepared into ceramic diaphragm.
2. the method according to claim 1 for preparing gluing ceramic diaphragm based on sol-gel technique, which is characterized in that institute
Stating nitrogen-containing group compound in step S1 is triazines nitrogen-containing group compound.
3. the method according to claim 2 for preparing gluing ceramic diaphragm based on sol-gel technique, which is characterized in that institute
One or both of formula 1 or the formula 2 that triazines nitrogen-containing group compound is as follows are stated,
4. the method according to claim 1 for preparing gluing ceramic diaphragm based on sol-gel technique, which is characterized in that institute
Stating halogen acids in step S1 is one of HCl or HF.
5. the method according to claim 1 for preparing gluing ceramic diaphragm based on sol-gel technique, which is characterized in that institute
Stating the organo-aluminum compound in step S2 is one of aluminium isopropoxide or aluminium secondary butylate.
6. the method according to claim 1 for preparing gluing ceramic diaphragm based on sol-gel technique, which is characterized in that institute
Stating epoxy analog derivative in step S3 is one of 1,2 epoxy prapane or propylene oxide.
7. the method according to claim 1 for preparing gluing ceramic diaphragm based on sol-gel technique, which is characterized in that institute
Stating Organic Alcohol in step S1 and step S2 is ethyl alcohol, isopropanol, the mixing of one or more of tert-butyl alcohol.
8. the method according to claim 1 for preparing gluing ceramic diaphragm based on sol-gel technique, which is characterized in that institute
Stating non-woven polyolefin in step S4 is cellulose basement membrane, polyimide basement membrane, one of PET basement membrane.
9. the method according to claim 1 for preparing gluing ceramic diaphragm based on sol-gel technique, which is characterized in that institute
Stating the organic matter coating micelle in step S5 is one of PMMA micelle or PVDF micelle.
10. the ceramic diaphragm prepared method according to claim 1, which is characterized in that the ceramic diaphragm includes diaphragm base
The first mixed gel composite coating, the second mixed gel composite coating of diaphragm basement membrane two sides is arranged in film, and setting exists
The first organic coating on the outside of first mixed gel composite coating and be arranged on the outside of the second mixed gel composite coating second
Organic coating.
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