CN108258170A - A kind of preparation method of polyether-ether-ketone base lithium battery diaphragm - Google Patents
A kind of preparation method of polyether-ether-ketone base lithium battery diaphragm Download PDFInfo
- Publication number
- CN108258170A CN108258170A CN201711273783.0A CN201711273783A CN108258170A CN 108258170 A CN108258170 A CN 108258170A CN 201711273783 A CN201711273783 A CN 201711273783A CN 108258170 A CN108258170 A CN 108258170A
- Authority
- CN
- China
- Prior art keywords
- parts
- ether
- polyether
- ketone
- lithium battery
- 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
-
- 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
-
- 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)
- Cell Separators (AREA)
- Polyethers (AREA)
Abstract
The invention belongs to polyether-ether-ketone polymeric material fields, specifically disclose a kind of preparation method of polyether-ether-ketone base lithium battery diaphragm, include the following steps：(1) chlorosulfonation fluorine one monomers synthesize, the synthesis of (2) sulfonated polyether-ether-ketone, the mixing of (3) solution, (4) film forming, dry, (5) pore-forming, drying.The polyether-ether-ketone base lithium battery diaphragm being prepared by the method for the present invention, there is following performance：With electronic isolation, ensure the mechanical isolation of positive and negative anodes；Electrolyte resistance corrodes, and has enough chemistry and electrochemical stability；With preferable mechanical property.
Description
Technical field
The invention belongs to polymeric material fields, and in particular to a kind of preparation method of polyether-ether-ketone base lithium battery diaphragm.
Background technology
Chinese lithium battery industry is in the ascendant, and under the excitation of 12 plans, existing production capacity is expanded production to be opened with potential production capacity
Hair occur the situation that doubles year by year between 2011-2013, as most have in layer assembly in lithium ion battery profit value every
Film is even more initiative development.Between the short several years, China has emerged more than 40 family producers, possesses the production of more than 200 items altogether
Line.The development of lithium battery diaphragm technology is promoted with the variation of lithium ion battery applications, and current the characteristics of protruding is lithium
Battery the more does the more big and lithium battery more does smaller both ends development trend.
At " small ", portable electronic consumer product lithium battery is mainly reflected in, such as mobile phone, digital camera, electronics diction
Allusion quotation etc., the beautiful high-energy density requirement proposed with miniaturization to lithium battery design, promote for this kind of lithium battery applications every
Film the more should do the more thin.Because the meaning of high-energy density is exactly that more electrode materials are accommodated in small volume, in positive and negative anodes
Under the conditions of material is fixed, the development of High-performance diaphragm and production become inevitable, this requires in the case where diaphragm is thinner,
Keep original battery capacity and cycle life.At " big ", it is mainly reflected in electric bicycle and electric vehicle is used
Lithium dynamical battery in terms of, be not difficult to find out through the electric vehicle auto-ignition event of country's exposure, security performance is current to restrict power
The bottleneck of lithium battery.Here the main reason for, shows three aspects：Safety is lithium ion battery separator physicochemical property
Core；Dynamic lithium battery uses the battery core of capacity bigger, and capacity is bigger, and the performance indicator of battery core just needs finer and smoother technique
Ensure；Since the consistency and combination technique of series connection battery core can bring security risk, this is required especially for the system of lithium battery diaphragm
It makes more accurate.
In the structure of lithium battery, diaphragm is one of crucial interior layer assembly, and the performance of diaphragm determines the interface knot of battery
Structure, internal resistance etc. directly affect the characteristics such as capacity, cycle and the security performance of battery, and the diaphragm haveing excellent performance is to improving battery
Comprehensive performance play an important role.For diaphragm between anode and cathode, main function is by positive and negative anodes active material point
It separates, prevents the two poles of the earth short-circuit due to contact；In addition in electrochemical reaction, necessary electrolyte can be kept, forms ion movement
Channel, so diaphragm have it is stronger tolerance organic bath ability, mechanical strength is big, and service life is long, relatively thin, meet
It is used under different size and operating mode；When quick heat production temperature starts, diaphragm melts, and micropore is closed, and is become insulator, is prevented
Electrolyte passes through, so as to block electric current；There should be higher wellability；Higher ionic conductivity, to reduce in battery
Resistance, higher electrical insulating property, higher cost performance.Gel polymer electrolyte passes through the liquid electric that is fixed in polymer network
It solves matter molecule and realizes ionic conduction, the stability of existing solid polymer, and have the high ion conductivity of liquid electrolyte, show
Go out good application prospect.
The diaphragm material of the marketization is mainly the polyolefins diaphragm based on polyethylene, polypropylene.In general, relatively
Temperature resistant grade is relatively low, density is smaller, mechanical property is more crisp, more sensitive to environment.Main diaphragm material product has individual layer PP, list
Layer PE, PP+ ceramic coated, PE+ ceramic coateds, bilayer PP/PE, double-deck PP/PP and three layer of PP/PE/PP etc., wherein preceding two class is produced
Product are mainly used for 3C baby batteries field, and rear a few class products are mainly used for dynamic lithium battery field.In dynamic lithium battery diaphragm material
Expect in product, double-deck PP/PP diaphragm materials are mainly produced by Chinese Enterprise, are used in China's Mainland, this is primarily due at present
Stage, there are no the technologies and ability that double-layered compound film can be made in PP and PE by Chinese Enterprise.And Global Auto dynamic lithium battery makes
Diaphragm using the diaphragm materials products such as three layers of PP/PE/PP, bilayer PP/PE and PP+ ceramic coateds, PE+ ceramic coateds as
It is main.
At the same time, some other new types of diaphragm material product is also continuing to bring out and is starting to realize application, but, because of amount
Few valency is high, is mainly also used in dynamic lithium battery manufacturing field.These products mainly have：Polyester film, cellulose membrane, polyimides
Film, PA membrane, spandex, aramid fiber film etc..The problem of existing lithium ion battery separator is primarily present has：1st, before due to lithium battery
The improvement of body material is driven, the development and improved technology for causing diaphragm material relatively lag behind；2nd, tolerable temperature is relatively low, typically up to makes
With temperature between 110~130 DEG C, 3, mechanical strength it is poor, lithium ion battery separator tensile strength generally 22~25MPa it
Between, 4, under overtemperature or short-circuit conditions, situation can be made to deteriorate rapidly, it is difficult to which the protection played in the case of battery short circuit is made
With.
Polyether-ether-ketone is the aromatic polymer compound of molecular backbone chain link, and structural units is oxygen-to phenylene-carbonyl
The structure of base-phenyl, is a kind of semi-crystalline aromatic thermoplastic resin and a few can be 250 in the world at present
DEG C or more one of the thermostability engineering plastic of long service.Polyether-ether-ketone developed first by ICI companies in 1978
A kind of engineering plastics with very-high performance by years of researches, and form the product with independent intellectual property right.Polyethers
Ether ketone is mainly used for aerospace, automobile, electronics, food, medical instrument and petrochemical industry, these fields are to material purity
It requires very high.
Polyether-ether-ketone is the product that more early developed, and due to the presence of ehter bonds a large amount of in segment, improves the soft of segment
It is pliable, while segment is more regular without branch, therefore, polyether-ether-ketone can form crystalline texture.The crystallinity of polyether-ether-ketone is most
It is big by reachable 48%, between general common 20~30%.Since polyether-ether-ketone not only has high-performance, while it is small also to possess proportion
Feature, so being usually used in some requirements of Aeronautics and Astronautics, automobile to mould on the parts of Dai Gang, simultaneously because main in structure
It is made of benzene radicals, improves polymer chain rigidity and heat resistance, along with it has crystallinity, belong to high temperature resistant thermoplastic
Property plastics.Polymer dielectric is formed to polyether-ether-ketone lithium ion battery separator, colloidal polymer covering together with polyether-ether-ketone
Or be filled in microporous barrier, compared with aseptate polymer electrolyte lithium-ion battery, there is more superior performance.
Invention content
In view of the problems of the existing technology, the present invention provides a kind of preparation method of polyether-ether-ketone base lithium battery diaphragm.
Technical scheme is as follows：
A kind of preparation method of polyether-ether-ketone base lithium battery diaphragm, includes the following steps：
(1) chlorosulfonation fluorine one monomers synthesize：
By 4,4 ,-difluoro benzophenone, methylsufonyl chloride, chlorosulfonic acid are put into reactor, are persistently stirred under room temperature
It mixes, stirs 30~60min；System is warming up to 55~65 DEG C, persistently stirs 120~150min, after complete reaction, reaction product
After the washing of filtered and deionized water, chlorosulfonation fluorine ketone crystal is obtained；
The proportioning of the substance of above-mentioned reaction is as follows：In terms of parts by weight, 4,4 ,-difluoro benzophenone：20~30 parts, methyl
Sulfonic acid chloride：25~35 parts, chlorosulfonic acid：45~55 parts.
Step (1) reaction equation is as follows：
(2) sulfonated polyether-ether-ketone synthesizes：
Chlorosulfonation fluorine one monomers, hydroquinone, sodium carbonate, the sulfolane in step (1) are added in into reactor, high-purity
It is reacted under the sustainable protection of nitrogen, is warming up to 120~130 DEG C, constant temperature 30min；After material is completely dissolved in system, open
Agitating device, 15~25r/min of mixing speed are opened, then system temperature is risen to 180~190 DEG C, 300~360min of constant temperature；Most
Reaction mass is poured into normal-temperature water afterwards and is cooled down, by cooling material input high speed disintegrator, is crushed, object after crushing
Material, which is put into air dry oven, to be dried, dry 60~90min under 100~105 DEG C of environment；It is taken after material completely cooling
Go out, obtain sulfonated polyether-ether-ketone；
The proportioning of the substance of above-mentioned reaction is as follows：In terms of parts by weight, chlorosulfonation fluorine one monomers：5~15 parts, to benzene two
Phenol：5~15 parts, sodium carbonate：5~10 parts, sulfolane：60~85 parts.
Step (2) reaction equation is as follows：
(3) solution mixes：
The reaction mass sulfonated polyether-ether-ketone of step (2), suspension type polyvinyl-chloride, sodium carbonate, dimethylformamide are thrown
Enter to high speed agitator and carry out high-speed stirred, 1100~1200r/min of mixing speed, and continue 60~120min of stirring, obtain
Slurry；
The proportioning of the substance of above-mentioned reaction is as follows：In terms of parts by weight, sulfonated polyether-ether-ketone：45~55 parts, suspension method gathers
Vinyl chloride：5~10 parts, sodium carbonate：3~5 parts, dimethylformamide：35~45 parts.
Above-mentioned sodium carbonate is selected from 500~550 mesh.
(4) it forms a film, is dry：The pasty material of step (3) is poured on a glass, is put into air dry oven, 55
In the environment of~65 DEG C, dry 60~120min；
(5) pore-forming, drying：By material after step (4) processing, dilute hydrochloric acid is immersed in, in sulfolane mixed solution, during immersion
Between 480~640min, the material that above-mentioned immersion is completed is taken out, is rinsed repeatedly using deionized water, up to flushing liquor pH
Until 7, the material after above-mentioned deionized water is rinsed, which is put into vacuum drying chamber, to be dried, 85~95 DEG C of drying temperature,
180~240min of drying time obtains polyether-ether-ketone base diaphragm.
The proportioning of the substance of above-mentioned reaction is as follows：In terms of parts by weight, material after step (4) processing：10~15 parts, dilute salt
Acid：65~75 parts, sulfolane：5~15 parts.
The dilute hydrochloric acid is the hydrochloric acid selected from mass percent 10%.
The reactor be with stirring, thermometer, condensation reflux device three-necked flask.
Advantageous effect
Polyether-ether-ketone base lithium battery diaphragm is prepared by five step reaction steps in the present invention, and first is used wherein in step 1
Chlorosulfonation fluorine one monomers are obtained by the reaction with chlorosulfonic acid in base sulfonic acid chloride jointly, and by introducing chlorosulfonic groups, diaphragm is to electrolyte
Wellability is improved, while has certain hydratability, plays the role of moisturizing；Polyvinyl chloride is used in step 3
As fenestra high temperature closure agent, by the processing of step 5, the separator product of preparation produces more uniform micropore, has certain
Aperture and porosity, ensure that relatively low resistance and high ionic conductivity, ensure be isolated electrolyte while, utilize chlorine
Sulfonation group is effectively conducted lithium ion.
The polyether-ether-ketone base lithium battery diaphragm being prepared by the method for the present invention, there is following performance：First, there is electronic isolation
Property ensures the mechanical isolation of positive and negative anodes：This is because the reason of polyether-ether-ketone backbone structure, insulating properties and mechanical strength compared with
Height, while this kind of material is insulator, can effectively achieve the purpose that prevent electron transfer, and two, electrolyte resistance corrosion, have enough
Chemistry and electrochemical stability；3rd, there is preferable mechanical property, which has extraordinary mechanical property, stretches, is curved
The performances such as bent, compression are higher, and main cause is with caused by macromolecular benzene ring structure；It 4th, can be as required to the thickness of film
Degree is adjusted, can be by film preparation into the product of different-thickness according to solution viscosity is different and the variation of mold；5th, space
Stability and planarization are good：Spatial configuration of molecules is more regular, and molding shrinkage is vertically and horizontally preferable；6th, it is hot
Stability and to automatically shut down protective value good：Since there is this kind of structural polyether ether ketone higher fusing point and relatively low vitrifying to turn
Temperature, in the case where battery temperature is excessively high, diaphragm can be viscoelastic state from Solid State Transformation, when temperature continues to increase, viscoelastic state
Flowing state transition can occur, most microcellular structure is closed at last, is finally reached the purpose of shutdown protection, to the safe handling of battery more
Favorably.
Description of the drawings
Fig. 1：20 μm of resolution scanning maps of diaphragm prepared by the present invention.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is described in further detail.It should be appreciated that specific embodiment described herein does not limit only to explain the present invention
In the present invention.
Embodiment 1：
1st, chlorosulfonation fluorine one monomers synthesize
By 4,4 ,-difluoro benzophenone (20 parts), methylsufonyl chloride (25 parts), chlorosulfonic acid (55 parts) are put into stirring
It mixes, in the three-necked flask of thermometer, condensation reflux device, is persistently stirred under room temperature, stir 60min；System is warming up to 55 DEG C,
Persistently stir 120min, after complete reaction, reaction product is filtered and deionized water washing after, obtain chlorosulfonation fluorine ketone crystalline substance
Body；
2nd, sulfonated polyether-ether-ketone synthesizes
Equipped with blender, thermometer, condensation reflux device three-necked flask in, add in step 1 in chlorosulfonation monomer (5
Part), hydroquinone (5 parts), sodium carbonate (5 parts), sulfolane (85 parts), reacted under the sustainable protection of high pure nitrogen, rise
Temperature is to 120 DEG C, constant temperature 30min；After material is completely dissolved in system, unlatching agitating device, mixing speed 20r/min, then will
System temperature rises to 185 DEG C, constant temperature 300min；Finally reaction mass is poured into normal-temperature water and is cooled down, cooling material is thrown
Enter in high speed disintegrator, crushed, broken rear material, which is put into air dry oven, to be dried, dry under 105 DEG C of environment
60min；It is taken out after material completely cooling；
3rd, solution mixes
By the reaction mass (45 parts) of step 2, suspension type polyvinyl-chloride (5 parts), 500 mesh sodium carbonate (5 parts), dimethyl methyl
Amide (45 parts) puts into high speed agitator and carries out high-speed stirred, mixing speed 1200r/min, and continues to stir 60min；
4th, it forms a film, is dry
The pasty material of step 3 is poured on a glass, is put into air dry oven, it is dry in the environment of 65 DEG C
120min；
5th, pore-forming, drying
Material (15 parts) after step 4 is handled is immersed in 10% dilute hydrochloric acid (75 parts), sulfolane (10 parts), during immersion
Between 480min, the material that above-mentioned immersion is completed is taken out, is rinsed repeatedly using deionized water, up to flushing liquor pH=7 is
Only, the material after above-mentioned deionized water is rinsed, which is put into vacuum drying chamber, to be dried, 85 DEG C of drying temperature, drying time
180min。
Embodiment 2：
1st, chlorosulfonation fluorine one monomers synthesize
By 4,4 ,-difluoro benzophenone (25 parts), methylsufonyl chloride (25 parts), chlorosulfonic acid (50 parts) are put into stirring
It mixes, in the three-necked flask of thermometer, condensation reflux device, is persistently stirred under room temperature, stir 60min；System is warming up to 55 DEG C,
Persistently stir 120min, after complete reaction, reaction product is filtered and deionized water washing after, obtain chlorosulfonation fluorine ketone crystalline substance
Body；
2nd, sulfonated polyether-ether-ketone synthesizes
Equipped with blender, thermometer, condensation reflux device three-necked flask in, add in step 1 in chlorosulfonation monomer (10
Part), hydroquinone (10 parts), sodium carbonate (10 parts), sulfolane (70 parts), reacted under the sustainable protection of high pure nitrogen,
120 DEG C are warming up to, constant temperature 30min；After material is completely dissolved in system, unlatching agitating device, mixing speed 20r/min, then
System temperature is risen to 185 DEG C, constant temperature 300min；Finally reaction mass is poured into normal-temperature water and is cooled down, material will be cooled down
It puts into high speed disintegrator, is crushed, broken rear material, which is put into air dry oven, to be dried, and is done under 105 DEG C of environment
Dry 60min；It is taken out after material completely cooling；
3rd, solution mixes
By the reaction mass (50 parts) of step 2, suspension type polyvinyl-chloride (5 parts), 500 mesh sodium carbonate (5 parts), dimethyl methyl
Amide (40 parts) puts into high speed agitator and carries out high-speed stirred, mixing speed 1200r/min, and continues to stir 60min；
4th, it forms a film, is dry
The pasty material of step 3 is poured on a glass, is put into air dry oven, it is dry in the environment of 65 DEG C
120min；
5th, pore-forming, drying
Material (10 parts) after step 4 is handled is immersed in 10% dilute hydrochloric acid (75 parts), sulfolane (10 parts), during immersion
Between 480min, the material that above-mentioned immersion is completed is taken out, is rinsed repeatedly using deionized water, up to flushing liquor pH=7 is
Only.Material after above-mentioned deionized water is rinsed, which is put into vacuum drying chamber, to be dried, 85 DEG C of drying temperature, drying time
180min。
Embodiment 3：
1st, chlorosulfonation fluorine one monomers synthesize
By 4,4 ,-difluoro benzophenone (30 parts), methylsufonyl chloride (25 parts), chlorosulfonic acid (45 parts) are put into stirring
It mixes, in the three-necked flask of thermometer, condensation reflux device, is persistently stirred under room temperature, stir 60min；System is warming up to 55 DEG C,
Persistently stir 120min, after complete reaction, reaction product is filtered and deionized water washing after, obtain chlorosulfonation fluorine ketone crystalline substance
Body；
2nd, sulfonated polyether-ether-ketone synthesizes
Equipped with blender, thermometer, condensation reflux device three-necked flask in, add in step 1 in chlorosulfonation monomer (15
Part), hydroquinone (15 parts), sodium carbonate (10 parts), sulfolane (60 parts), reacted under the sustainable protection of high pure nitrogen,
120 DEG C are warming up to, constant temperature 30min；After material is completely dissolved in system, unlatching agitating device, mixing speed 20r/min, then
System temperature is risen to 185 DEG C, constant temperature 300min；Finally reaction mass is poured into normal-temperature water and is cooled down, material will be cooled down
It puts into high speed disintegrator, is crushed, broken rear material, which is put into air dry oven, to be dried, and is done under 105 DEG C of environment
Dry 60min；It is taken out after material completely cooling；
3rd, solution mixes
By the reaction mass (50 parts) of step 2, suspension type polyvinyl-chloride (10 parts), 500 mesh sodium carbonate (5 parts), dimethyl
Formamide (35 parts) puts into high speed agitator and carries out high-speed stirred, mixing speed 1200r/min, and continues to stir 60min；
4th, it forms a film, is dry
The pasty material of step 3 is poured on a glass, is put into air dry oven, it is dry in the environment of 65 DEG C
120min；
5th, pore-forming, drying
Material (15 parts) after step 4 is handled is immersed in 10% dilute hydrochloric acid (70 parts), sulfolane (15 parts), during immersion
Between 480min, the material that above-mentioned immersion is completed is taken out, is rinsed repeatedly using deionized water, up to flushing liquor pH=7 is
Only.Material after above-mentioned deionized water is rinsed, which is put into vacuum drying chamber, to be dried, 85 DEG C of drying temperature, drying time
180min。
Table 1：Membrane properties tables of data prepared by embodiment 1-3
Claims (8)
1. a kind of preparation method of polyether-ether-ketone base lithium battery diaphragm, it is characterised in that：Include the following steps：
(1) chlorosulfonation fluorine one monomers synthesize：
By 4,4 ,-difluoro benzophenone, methylsufonyl chloride, chlorosulfonic acid are put into reactor, are persistently stirred under room temperature, are stirred
Mix 30~60min；System is warming up to 55~65 DEG C, persistently stirs 120~150min, and after complete reaction, reaction product is passed through
After filter and deionized water washing, chlorosulfonation fluorine ketone crystal is obtained；
(2) sulfonated polyether-ether-ketone synthesizes：
Chlorosulfonation fluorine one monomers, hydroquinone, sodium carbonate, the sulfolane in step (1) are added in into reactor, in high pure nitrogen
Sustainable protection under reacted, be warming up to 120~130 DEG C, constant temperature 30min；After material is completely dissolved in system, unlatching is stirred
Device, 15~25r/min of mixing speed are mixed, then system temperature is risen to 180~190 DEG C, 300~360min of constant temperature；Finally will
Reaction mass is poured into normal-temperature water and is cooled down, and by cooling material input high speed disintegrator, is crushed, broken rear material is put
Enter in air dry oven and be dried, dry 60~90min under 100~105 DEG C of environment；It is taken out after material completely cooling,
Obtain sulfonated polyether-ether-ketone；
(3) solution mixes：
Reaction mass sulfonated polyether-ether-ketone, suspension type polyvinyl-chloride, sodium carbonate, the dimethylformamide of step (2) are put into
High speed agitator carries out high-speed stirred, 1100~1200r/min of mixing speed, and continues 60~120min of stirring, obtains pulpous state
Object；
(4) it forms a film, is dry：The pasty material of step (3) is poured on a glass, is put into air dry oven, 55~65
In the environment of DEG C, dry 60~120min；
(5) pore-forming, drying：By material after step (4) processing, it is immersed in dilute hydrochloric acid, in sulfolane mixed solution, soaking time
480~640min, the material that above-mentioned immersion is completed are taken out, are rinsed repeatedly using deionized water, until flushing liquor pH is 7
Until, the material after above-mentioned deionized water is rinsed, which is put into vacuum drying chamber, to be dried, and 85~95 DEG C of drying temperature is dry
180~240min of time obtains polyether-ether-ketone base diaphragm.
2. a kind of preparation method of polyether-ether-ketone base lithium battery diaphragm according to claim 1, it is characterised in that：Step
(1) proportioning of substance is as follows in：In terms of parts by weight, 4,4 ,-difluoro benzophenone：20~30 parts, methylsufonyl chloride：25~35
Part, chlorosulfonic acid：45~55 parts.
3. a kind of preparation method of polyether-ether-ketone base lithium battery diaphragm according to claim 1, it is characterised in that：Step
(2) proportioning of substance is as follows：In terms of parts by weight, chlorosulfonation fluorine one monomers：5~15 parts, hydroquinone：5~15 parts, carbonic acid
Sodium：5~10 parts, sulfolane：60~85 parts.
4. a kind of preparation method of polyether-ether-ketone base lithium battery diaphragm according to claim 1, it is characterised in that：Step
(3) proportioning of substance is as follows：In terms of parts by weight, sulfonated polyether-ether-ketone：45~55 parts, suspension type polyvinyl-chloride：5~10
Part, sodium carbonate：3~5 parts, dimethylformamide：35~45 parts.
5. a kind of preparation method of polyether-ether-ketone base lithium battery diaphragm according to claim 1 or 4, it is characterised in that：Step
Suddenly the sodium carbonate described in (3) is selected from 500~550 mesh.
6. a kind of preparation method of polyether-ether-ketone base lithium battery diaphragm according to claim 1, it is characterised in that：Step
(5) proportioning of the substance of reaction is as follows：In terms of parts by weight, material after step (4) processing：10~15 parts, dilute hydrochloric acid：65~75
Part, sulfolane：5~15 parts.
7. a kind of preparation method of polyether-ether-ketone base lithium battery diaphragm according to claim 1 or 6, it is characterised in that：Institute
The dilute hydrochloric acid stated is the hydrochloric acid selected from mass percent 10%.
8. a kind of preparation method of polyether-ether-ketone base lithium battery diaphragm according to claim 1, it is characterised in that：Described
Reactor be with stirring, thermometer, condensation reflux device three-necked flask.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711273783.0A CN108258170B (en) | 2017-12-05 | 2017-12-05 | Preparation method of polyether-ether-ketone-based lithium battery diaphragm |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711273783.0A CN108258170B (en) | 2017-12-05 | 2017-12-05 | Preparation method of polyether-ether-ketone-based lithium battery diaphragm |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108258170A true CN108258170A (en) | 2018-07-06 |
| CN108258170B CN108258170B (en) | 2021-07-16 |
Family
ID=62721125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711273783.0A Active CN108258170B (en) | 2017-12-05 | 2017-12-05 | Preparation method of polyether-ether-ketone-based lithium battery diaphragm |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108258170B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110265714A (en) * | 2019-06-10 | 2019-09-20 | 中国地质大学（武汉） | A kind of Ionomer electrolyte and its preparation method and application |
| CN110323390A (en) * | 2019-07-10 | 2019-10-11 | 哈尔滨理工大学 | A kind of new method preparing high heat resistance high intensity battery diaphragm |
| CN114243205A (en) * | 2021-11-19 | 2022-03-25 | 惠州锂威新能源科技有限公司 | Diaphragm, preparation method thereof and electrochemical device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999067304A1 (en) * | 1998-06-25 | 1999-12-29 | E.I. Du Pont De Nemours And Company | Aromatic polymers with pendant fluorinated ionic groups |
| CN1440438A (en) * | 2000-05-19 | 2003-09-03 | 斯图加特大学化工研究所 | Polymers and polymer membranes covalently cross-linked sulphinate alkylation |
| CN1556100A (en) * | 2003-12-30 | 2004-12-22 | 吉林大学 | Sulfonated monomer, polymer and its synthesis method |
| CN102071485A (en) * | 2010-12-06 | 2011-05-25 | 北京化工大学常州先进材料研究院 | Method for preparing nanofiber containing pore structure |
| CN105085847A (en) * | 2014-05-23 | 2015-11-25 | 中国科学院宁波材料技术与工程研究所 | Aromatic polymer sulfonamide, and preparation method and application thereof |
-
2017
- 2017-12-05 CN CN201711273783.0A patent/CN108258170B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999067304A1 (en) * | 1998-06-25 | 1999-12-29 | E.I. Du Pont De Nemours And Company | Aromatic polymers with pendant fluorinated ionic groups |
| CN1440438A (en) * | 2000-05-19 | 2003-09-03 | 斯图加特大学化工研究所 | Polymers and polymer membranes covalently cross-linked sulphinate alkylation |
| CN1556100A (en) * | 2003-12-30 | 2004-12-22 | 吉林大学 | Sulfonated monomer, polymer and its synthesis method |
| CN102071485A (en) * | 2010-12-06 | 2011-05-25 | 北京化工大学常州先进材料研究院 | Method for preparing nanofiber containing pore structure |
| CN105085847A (en) * | 2014-05-23 | 2015-11-25 | 中国科学院宁波材料技术与工程研究所 | Aromatic polymer sulfonamide, and preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110265714A (en) * | 2019-06-10 | 2019-09-20 | 中国地质大学（武汉） | A kind of Ionomer electrolyte and its preparation method and application |
| CN110323390A (en) * | 2019-07-10 | 2019-10-11 | 哈尔滨理工大学 | A kind of new method preparing high heat resistance high intensity battery diaphragm |
| CN114243205A (en) * | 2021-11-19 | 2022-03-25 | 惠州锂威新能源科技有限公司 | Diaphragm, preparation method thereof and electrochemical device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108258170B (en) | 2021-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wu et al. | A sustainable chitosan-zinc electrolyte for high-rate zinc-metal batteries | |
| Yan et al. | In situ polymerization permeated three‐dimensional Li+‐percolated porous oxide ceramic framework boosting all solid‐state lithium metal battery | |
| Yu et al. | Selectively wetted rigid–flexible coupling polymer electrolyte enabling superior stability and compatibility of high‐voltage lithium metal batteries | |
| CN103531736B (en) | A kind of high heat-resisting lithium ion battery separator and preparation method thereof | |
| Li et al. | Enhancing the selectivity of Nafion membrane by incorporating a novel functional skeleton molecule to improve the performance of direct methanol fuel cells | |
| CN108258170A (en) | A kind of preparation method of polyether-ether-ketone base lithium battery diaphragm | |
| Wang et al. | Composite polymer electrolyte with three-dimensional ion transport channels constructed by NaCl template for solid-state lithium metal batteries | |
| Wu et al. | A novel electrospun TPU/PVdF porous fibrous polymer electrolyte for lithium ion batteries | |
| Lu et al. | Inorganic-organic gel electrolytes with 3D cross-linking star-shaped structured networks for lithium ion batteries | |
| CN110676509B (en) | Room-temperature solid polymer electrolyte and preparation method thereof, electrode/electrolyte composite and preparation method and application thereof | |
| CN102593403B (en) | Diaphragm for high thermal safety temperature lithium ion cell and preparation method thereof | |
| CN107394240B (en) | Preparation method and application of sulfonated polyaryletherketone ion exchange membrane | |
| Amarilla et al. | Antimonic acid and sulfonated polystyrene proton-conducting polymeric composites | |
| CN106450445B (en) | Based on fluorinated polyimide polymer dielectric and its preparation method and application | |
| Hu et al. | Hydroxyl-rich single-ion conductors enable solid hybrid polymer electrolytes with excellent compatibility for dendrite-free lithium metal batteries | |
| Tan et al. | Flexible, high-wettability and thermostable separator based on fluorinated polyimide for lithium-ion battery | |
| CN109037766A (en) | A kind of biodegradable composite solid electrolyte film and preparation method thereof | |
| Jia et al. | Multifunctional polymer bottlebrush-based gel polymer electrolytes for lithium metal batteries | |
| Liu et al. | A novel polyacrylonitrile-based porous structure gel polymer electrolyte composited by incorporating polyhedral oligomeric silsesquioxane by phase inversion method | |
| Yang et al. | A highly proton-/vanadium-selective perfluorosulfonic acid membrane for vanadium redox flow batteries | |
| Wang et al. | High-rate solid polymer electrolyte based flexible all-solid-state lithium metal batteries | |
| JP2002184427A (en) | Proton conductive substance | |
| Zhou et al. | A Gel Polymer Electrolyte with 2D Filler‐reinforced for Dendrite Suppression Li‐Ion Batteries | |
| CN109301133A (en) | A kind of diaphragm preparation method for high security, lithium ion battery with high energy density | |
| CN105932330B (en) | Solid polymer electrolyte and preparation method thereof |
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 |