CN108832057A - A kind of septum for lithium ion battery and preparation method thereof - Google Patents
A kind of septum for lithium ion battery and preparation method thereof Download PDFInfo
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- CN108832057A CN108832057A CN201810633137.9A CN201810633137A CN108832057A CN 108832057 A CN108832057 A CN 108832057A CN 201810633137 A CN201810633137 A CN 201810633137A CN 108832057 A CN108832057 A CN 108832057A
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- lithium ion
- septum
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
-
- 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
-
- 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 present invention provides a kind of preparation methods of septum for lithium ion battery, first by sulfuryl polyethers amide, 3- (3- phenylsulfamoyl benzene) acrylic acid, surface modification polypyrrole pipe, vinyl-POSS, 2- trifluoromethyl acrylonitrile, nanometer calcium carbonate, polyethyleneimine, initiator in mass ratio 2:1:0.5:0.3:1:0.1:0.3:(0.03-0.05) is uniformly mixed, and through molten crowded and heat setting process, septum for lithium ion battery is made by pickling, ion exchange afterwards.The method of the present invention is simple and easy, not high to device dependence, and lithium battery diaphragm obtained has the advantages that low in cost, good, good stability, high temperature resistance be excellent to electrolyte wetability, lithium ion conductivity is big.
Description
Technical field
The invention belongs to novel energy resource material technology fields, are related to a kind of lithium cell component, specifically, being related to a kind of lithium electricity
Pond diaphragm and preparation method thereof.
Background technique
Lithium battery the advantages that having extended cycle life, is widely used in portable electronic device, power due to energy density height
The fields such as battery and energy-storage battery.It is mainly made of positive/negative material, electrolyte, diaphragm and battery case packaging material.
Diaphragm is the important component of lithium ion battery, plays separation positive and negative electrode, prevents internal short-circuit of battery, allow electrolyte from
Son passes freely through, and completes the effect of charge discharge process.Its performance determines the interfacial structure of battery, internal resistance etc., directly
The characteristics such as capacity, cycle performance and the security performance of battery are influenced, the diaphragm haveing excellent performance is to the comprehensive performance for improving battery
It plays an important role, " the third electrode " of battery is known as by industry.
Currently, the lithium battery diaphragm of commercialization is mainly independent as the MIcroporous polyolefin film of material using polyethylene and polypropylene
Or mixture composition.However the fusing point of these conventional polyolefins diaphragms is lower, when using these traditional polyalkene diaphragms, due to
In the presence of overcharge with high power discharge phenomenon, will lead to local diaphragm temperature it is excessively high so that inside battery be heat-shrinked, cause electricity
Pond positive and negative anodes contact short circuit；In addition, polyolefins diaphragm itself is poor to electrolyte wetability, imbibition rate is not high, to influence
The cycle performance of battery.
Chinese invention patent notification number is that CN102529247B discloses a kind of inorganic/organic composite polypropylene non-woven fabric base
Lithium battery diaphragm and preparation method thereof.The inorganic/organic composite porous lithium battery diaphragm by substrate layer and is arranged in substrate
The inorganic/organic composite porous film layer of layer surface is constituted, and the substrate layer is polypropylene non-woven fabric；Inorganic/the organic composite
Porous membrane layer is Kynoar-hexafluoropropylene copolymer containing inorganic nano-particle and hydrophilic agent, the inorganic nano-particle
Son is Nano particles of silicon dioxide or coupling agent modified Nano particles of silicon dioxide, foregoing invention is inorganic/organic composite poly- third
Alkene nonwoven fabric base lithium battery diaphragm guarantee high ionic conductivity, excellent electrochemical performance,
While high mechanical strength and low heat shrinkage, the production cost of lithium battery diaphragm is reduced.But the diaphragm
Material is only capable of playing the role of obstructing electronics, cannot achieve and combine with the lithium ion in electrolyte, diversion sub-feature is inevitable
It will receive influence.
Therefore, it develops a kind of with higher lithium ion conductivity, superior thermal stability, chemical stability and electrification
Stability is learned, keeps the septum for lithium ion battery of height wellability and more preferably mechanical performance during repeated charge to electrolyte
It is imperative.
Summary of the invention
In order to overcome the defects of the prior art, the present invention is intended to provide a kind of septum for lithium ion battery and preparation method thereof,
Preparation method is simple for this, and raw material is easy to get, cheap, little to device dependence, is suitble to industrialized production；By described
The septum for lithium ion battery that preparation method is prepared overcomes expensive, fusing point existing for conventional membrane material in the prior art
Lower, poor to electrolyte wetability, imbibition rate is not high, influences the defect of the cycle performance of battery, have it is low in cost, to electricity
Solve that liquid wetability is good, good stability, the advantage that high temperature resistance is excellent, lithium ion conductivity is big.
The invention is realized by the following technical scheme：A kind of preparation method of septum for lithium ion battery, includes the following steps：
I under nitrogen or atmosphere of inert gases, and by furans -2,3- dicarboxylic acids and butadiene -2,2,5,5-D4 sulfones are added to
Equipped with reflux condensing tube, electric mixer there-necked flask in, then organic solvent is added into bottle, flows back and stir at 120-130 DEG C
Reaction 4-6 hours is mixed, solvent is evaporated off in back spin, obtains intermediate product A.
Intermediate product A, 4,4'- diaminodiphenyl ether being prepared by step I is dissolved in shape in high boiling solvent by II
At solution, then into solution be added ionic liquid, 1,4-naphthoquinone, be placed in autoclave, after in 200-210 DEG C, pressure
Be maintained at 2-2.2MPa, be stirred to react 5-7h, after continue at 1-1.2MPa, 210-220 DEG C of temperature instead in nitrogen atmosphere pressure
Answer 10-15h, after settle out in water, with ethanol washing 5-7 times, be placed at 95-105 DEG C of vacuum oven and dry 15-24 hours,
Obtain sulfuryl polyethers amide；
III disperses polypyrrole pipe in ethyl alcohol, 2- chloracrylic acid ethyl ester, basic catalyst is then added thereto, in room
It is stirred to react under temperature 10-12 hours, it is rear to filter, and washed 3-5 times with methylene chloride, finally revolving removes methylene chloride, obtains table
Polypyrrole pipe is modified in face；
IV sulfuryl polyethers amide, 3- (3- phenylsulfamoyl benzene) acrylic acid, process that will be prepared by step II
Surface modification polypyrrole pipe that step III is prepared, vinyl-POSS, 2- trifluoromethyl acrylonitrile, nanometer calcium carbonate, poly- second
Alkene imines, initiator are uniformly mixed, and finally obtain composite membrane with heat setting process through molten squeeze；
V is immersed in composite membrane made from step IV 50- in the hydrochloric acid solution that mass fraction at 50-60 DEG C is 10-15%
60 hours, after be rinsed with water film to eluent and be in neutrality, then be immersed in the chlorine that mass fraction at 50-60 DEG C is 10-20%
Change 30-40 hours progress ion exchanges in lithium solution, takes out be washed with deionized water 3-5 times later, place into 80-90 DEG C of vacuum
Drying box dries 6-8 hours.
Preferably, furans -2,3- dicarboxylic acids described in step I, butadiene -2,2, the quality of 5,5-D4 sulfones, organic solvent
Than being 1.32:1:(5-8).
Preferably, the inert gas is selected from one or more of helium, neon, argon gas；The organic solvent is selected from
One or more of acetonitrile, acetone, ethyl acetate, tetrahydrofuran.
Preferably, intermediate product A described in step II, 4,4'- diaminodiphenyl ether, high boiling solvent, ionic liquid, 1,
The mass ratio of 4- naphthoquinones is 1.37:1:(5-8):(0.5-0.8):(0.1-0.3).
Preferably, the high boiling solvent is in dimethyl sulfoxide, n,N-Dimethylformamide, N-Methyl pyrrolidone
It is one or more of；The ionic liquid is selected from four butyl bromation amine, 1-butyl-3-methylimidazolium bromide, N- methyl, butyl pyrroles
One or more of alkane bis-trifluoromethylsulfoandimide salt.
Preferably, polypyrrole pipe described in step III, ethyl alcohol, 2- chloracrylic acid ethyl ester, basic catalyst mass ratio be
(3-4):(10-15):1:(0.3-0.5)。
Preferably, the basic catalyst is several selected from one of sodium hydroxide, potassium carbonate, potassium hydroxide, sodium carbonate.
Preferably, the amide of sulfuryl polyethers described in step IV, 3- (3- phenylsulfamoyl benzene) acrylic acid, surface modification are poly-
Pyrroles's pipe, vinyl-POSS, 2- trifluoromethyl acrylonitrile, nanometer calcium carbonate, polyethyleneimine, initiator mass ratio be 2:
1:0.5:0.3:1:0.1:0.3:(0.03-0.05)。
Preferably, the initiator is selected from one or more of azodiisobutyronitrile, azobisisoheptonitrile.
Preferably, the molten extruding process temperature is 290-350 DEG C, the temperature of heat setting process is 180-240 DEG C, when sizing
Between be 40-50min.
Preferably, composite membrane described in step V, hydrochloric acid solution, lithium chloride solution mass ratio be 1:(30-40):(50-
60)。
A kind of septum for lithium ion battery is prepared using the preparation method of septum for lithium ion battery as described above.
A kind of lithium battery, using the septum for lithium ion battery as diaphragm.
Generated beneficial effect is by adopting the above technical scheme：
1) septum for lithium ion battery provided by the invention, preparation method is simple, and raw material is easy to get, cheap, to equipment
Dependence is little, is suitble to industrialized production.
2) it is high to overcome price existing for conventional membrane material in the prior art for septum for lithium ion battery provided by the invention
Expensive, fusing point is lower, poor to electrolyte wetability, and imbibition rate is not high, influences the defect of the cycle performance of battery, has at low cost
Advantage honest and clean, good, good stability, high temperature resistance are excellent to electrolyte wetability, lithium ion conductivity is big.
3) septum for lithium ion battery provided by the invention is mixed using the structure polyamide polymer of polyarylether containing sulfuryl with monomer
Afterwards, then polyaddition reaction occurs, forms three-dimensional net structure, be conducive to the stability, mechanical property and the weatherability that improve film.
POSS, polypyrrole pipe structure are introduced by polymerization, and the modification of polypyrrole pipe surface makes its lotus positive electricity again, forms specific lithium ion
Channel is conducive to the conduction of lithium ion, in addition introduces polyethyleneimine in diaphragm, can be positive electricity lithium with positive electricity feature
Ion provides clear passage, and in addition it is conducive to keep electrolyte during film repeated charge with preferable affinity
Height wellability forms compact-sized, Mechanics of Machinery secondly, being conducive to interact between each ingredient by gantry after being added
Performance, high temperature resistance, excellent in stability lithium-ion membrane.
4) septum for lithium ion battery provided by the invention occurs ion exchange by the carboxyl on strand and introduces lithium ion,
Lithium ion polymer is formed, the lithium ion conduction ability for further increasing diaphragm is conducive to.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, and make features described above of the invention,
Purpose and advantage are more clear understandable, and the present invention will be further explained with reference to the examples below.Embodiment is only used for
It is bright the present invention rather than limit the scope of the invention.
The present invention polypyrrole pipe as used in the following examples is previously prepared, preparation method reference：Peng Yingjing,
The preparation of polypyrrole nanotube Pt based nano composite material and its research of catalytic performance, University Of Suzhou, 2013；The purchase of other raw materials
From in upper Haiquan sunrise foreign trade Co., Ltd.
Embodiment 1
A kind of preparation method of septum for lithium ion battery, includes the following steps：
I under nitrogen atmosphere, and by furans -2,3- dicarboxylic acids 13.2g and butadiene -2,2,5,5-D4 sulfone 10g are added to dress
In the there-necked flask for having reflux condensing tube, electric mixer, then acetonitrile 50g is added into bottle, reflux is stirred to react 4 at 120 DEG C
Hour, back spin is evaporated off acetonitrile, obtains intermediate product A；
Intermediate product A13.7g, 4,4'- diaminodiphenyl ether 10g being prepared by step I is dissolved in diformazan Asia by II
Solution is formed in sulfone 50g, then four butyl bromation amine 5g, 1,4-naphthoquinone 1g are added into solution, is placed in autoclave, after
Be maintained at 2MPa in 200 DEG C, pressure, be stirred to react 5h, after in nitrogen atmosphere pressure, the reaction was continued at 1MPa, 210 DEG C of temperature
10h, after settle out in water, with ethanol washing 5 times, be placed at 95 DEG C of vacuum oven and dry 15 hours, obtain sulfuryl polyethers
Amide；
III disperses polypyrrole pipe 30g in ethyl alcohol 100g, and 2- chloracrylic acid ethyl ester 10g, hydrogen-oxygen are then added thereto
Change sodium 3g, reaction 10 hours is stirred at room temperature, it is rear to filter, and washed 3 times with methylene chloride, finally revolving removes methylene chloride,
Obtain surface modification polypyrrole pipe；
IV sulfuryl polyethers amide 20g, 3- (3- phenylsulfamoyl benzene) acrylic acid that will be prepared by step II
10g, the surface modification polypyrrole pipe 5g being prepared by step III, vinyl-POSS3g, 2- trifluoromethyl acrylonitrile 10g,
Nanometer calcium carbonate 1g, polyethyleneimine 3g, azodiisobutyronitrile 0.3g are uniformly mixed, and are finally obtained through molten squeeze with heat setting process
Composite membrane；The molten extruding process temperature is 290 DEG C, and the temperature of heat setting process is 180 DEG C, setting time 40min.
V is immersed in composite membrane 20g made from step IV 50 in the hydrochloric acid solution 600g that mass fraction is 10% at 50 DEG C
Hour, after be rinsed with water film to eluent and be in neutrality, then be immersed in the lithium chloride solution that mass fraction is 10% at 50 DEG C
30 hours progress ion exchanges in 1000g are taken out be washed with deionized water 3 times later, and it is small to place into 80 DEG C of vacuum oven baking 6
When.
A kind of septum for lithium ion battery is prepared using the preparation method of septum for lithium ion battery as described above.
A kind of lithium battery, using the septum for lithium ion battery as diaphragm.
Using septum for lithium ion battery made from the above method, through detecting, surface lithium ion conductivity is 7.9 × 10-3S·
cm-1。
Embodiment 2
A kind of preparation method of septum for lithium ion battery, includes the following steps：
I under helium atmosphere, and by furans -2,3- dicarboxylic acids 13.2g and butadiene -2,2,5,5-D4 sulfone 10g are added to dress
In the there-necked flask for having reflux condensing tube, electric mixer, then acetone 60g is added into bottle, flows back and be stirred to react at 122 DEG C
4.5 hours, acetone was evaporated off in back spin, obtained intermediate product A；
Intermediate product A13.7g, 4,4'- diaminodiphenyl ether 10g being prepared by step I is dissolved in N, N- bis- by II
Solution is formed in methylformamide 60g, then 1-butyl-3-methylimidazolium bromide 6g, 1,4-naphthoquinone 1.5g are added into solution, and
Be placed in autoclave, after in 202 DEG C, pressure be maintained at 2.1MPa, be stirred to react 5.5h, after exist in nitrogen atmosphere pressure
1.1MPa, the reaction was continued at 212 DEG C of temperature 11h, after settle out in water, with ethanol washing 6 times, be placed on 98 DEG C of vacuum oven
It is lower to dry 16 hours, obtain sulfuryl polyethers amide；
III disperses polypyrrole pipe 32g in ethyl alcohol 120g, and 2- chloracrylic acid ethyl ester 10g, carbonic acid are then added thereto
Reaction 10.5 hours is stirred at room temperature in potassium 3.5g, rear to filter, and is washed 4 times with methylene chloride, and finally revolving removes dichloromethane
Alkane obtains surface modification polypyrrole pipe；
IV sulfuryl polyethers amide 20g, 3- (3- phenylsulfamoyl benzene) acrylic acid that will be prepared by step II
10g, the surface modification polypyrrole pipe 5g being prepared by step III, vinyl-POSS3g, 2- trifluoromethyl acrylonitrile 10g,
Nanometer calcium carbonate 1g, polyethyleneimine 3g, azobisisoheptonitrile 0.35g are uniformly mixed, and are finally obtained through molten squeeze with heat setting process
Obtain composite membrane；The molten extruding process temperature is 300 DEG C, and the temperature of heat setting process is 200 DEG C, setting time 43min.
V is immersed in composite membrane 20g made from step IV 53 in the hydrochloric acid solution 650g that mass fraction is 12% at 53 DEG C
Hour, after be rinsed with water film to eluent and be in neutrality, then be immersed in the lithium chloride solution that mass fraction is 14% at 54 DEG C
34 hours progress ion exchanges in 1080g are taken out be washed with deionized water 4 times later, place into 84 DEG C of vacuum oven and dry 6.5
Hour.
A kind of septum for lithium ion battery is prepared using the preparation method of septum for lithium ion battery as described above.
A kind of lithium battery, using the septum for lithium ion battery as diaphragm.
Using septum for lithium ion battery made from the above method, through detecting, surface lithium ion conductivity is 8.3 × 10-3S·
cm-1。
Embodiment 3
A kind of preparation method of septum for lithium ion battery, includes the following steps：
I under neon atmosphere, and by furans -2,3- dicarboxylic acids 13.2g and butadiene -2,2,5,5-D4 sulfone 10g are added to dress
In the there-necked flask for having reflux condensing tube, electric mixer, then ethyl acetate 65g is added into bottle, is refluxed at 125 DEG C anti-
It answers 5 hours, ethyl acetate is evaporated off in back spin, obtains intermediate product A.
Intermediate product A13.7g, 4,4'- diaminodiphenyl ether 10g being prepared by step I is dissolved in N- methyl by II
Solution is formed in pyrrolidones 70g, then the addition N- methyl into solution, butyl pyrrolidine bis-trifluoromethylsulfoandimide salt 7g, 1,
4- naphthoquinones 2g, is placed in autoclave, after in 205 DEG C, pressure be maintained at 2.2MPa, be stirred to react 6.1h, after in nitrogen
Atmosphere pressure the reaction was continued at 1.2MPa, 216 DEG C of temperature 13h, after settle out in water, with ethanol washing 6 times, be placed on vacuum
It is dried 19 hours at 100 DEG C of drying box, obtains sulfuryl polyethers amide；
III disperses polypyrrole pipe 36g in ethyl alcohol 132g, and 2- chloracrylic acid ethyl ester 10g, hydrogen-oxygen are then added thereto
Change potassium 4.2g, reaction 11.2 hours is stirred at room temperature, it is rear to filter, and washed 5 times with methylene chloride, finally revolving removes dichloromethane
Alkane obtains surface modification polypyrrole pipe；
IV sulfuryl polyethers amide 20g, 3- (3- phenylsulfamoyl benzene) acrylic acid that will be prepared by step II
10g, the surface modification polypyrrole pipe 5g being prepared by step III, vinyl-POSS3g, 2- trifluoromethyl acrylonitrile 10g,
Nanometer calcium carbonate 1g, polyethyleneimine 3g, azobisisoheptonitrile 0.42g are uniformly mixed, and are finally obtained through molten squeeze with heat setting process
Obtain composite membrane；The molten extruding process temperature is 320 DEG C, and the temperature of heat setting process is 220 DEG C, setting time 46min；
V is immersed in composite membrane 20g made from step IV 57 in the hydrochloric acid solution 740g that mass fraction is 13% at 57 DEG C
Hour, after be rinsed with water film to eluent and be in neutrality, then be immersed in the lithium chloride solution that mass fraction is 17% at 56 DEG C
37 hours progress ion exchanges in 1120g are taken out be washed with deionized water 5 times later, and it is small to place into 86 DEG C of vacuum oven baking 7
When.
A kind of septum for lithium ion battery is prepared using the preparation method of septum for lithium ion battery as described above.
A kind of lithium battery, using the septum for lithium ion battery as diaphragm.
Using septum for lithium ion battery made from the above method, through detecting, surface lithium ion conductivity is 8.6 × 10-3S·
cm-1。
Embodiment 4
A kind of preparation method of septum for lithium ion battery, includes the following steps：
I under argon atmosphere, and by furans -2,3- dicarboxylic acids 13.2g and butadiene -2,2,5,5-D4 sulfone 10g are added to dress
In the there-necked flask for having reflux condensing tube, electric mixer, then tetrahydrofuran 75g is added into bottle, is refluxed at 128 DEG C anti-
It answers 5.5 hours, tetrahydrofuran is evaporated off in back spin, obtains intermediate product A.
Intermediate product A13.7g, 4,4'- diaminodiphenyl ether 10g being prepared by step I is dissolved in diformazan Asia by II
Solution is formed in sulfone 75g, then four butyl bromation amine 7.5g, 1,4-naphthoquinone 2.5g are added into solution, is placed in autoclave
In, after in 208 DEG C, pressure be maintained at 2.2MPa, be stirred to react 6.5h, after in nitrogen atmosphere pressure in 1.2MPa, 218 DEG C of temperature
Lower the reaction was continued 14.5h, after settle out in water, with ethanol washing 7 times, be placed at 103 DEG C of vacuum oven and dry 23 hours, obtain
To sulfuryl polyethers amide；
III disperses polypyrrole pipe 38g in ethyl alcohol 145g, and 2- chloracrylic acid ethyl ester 10g, alkalinity are then added thereto
Reaction 11.5 hours is stirred at room temperature in catalyst 4.8g, rear to filter, and is washed 5 times with methylene chloride, and finally revolving removes dichloro
Methane obtains surface modification polypyrrole pipe；The basic catalyst is sodium hydroxide, potassium carbonate, potassium hydroxide, sodium carbonate by matter
Measure ratio 1:2:2:3 mixtures mixed；
IV sulfuryl polyethers amide 20g, 3- (3- phenylsulfamoyl benzene) acrylic acid that will be prepared by step II
10g, the surface modification polypyrrole pipe 5g being prepared by step III, vinyl-POSS3g, 2- trifluoromethyl acrylonitrile 10g,
Nanometer calcium carbonate 1g, polyethyleneimine 3g, initiator 0.45g are uniformly mixed, and are finally obtained through molten crowded and heat setting process compound
Film；The initiator is azodiisobutyronitrile, azobisisoheptonitrile in mass ratio 1:3 mixtures mixed；It is described molten crowded
Technological temperature is 340 DEG C, and the temperature of heat setting process is 230 DEG C, setting time 48min；
V is immersed in composite membrane 20g made from step IV 58 in the hydrochloric acid solution 760g that mass fraction is 14% at 58 DEG C
Hour, after be rinsed with water film to eluent and be in neutrality, then be immersed in the lithium chloride solution that mass fraction is 19% at 58 DEG C
39 hours progress ion exchanges in 1150g are taken out be washed with deionized water 5 times later, place into 88 DEG C of vacuum oven and dry 7.5
Hour.
A kind of septum for lithium ion battery is prepared using the preparation method of septum for lithium ion battery as described above.
A kind of lithium battery, using the septum for lithium ion battery as diaphragm.
Using septum for lithium ion battery made from the above method, through detecting, surface lithium ion conductivity is 8.9 × 10-3S·
cm-1。
Embodiment 5
A kind of preparation method of septum for lithium ion battery, includes the following steps：
I under nitrogen atmosphere, and by furans -2,3- dicarboxylic acids 13.2g and butadiene -2,2,5,5-D4 sulfone 10g are added to dress
In the there-necked flask for having reflux condensing tube, electric mixer, then tetrahydrofuran 80g is added into bottle, is refluxed at 130 DEG C anti-
It answers 6 hours, tetrahydrofuran is evaporated off in back spin, obtains intermediate product A.
Intermediate product A13.7g, 4,4'- diaminodiphenyl ether 10g being prepared by step I is dissolved in N, N- bis- by II
Solution is formed in methylformamide 80g, then ionic liquid 8g, 1,4-naphthoquinone 3g are added into solution, is placed in autoclave
In, after in 210 DEG C, pressure be maintained at 2.2MPa, be stirred to react 7h, after in nitrogen atmosphere pressure at 1.2MPa, 220 DEG C of temperature
The reaction was continued 15h, after settle out in water, with ethanol washing 7 times, be placed at 105 DEG C of vacuum oven and dry 24 hours, obtain sulfone
Base polyethers amide；The ionic liquid is four butyl bromation amine, 1-butyl-3-methylimidazolium bromide, N- methyl, butyl pyrroles
Alkane bis-trifluoromethylsulfoandimide salt in mass ratio 2:1:3 mixtures mixed；
III disperses polypyrrole pipe 40g in ethyl alcohol 150g, and 2- chloracrylic acid ethyl ester 10g, carbonic acid are then added thereto
Reaction 12 hours is stirred at room temperature in sodium 5g, rear to filter, and is washed 5 times with methylene chloride, and finally revolving removes methylene chloride, obtains
To surface modification polypyrrole pipe；
IV sulfuryl polyethers amide 20g, 3- (3- phenylsulfamoyl benzene) acrylic acid that will be prepared by step II
10g, the surface modification polypyrrole pipe 5g being prepared by step III, vinyl-POSS3g, 2- trifluoromethyl acrylonitrile 10g,
Nanometer calcium carbonate 1g, polyethyleneimine 3g, azodiisobutyronitrile 0.5g are uniformly mixed, and are finally obtained through molten squeeze with heat setting process
Composite membrane；The molten extruding process temperature is 350 DEG C, and the temperature of heat setting process is 240 DEG C, setting time 50min；
V is immersed in composite membrane 20g made from step IV 60 in the hydrochloric acid solution 800g that mass fraction is 15% at 60 DEG C
Hour, after be rinsed with water film to eluent and be in neutrality, then be immersed in the lithium chloride solution that mass fraction is 20% at 60 DEG C
40 hours progress ion exchanges in 1200g are taken out be washed with deionized water 5 times later, and it is small to place into 90 DEG C of vacuum oven baking 8
When.
A kind of septum for lithium ion battery is prepared using the preparation method of septum for lithium ion battery as described above.
A kind of lithium battery, using the septum for lithium ion battery as diaphragm.
Using septum for lithium ion battery made from the above method, through detecting, surface lithium ion conductivity is 9.3 × 10-3S·
cm-1。
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention
Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and
Improvement is both fallen in the range of claimed invention.The present invention claims protection scope by appended claims and its
Equivalent defines.
Claims (10)
1. a kind of preparation method of septum for lithium ion battery, which is characterized in that include the following steps：
I under nitrogen or atmosphere of inert gases, and by furans -2,3- dicarboxylic acids and butadiene -2,2,5,5-D4 sulfones, which are added to, to be equipped with
Reflux condensing tube, electric mixer there-necked flask in, then organic solvent is added into bottle, is refluxed at 120-130 DEG C anti-
It answers 4-6 hours, solvent is evaporated off in back spin, obtains intermediate product A；
II intermediate product A, 4,4'- diaminodiphenyl ether being prepared by step I is dissolved in high boiling solvent formed it is molten
Liquid, then into solution be added ionic liquid, 1,4-naphthoquinone, be placed in autoclave, after 200-210 DEG C, pressure keep
In 2-2.2MPa, be stirred to react 5-7h, after in nitrogen atmosphere pressure the reaction was continued at 1-1.2MPa, 210-220 DEG C of temperature 10-
15h, after settle out in water, with ethanol washing 5-7 times, be placed at 95-105 DEG C of vacuum oven and dry 15-24 hours, obtain sulfone
Base polyethers amide；
III disperses polypyrrole pipe in ethyl alcohol, 2- chloracrylic acid ethyl ester, basic catalyst is then added thereto, at room temperature
It is stirred to react 10-12 hours, it is rear to filter, and washed 3-5 times with methylene chloride, finally revolving removes methylene chloride, obtains to surface and repairs
Adorn polypyrrole pipe；
IV by the sulfuryl polyethers amide being prepared by step II, 3- (3- phenylsulfamoyl benzene) acrylic acid, by step
III surface modification polypyrrole pipe, vinyl-POSS, the 2- trifluoromethyl acrylonitrile, nanometer calcium carbonate, polyethyleneimine being prepared
Amine, initiator are uniformly mixed, and finally obtain composite membrane with heat setting process through molten squeeze；
V that composite membrane made from step IV is immersed in 50-60 in the hydrochloric acid solution that mass fraction at 50-60 DEG C is 10-15% is small
When, after be rinsed with water film to eluent and be in neutrality, then be immersed in the lithium chloride that mass fraction at 50-60 DEG C is 10-20%
30-40 hours progress ion exchanges in solution are taken out be washed with deionized water 3-5 times later, place into 80-90 DEG C of vacuum drying
Case dries 6-8 hours.
2. the preparation method of septum for lithium ion battery according to claim 1, which is characterized in that furans -2 described in step I,
3- dicarboxylic acids, butadiene -2,2,5,5-D4 sulfone, organic solvent mass ratio be 1.32:1:(5-8).
3. the preparation method of septum for lithium ion battery according to claim 1, which is characterized in that the inert gas is selected from helium
One or more of gas, neon, argon gas；The organic solvent in acetonitrile, acetone, ethyl acetate, tetrahydrofuran one
Kind is several.
4. the preparation method of septum for lithium ion battery according to claim 1, which is characterized in that intermediate described in step II to produce
Object A, 4,4'- diaminodiphenyl ether, high boiling solvent, ionic liquid, 1,4- naphthoquinones mass ratio be 1.37:1:(5-8):
(0.5-0.8):(0.1-0.3)。
5. the preparation method of septum for lithium ion battery according to claim 1, which is characterized in that the high boiling solvent is selected from
One or more of dimethyl sulfoxide, N,N-dimethylformamide, N-Methyl pyrrolidone；The ionic liquid is selected from the tetrabutyl
Amine bromide, 1-butyl-3-methylimidazolium bromide, N- methyl, one of butyl pyrrolidine bis-trifluoromethylsulfoandimide salt or several
Kind.
6. the preparation method of septum for lithium ion battery according to claim 1, which is characterized in that polypyrrole described in step III
Pipe, ethyl alcohol, 2- chloracrylic acid ethyl ester, basic catalyst mass ratio be (3-4):(10-15):1:(0.3-0.5)；The alkalinity
It is several that catalyst is selected from one of sodium hydroxide, potassium carbonate, potassium hydroxide, sodium carbonate.
7. the preparation method of septum for lithium ion battery according to claim 1, which is characterized in that sulfuryl described in step IV is poly-
Ethers amide, 3- (3- phenylsulfamoyl benzene) acrylic acid, surface modification polypyrrole pipe, vinyl-POSS, 2- trifluoromethyl propylene
Nitrile, nanometer calcium carbonate, polyethyleneimine, initiator mass ratio be 2:1:0.5:0.3:1:0.1:0.3:(0.03-0.05)；Institute
It states initiator and is selected from one or more of azodiisobutyronitrile, azobisisoheptonitrile.
8. the preparation method of septum for lithium ion battery according to claim 1, which is characterized in that the molten extruding process temperature is
290-350 DEG C, the temperature of heat setting process is 180-240 DEG C, setting time 40-50min；Composite membrane described in step V,
Hydrochloric acid solution, lithium chloride solution mass ratio be 1:(30-40):(50-60).
9. a kind of lithium battery that the preparation method using the described in any item septum for lithium ion battery of claim 1-8 is prepared is used
Diaphragm.
10. a kind of lithium battery using septum for lithium ion battery described in claim 9 as diaphragm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110600758A (en) * | 2019-10-24 | 2019-12-20 | 湖南辰砾新材料有限公司 | Fuel cell diaphragm and preparation method thereof |
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| CN104124417A (en) * | 2014-07-02 | 2014-10-29 | 上海大学 | A constitution method of a lithium ion battery diaphragm surface supermolecule membrane |
| EP2822084A4 (en) * | 2013-05-07 | 2016-01-13 | Lg Chemical Ltd | Cable-type secondary battery |
| CN106159161A (en) * | 2016-08-26 | 2016-11-23 | 先进储能材料国家工程研究中心有限责任公司 | A kind of septum for lithium ion battery and preparation method thereof |
| CN107978769A (en) * | 2017-11-19 | 2018-05-01 | 湖南辰砾新材料有限公司 | A kind of vanadium cell is used based on pyrrolotriazine derivatives membrane and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1269889A (en) * | 1997-09-02 | 2000-10-11 | 诺瓦提斯公司 | Process for mfg. of moulding |
| EP2822084A4 (en) * | 2013-05-07 | 2016-01-13 | Lg Chemical Ltd | Cable-type secondary battery |
| CN104124417A (en) * | 2014-07-02 | 2014-10-29 | 上海大学 | A constitution method of a lithium ion battery diaphragm surface supermolecule membrane |
| CN106159161A (en) * | 2016-08-26 | 2016-11-23 | 先进储能材料国家工程研究中心有限责任公司 | A kind of septum for lithium ion battery and preparation method thereof |
| CN107978769A (en) * | 2017-11-19 | 2018-05-01 | 湖南辰砾新材料有限公司 | A kind of vanadium cell is used based on pyrrolotriazine derivatives membrane and preparation method thereof |
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| CN110600758A (en) * | 2019-10-24 | 2019-12-20 | 湖南辰砾新材料有限公司 | Fuel cell diaphragm and preparation method thereof |
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