CN109873107A - The preparation process of new energy lithium ion battery separator - Google Patents
The preparation process of new energy lithium ion battery separator Download PDFInfo
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- CN109873107A CN109873107A CN201910205183.3A CN201910205183A CN109873107A CN 109873107 A CN109873107 A CN 109873107A CN 201910205183 A CN201910205183 A CN 201910205183A CN 109873107 A CN109873107 A CN 109873107A
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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
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- 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 preparation processes of new energy lithium ion battery separator, specific preparation process is as follows: polyethylene and high liquid sucting copolymer are added in stirred tank simultaneously, then repefral and polyethylene glycol are added thereto, it is warming up to 200 DEG C, it is uniformly mixed, two kinds of polymer is melted into molten condition at this time, obtains casting solution；The casting solution prepared in the first step is poured into mold, heating plate is sulfided into film；The perforated membrane of preparation is impregnated in imbibition foaming solution, rear foamed solidification is then pulled out, obtains battery diaphragm.The present invention prepares perforated membrane by merge with high liquid sucting copolymer polyethylene, then in the composite foamed film in the surface of perforated membrane and bottom surface, so that diaphragm forms three-layer sandwich structure, central mode imbibition liquid-keeping property with higher, the imbibition water retainability of the porous imbibition film of two layers of abscess greatly enhances, by three-layer sandwich structure, the water retainability of central mode can be improved, also improve the mechanical strength of diaphragm.
Description
Technical field
The invention belongs to lithium ion battery preparation fields, are related to a kind of preparation process of new energy lithium ion battery separator.
Background technique
Significant components one of of the diaphragm as lithium battery can allow lithium ion to pass through while obstruct positive and negative anodes, prevent short circuit,
The height of the absorbent of diaphragm influences the absorption of electrolyte simultaneously, since diaphragm is as ion channel, it is necessary to ensure electrolyte
Pass through, while the mechanical performance of diaphragm determines whether diaphragm will cause breakage, while the suction of diaphragm under rugged environment
Liquid water retainability and ionic conductivity；
The diaphragm of prior art preparation usually uses polythene material preparation, obtained diaphragm although machine with higher
Tool performance, but its imbibition water retainability is lower, while the thermal stability of polythene material at high temperature is poor, is not able to satisfy
Demand.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation process of new energy lithium ion battery separator, by by polyethylene with
High liquid sucting copolymer carries out fusion and prepares perforated membrane, then in the composite foamed film in the surface of perforated membrane and bottom surface, so that diaphragm has
High imbibition central mode and the porous imbibition film composition of two layers of abscess；Due to high liquid sucting copolymer absorbent with higher itself,
So that central mode imbibition liquid-keeping property with higher, while forming a large amount of abscess after foaming and increasing specific surface area,
And then imbibition area is increased, so that the imbibition water retainability of the porous imbibition film of two layers of abscess greatly enhances, pass through three-layer sandwich
The water retainability of central mode can be improved in structure, and three-decker also improves the mechanical strength of diaphragm, breaking strength simultaneously
Reach 52.13MPa, while imbibition rate reaches 286.31%, protects liquid rate and reach 92.23%, and then improve the circulation longevity of lithium battery
Life, solves the problems, such as that existing lithium battery diaphragm imbibition water retainability is lower.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation process of new energy lithium ion battery separator, specific preparation process are as follows:
Polyethylene and high liquid sucting copolymer are added in stirred tank simultaneously, O-phthalic are then added thereto by the first step
Dimethyl phthalate and polyethylene glycol are warming up to 200 DEG C, are uniformly mixed, and two kinds of polymer is smelted into molten condition at this time, obtains
To casting solution；Wherein the mass ratio of polyethylene and high liquid sucting copolymer is 1:3.2-3.3, is added in every kilogram of rutgers
The gross mass for entering polyethylene and high liquid sucting copolymer is 295-302g, and the quality that polyethylene glycol is added is 134-138g；
Wherein the preparation process of high liquid sucting copolymer is as follows:
1. weighing a certain amount of melamine to be dissolved in methanol, three hydroxyl first are added after then heating to 70-75 DEG C thereto
Base propane triglycidyl ether, 2,3- epoxypropyltrimethylchloride chloride is added after isothermal reaction 1h thereto, and constant temperature reflux is anti-
8-9h is answered, is then evaporated and removes solvent methanol therein, obtain polymer, while baking is washed with deionized in polymer
It is dry, obtain polymer；Wherein in melamine rings containing there are three amino, can in trihydroxymethylpropanyltri diglycidyl ether
Epoxy group carry out ring-opening polymerization, since three amino are evenly arranged on the different directions on ring, while trimethylolpropane
Three epoxy groups in triglycidyl ether are also evenly arranged on three different directions, are formed in the course of the polymerization process irregular super
Branched structure, while 2 being added in the course of the polymerization process, 3- epoxypropyltrimethylchloride chloride, 2,3- epoxypropyl trimethylammonium chlorides
Epoxy group in ammonium is also reacted with amino unreacted in melamine, so that ammonium chloride group introduces polymer
In skeleton, simultaneously because ammonium chloride hydrophilicity with higher, so that the hydrophilic moisture pick-up properties of the polymer of preparation increases
By force；Simultaneously because the polymer of preparation is polymerize by melamine monomer, so that polymer corrosion resistance with higher
Energy and heat resistance；Wherein the molar ratio of melamine and trihydroxymethylpropanyltri diglycidyl ether is 1:0.73-0.76, simultaneously
The molar ratio of melamine and 2,3- epoxypropyltrimethylchloride chloride is 1:0.28-0.29；
2. the polymer adding into acetone that will be prepared in the first step, sodium isethionate is then added thereto, is warming up to
50-60 DEG C is stirred 3-5min, and toluene di-isocyanate(TDI) is then added dropwise thereto, and constant temperature is stirred to react after being added dropwise completely
Then 6-7h is filtered washing and obtains high liquid sucting copolymer；Sodium isethionate 1.49- is wherein added in every gram of polymer
1.51g, while toluene di-isocyanate(TDI) 1.79-1.82g is added；Due to polymer the opening by amino and epoxy group of preparation
There is hydroxyl generation after ring reactive polymeric, amino and epoxy ring-opening, at this time the equal energy of hydroxyl in hydroxyl and sodium isethionate
It is enough to be reacted with the isocyanate groups in toluene di-isocyanate(TDI), it carries out so that sodium isethionate is grafted on polymer backbone
On, so that introducing sulfonate ion on polymer, and then improve the absorbent of polymer；
Second step pours into the casting solution prepared in the first step in mold, heating plate is sulfided into film, then by mold
It moves into cooling bath and cools and solidifies rapidly, then take out the film after solidifying and be put into ethyl alcohol and impregnate 24-26h, replaced by solvent
Rutgers and polyethylene glycol therein are removed, finally dry the composite membrane after immersion in 50-60 DEG C of drying room
It is dry, the ethyl alcohol wherein replaced is removed, porous composite film is obtained；
Third step, by the perforated membrane prepared in second step imbibition foaming solution in impregnate 1-2min, after then pulling out
Foamed solidification 5-6h, obtains battery diaphragm at 80-85 DEG C.
The preparation process of imbibition foaming solution is as follows: the high liquid sucting copolymer of preparation being added in isopropyl acetate, stirring
Dissolution, hydroxy silicon oil is then added thereto, is uniformly mixed, and pentane and Tween 80 are then added thereto, and mixing is equal
The sulfuric acid solution that concentration is 20% is added after even thereto, controlled at being uniformly mixed at 25-30 DEG C, obtains imbibition hair
Solution is steeped, wherein isopropyl acetate 8-10mL is added in every gram high liquid sucting copolymer, hydroxy silicon oil 0.21-0.23g is added, is added
Tween 80 quality is 0.09-0.1g, and pentane 0.09-0.11g is added, 20% sulfuric acid solution 0.11-0.13g is added；Due to
Imbibition foaming solution itself contains higher absorbent, forms foam structure on the surface of perforated membrane after foaming, not only will not
The blocking in perforated membrane gap is caused, while improving abscess quantity, and then increases specific surface area, improves imbibition water retention property, and
The hydroxy silicon oil contained in foamed material can be improved the corrosion resistance and thermal stability of diaphragm, while by perforated membrane
Two sides directly foam, due to perforated membrane imbibition water retention property with higher itself, and two layers of foam films all have it is higher
Absorbency, so that there is the diaphragm of preparation stronger inside and surface to all have higher imbibition water retention property.
Beneficial effects of the present invention:
The present invention prepares perforated membrane by merge with high liquid sucting copolymer polyethylene, then on the surface of perforated membrane
With the composite foamed film in bottom surface so that diaphragm is made of high imbibition central mode and the porous imbibition film of two layers of abscess；Since high imbibition is poly-
Object absorbent with higher itself is closed, so that central mode imbibition liquid-keeping property with higher, while the shape after foaming
Specific surface area is increased at a large amount of abscess, and then increases imbibition area, so that the imbibition of the porous imbibition film of two layers of abscess is protected
Fluidity can greatly enhance, and by three-layer sandwich structure, the water retainability of central mode can be improved, and three-decker also mentions simultaneously
The high mechanical strength of diaphragm, breaking strength reaches 52.13MPa, while imbibition rate reaches 286.31%, protects liquid rate and reaches
92.23%, and then improve the cycle life of lithium battery.
The present invention is carried out when preparing high liquid sucting copolymer by melamine rings and trihydroxymethylpropanyltri diglycidyl ether
Polymerization generates dissaving polymer, 2,3- epoxypropyltrimethylchloride chloride, 2,3- glycidyl three is added in the course of the polymerization process
Epoxy group in ammonio methacrylate is also reacted with amino unreacted in melamine, so that ammonium chloride group draws
Enter in polymer backbone, simultaneously because ammonium chloride hydrophilicity with higher, so that the hydrophilic suction of the polymer of preparation
Wet performance enhancing；Simultaneously because the polymer of preparation is polymerize by amino with the ring-opening reaction of epoxy group, amino and epoxy group
Have hydroxyl generation after open loop, at this time hydroxyl and the hydroxyl in sodium isethionate can with it is different in toluene di-isocyanate(TDI)
Cyanate group reaction, carries out so that sodium isethionate is grafted on polymer backbone, so that introducing sulfonate radical on polymer
Ion further improves the absorbent of polymer.
The present invention is by adding hydroxy silicon oil in imbibition foaming solution preparation process, so that containing big in surface blister film
The siloxanes key of amount, and then the high temperature resistance of foam films is improved, entire isolation film is realized by the barrier action of foam films
High temperature resistance, and then the thermal stability for solving existing polythene material is poor, the problem of being unable to meet demand.
Specific embodiment
Embodiment 1:
The preparation process of high liquid sucting copolymer is as follows:
1. weighing 1.26kg melamine to be dissolved in 12L methanol, 2.2kg is added after then heating to 70-75 DEG C thereto
0.42kg2,3- epoxypropyl trimethylammonium chloride is added after isothermal reaction 1h in trihydroxymethylpropanyltri diglycidyl ether thereto
Then ammonium, constant temperature back flow reaction 8-9h are evaporated and remove solvent methanol therein, obtain polymer；
2. the polymer prepared in the 1kg first step is added in 12L acetone, 1.49kg ethoxy sulphur is then added thereto
Sour sodium is warming up to 50-60 DEG C and is stirred 3-5min, and 1.79kg toluene di-isocyanate(TDI) is then added dropwise thereto, is added dropwise
Constant temperature is stirred to react 6-7h after completely, is then filtered washing and obtains high liquid sucting copolymer.
Embodiment 2:
The preparation process of high liquid sucting copolymer is as follows: weighing 1.26kg melamine and is dissolved in 12L methanol, then heats to
2.2kg trihydroxymethylpropanyltri diglycidyl ether is added after 70-75 DEG C thereto, is added thereto after isothermal reaction 1h
Then 0.42kg2,3- epoxypropyltrimethylchloride chloride, constant temperature back flow reaction 8-9h are evaporated and remove solvent first therein
Alcohol obtains polymer.
Embodiment 3:
A kind of preparation process of new energy lithium ion battery separator, specific preparation process are as follows:
The first step by high liquid sucting copolymer prepared by 1kg polyethylene and 3.2kg embodiment 1 while being added in stirred tank, so
14.24kg repefral and 1.91kg polyethylene glycol is added thereto afterwards, is warming up to 200 DEG C, is uniformly mixed,
Two kinds of polymer is smelted into molten condition at this time, obtains casting solution；
Second step pours into the casting solution prepared in the first step in mold, heating plate is sulfided into film, then by mold
It moves into cooling bath and cools and solidifies rapidly, then take out the film after solidifying and be put into ethyl alcohol and impregnate 24-26h, replaced by solvent
Rutgers and polyethylene glycol therein are removed, finally dry the composite membrane after immersion in 50-60 DEG C of drying room
It is dry, the ethyl alcohol wherein replaced is removed, porous composite film is obtained；
Third step, by the perforated membrane prepared in second step imbibition foaming solution in impregnate 1-2min, after then pulling out
Foamed solidification 5-6h, obtains battery diaphragm at 80-85 DEG C；Wherein the preparation process of imbibition foaming solution is as follows: by 1kg embodiment
The high liquid sucting copolymer of 1 preparation is added in 8L isopropyl acetate, then 0.21kg hydroxy silicon oil is added in stirring and dissolving thereto,
It is uniformly mixed, 0.09kg pentane and 0.09kg Tween 80 is then added thereto, is added thereto after mixing
The sulfuric acid solution that 0.11kg concentration is 20% obtains imbibition foaming solution controlled at being uniformly mixed at 25-30 DEG C.
Embodiment 4:
A kind of preparation process of new energy lithium ion battery separator, specific preparation process are as follows:
The first step by high liquid sucting copolymer prepared by 1kg polyethylene and 3.2kg embodiment 1 while being added in stirred tank, so
14.24kg repefral and 1.91kg polyethylene glycol is added thereto afterwards, is warming up to 200 DEG C, is uniformly mixed,
Two kinds of polymer is smelted into molten condition at this time, obtains casting solution；
Second step pours into the casting solution prepared in the first step in mold, heating plate is sulfided into film, then by mold
It moves into cooling bath and cools and solidifies rapidly, then take out the film after solidifying and be put into ethyl alcohol and impregnate 24-26h, replaced by solvent
Rutgers and polyethylene glycol therein are removed, finally dry the composite membrane after immersion in 50-60 DEG C of drying room
It is dry, the ethyl alcohol wherein replaced is removed, porous composite film is obtained；
Third step, by the perforated membrane prepared in second step imbibition foaming solution in impregnate 1-2min, after then pulling out
Foamed solidification 5-6h, obtains battery diaphragm at 80-85 DEG C；Wherein the preparation process of imbibition foaming solution is as follows: by 1kg embodiment
The high liquid sucting copolymer of 2 preparations is added in 8L isopropyl acetate, then 0.21kg hydroxy silicon oil is added in stirring and dissolving thereto,
It is uniformly mixed, 0.09kg pentane and 0.09kg Tween 80 is then added thereto, is added thereto after mixing
The sulfuric acid solution that 0.11kg concentration is 20% obtains imbibition foaming solution controlled at being uniformly mixed at 25-30 DEG C.
Embodiment 5:
A kind of preparation process of new energy lithium ion battery separator, specific preparation process are as follows:
The first step by high liquid sucting copolymer prepared by 1kg polyethylene and 3.2kg embodiment 2 while being added in stirred tank, so
14.24kg repefral and 1.91kg polyethylene glycol is added thereto afterwards, is warming up to 200 DEG C, is uniformly mixed,
Two kinds of polymer is smelted into molten condition at this time, obtains casting solution；
Second step pours into the casting solution prepared in the first step in mold, heating plate is sulfided into film, then by mold
It moves into cooling bath and cools and solidifies rapidly, then take out the film after solidifying and be put into ethyl alcohol and impregnate 24-26h, replaced by solvent
Rutgers and polyethylene glycol therein are removed, finally dry the composite membrane after immersion in 50-60 DEG C of drying room
It is dry, the ethyl alcohol wherein replaced is removed, porous composite film is obtained；
Third step, by the perforated membrane prepared in second step imbibition foaming solution in impregnate 1-2min, after then pulling out
Foamed solidification 5-6h, obtains battery diaphragm at 80-85 DEG C；Wherein the preparation process of imbibition foaming solution is as follows: by 1kg embodiment
The high liquid sucting copolymer of 2 preparations is added in 8L isopropyl acetate, then 0.21kg hydroxy silicon oil is added in stirring and dissolving thereto,
It is uniformly mixed, 0.09kg pentane and 0.09kg Tween 80 is then added thereto, is added thereto after mixing
The sulfuric acid solution that 0.11kg concentration is 20% obtains imbibition foaming solution controlled at being uniformly mixed at 25-30 DEG C.
Embodiment 6:
A kind of preparation process of new energy lithium ion battery separator, specific preparation process are as follows:
4kg polyethylene is added in stirred tank the first step, and 14.24kg repefral is then added thereto
With 1.91kg polyethylene glycol, 200 DEG C are warming up to, is uniformly mixed, two kinds of polymer is smelted into molten condition at this time, obtains
Casting solution；
Second step pours into the casting solution prepared in the first step in mold, heating plate is sulfided into film, then by mold
It moves into cooling bath and cools and solidifies rapidly, then take out the film after solidifying and be put into ethyl alcohol and impregnate 24-26h, replaced by solvent
Rutgers and polyethylene glycol therein are removed, finally dry the composite membrane after immersion in 50-60 DEG C of drying room
It is dry, the ethyl alcohol wherein replaced is removed, porous composite film is obtained；
Third step, by the perforated membrane prepared in second step imbibition foaming solution in impregnate 1-2min, after then pulling out
Foamed solidification 5-6h, obtains battery diaphragm at 80-85 DEG C；Wherein the preparation process of imbibition foaming solution is as follows: by 1kg embodiment
The high liquid sucting copolymer of 1 preparation is added in 8L isopropyl acetate, then 0.21kg hydroxy silicon oil is added in stirring and dissolving thereto,
It is uniformly mixed, 0.09kg pentane and 0.09kg Tween 80 is then added thereto, is added thereto after mixing
The sulfuric acid solution that 0.11kg concentration is 20% obtains imbibition foaming solution controlled at being uniformly mixed at 25-30 DEG C.
Embodiment 7:
A kind of preparation process of new energy lithium ion battery separator, specific preparation process are as follows:
The first step by high liquid sucting copolymer prepared by 4kg embodiment 1 while being added in stirred tank, is then added thereto
14.24kg repefral and 1.91kg polyethylene glycol, are warming up to 200 DEG C, are uniformly mixed, at this time two kinds of polymerizations
Object is smelted into molten condition, obtains casting solution；
Second step pours into the casting solution prepared in the first step in mold, heating plate is sulfided into film, then by mold
It moves into cooling bath and cools and solidifies rapidly, then take out the film after solidifying and be put into ethyl alcohol and impregnate 24-26h, replaced by solvent
Rutgers and polyethylene glycol therein are removed, finally dry the composite membrane after immersion in 50-60 DEG C of drying room
It is dry, the ethyl alcohol wherein replaced is removed, porous composite film is obtained；
Third step, by the perforated membrane prepared in second step imbibition foaming solution in impregnate 1-2min, after then pulling out
Foamed solidification 5-6h, obtains battery diaphragm at 80-85 DEG C；Wherein the preparation process of imbibition foaming solution is as follows: by 1kg embodiment
The high liquid sucting copolymer of 1 preparation is added in 8L isopropyl acetate, then 0.21kg hydroxy silicon oil is added in stirring and dissolving thereto,
It is uniformly mixed, 0.09kg pentane and 0.09kg Tween 80 is then added thereto, is added thereto after mixing
The sulfuric acid solution that 0.11kg concentration is 20% obtains imbibition foaming solution controlled at being uniformly mixed at 25-30 DEG C.
Embodiment 8:
A kind of preparation process of new energy lithium ion battery separator, specific preparation process are as follows:
The first step by high liquid sucting copolymer prepared by 1kg polyethylene and 3.2kg embodiment 1 while being added in stirred tank, so
14.24kg repefral and 1.91kg polyethylene glycol is added thereto afterwards, is warming up to 200 DEG C, is uniformly mixed,
Two kinds of polymer is smelted into molten condition at this time, obtains casting solution；
Second step pours into the casting solution prepared in the first step in mold, heating plate is sulfided into film, then by mold
It moves into cooling bath and cools and solidifies rapidly, then take out the film after solidifying and be put into ethyl alcohol and impregnate 24-26h, replaced by solvent
Rutgers and polyethylene glycol therein are removed, finally dry the composite membrane after immersion in 50-60 DEG C of drying room
It is dry, the ethyl alcohol wherein replaced is removed, porous composite film, as battery diaphragm are obtained.
Embodiment 9:
A kind of preparation process of new energy lithium ion battery separator, specific preparation process are as follows:
The first step by high liquid sucting copolymer prepared by 1kg polyethylene and 3.2kg embodiment 2 while being added in stirred tank, so
14.24kg repefral and 1.91kg polyethylene glycol is added thereto afterwards, is warming up to 200 DEG C, is uniformly mixed,
Two kinds of polymer is smelted into molten condition at this time, obtains casting solution；
Second step pours into the casting solution prepared in the first step in mold, heating plate is sulfided into film, then by mold
It moves into cooling bath and cools and solidifies rapidly, then take out the film after solidifying and be put into ethyl alcohol and impregnate 24-26h, replaced by solvent
Rutgers and polyethylene glycol therein are removed, finally dry the composite membrane after immersion in 50-60 DEG C of drying room
It is dry, the ethyl alcohol wherein replaced is removed, porous composite film, as battery diaphragm are obtained.
Embodiment 10:
Performance measurement is carried out to the diaphragm prepared in embodiment 3-9, specific continuous mode is as follows:
(1) Measuring Mechanical Properties: since lithium battery must have certain mechanical performance, it just can guarantee in use process and pacify
Entirely, therefore by electronic tension tester to isolation film Measuring Mechanical Properties are carried out, diaphragm is cut into 20mm × 150mm when test
Sample be measured.
(2) diaphragm: being cut into the sample of 40mm × 40mm by electrolyte measurement method, and sample is done at 80-90 DEG C
Dry 2h weighs after cooling and is denoted as m0, then diaphragm is immersed in electrolyte, is taken out after impregnating 2h, wherein electrolyte is by 1mol
1g ethylene carbonate and the preparation of 1g dimethyl carbonate are added in lithium hexafluoro phosphate, then with filter paper by the extra electrolysis of membrane surface
It weighs after liquid exhaustion, is denoted as m1, wherein imbibition rate P=(m1-m0)/m0× 100%.
(3) it protects liquid measurement: diaphragm is cut into the sample of 40mm × 40mm, dry 2h, cooling at 80-90 DEG C by sample
Weighing is denoted as m afterwards0, then diaphragm is immersed in electrolyte, is taken out after impregnating 2h, wherein electrolyte is by 1mol lithium hexafluoro phosphate
Diaphragm, is then placed between two layers of filter paper, in upper layer filter paper by middle addition 1g ethylene carbonate and the preparation of 1g dimethyl carbonate
Surface place weight be 100g weight, suppress 30s after measure diaphragm quality be m1, wherein protecting liquid rate R=(m1-m0)/m0
× 100%；The measurement structure of the above-mentioned performance of isolation film is as shown in table 1:
Table 1: the performance measurement result of the isolation film of embodiment 3-8 preparation:
As shown in Table 1, the isolation film strength that prepared by embodiment 3 reaches 52.13MPa, while imbibition rate reaches
286.31%, it protects liquid rate and reaches 92.23%, and the high liquid sucting copolymer that will be prepared in embodiment 1 in embodiment 4 and embodiment 5
It is substituted for the high liquid sucting copolymer of the preparation of embodiment 2, so that its breaking strength, imbibition rate and guarantor's liquid rate reduce, due to
There is no graft polymerization sodium group in embodiment 2 in polymer preparation process, so that imbibition group content in polymer
It reduces, simultaneously because improving the poly- of polymer by the grafting fixed function between polymer when polymerizeing then sodium sulfonate
Conjunction degree, and then improve the breaking strength of polymer；High imbibition polymerization is not added when for preparing perforated membrane in embodiment 6
Object directly uses polyethylene polymer, greatly reduces its imbibition water retention property, but its mechanical strength enhances, and embodiment 7
It is middle all using high liquid sucting copolymer without the use of polyethylene polymer so that the mechanical strength of its isolation film reduces, while right
The adsorption area of isolation film is not greatly reduced in the surface recombination foam films of perforated membrane in embodiment 8 and embodiment 9, into
And its breaking strength, imbibition rate and guarantor's liquid rate are largely reduced.
Present invention disclosed above preferred embodiment is only intended to help to illustrate the present invention.There is no detailed for preferred embodiment
All details are described, are not limited the invention to the specific embodiments described.Obviously, according to the content of this specification,
It can make many modifications and variations.These embodiments are chosen and specifically described to this specification, is in order to better explain the present invention
Principle and practical application, so that skilled artisan be enable to better understand and utilize the present invention.The present invention is only
It is limited by claims and its full scope and equivalent.
Claims (7)
1. the preparation process of new energy lithium ion battery separator, which is characterized in that specific preparation process is as follows:
Polyethylene and high liquid sucting copolymer are added in stirred tank simultaneously, phthalic acid two are then added thereto by the first step
Methyl esters and polyethylene glycol are warming up to 200 DEG C, are uniformly mixed, and two kinds of polymer is smelted into molten condition at this time, is cast
Film liquid；
Second step pours into the casting solution prepared in the first step in mold, and heating plate is sulfided into film, then moves into mold
It is cooled and solidified rapidly in cooling bath, then takes out the film after solidifying and be put into ethyl alcohol and impregnate 24-26h, replaced and removed by solvent
Composite membrane after immersion is finally dried in 50-60 DEG C of drying room, is removed by rutgers and polyethylene glycol therein
The ethyl alcohol wherein replaced is removed, porous composite film is obtained；
The perforated membrane prepared in second step is impregnated 1-2min in imbibition foaming solution, in 80-85 after then pulling out by third step
Foamed solidification 5-6h at DEG C, obtains battery diaphragm.
2. the preparation process of new energy lithium ion battery separator according to claim 1, which is characterized in that gather in the first step
The mass ratio of ethylene and high liquid sucting copolymer is 1:3.2-3.3, and polyethylene and high suction are added in every kilogram of rutgers
The gross mass of liquid polymer is 295-302g, and the quality that polyethylene glycol is added is 134-138g.
3. the preparation process of new energy lithium ion battery separator according to claim 1, which is characterized in that high imbibition polymerization
The preparation process of object is as follows:
1. weighing a certain amount of melamine to be dissolved in methanol, trihydroxy methyl third is added after then heating to 70-75 DEG C thereto
2,3- epoxypropyltrimethylchloride chloride, constant temperature back flow reaction 8- is added after isothermal reaction 1h in alkane triglycidyl ether thereto
Then 9h is evaporated and removes solvent methanol therein, obtains polymer, while drying is washed with deionized in polymer,
Obtain polymer；
2. the polymer adding into acetone that will be prepared in the first step, sodium isethionate is then added thereto, is warming up to 50-60
DEG C it being stirred 3-5min, toluene di-isocyanate(TDI) is then added dropwise thereto, constant temperature is stirred to react 6-7h after being added dropwise completely,
Then it is filtered washing and obtains high liquid sucting copolymer.
4. the preparation process of new energy lithium ion battery separator according to claim 3, which is characterized in that step 1. in three
The molar ratio of poly cyanamid and trihydroxymethylpropanyltri diglycidyl ether is 1:0.73-0.76, while melamine and 2,3- epoxy
The molar ratio of hydroxypropyltrimonium chloride is 1:0.28-0.29.
5. a kind of preparation process of new energy lithium ion battery separator according to claim 3, which is characterized in that step is 2.
In sodium isethionate 1.49-1.51g is added in every gram of polymer, while toluene di-isocyanate(TDI) 1.79-1.82g is added.
6. the preparation process of new energy lithium ion battery separator according to claim 1, which is characterized in that imbibition foaming is molten
The preparation process of body is as follows: the high liquid sucting copolymer of preparation being added in isopropyl acetate, then stirring and dissolving is added thereto
Hydroxy silicon oil is uniformly mixed, and pentane and Tween 80 are then added thereto, and concentration is added thereto after mixing and is
20% sulfuric acid solution obtains imbibition foaming solution controlled at being uniformly mixed at 25-30 DEG C.
7. the preparation process of new energy lithium ion battery separator according to claim 6, which is characterized in that every gram high imbibition
Isopropyl acetate 8-10mL is added in polymer, hydroxy silicon oil 0.21-0.23g is added, addition Tween 80 quality is 0.09-
0.1g is added pentane 0.09-0.11g, 20% sulfuric acid solution 0.11-0.13g is added.
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| CN201910205183.3A CN109873107B (en) | 2019-03-18 | 2019-03-18 | Preparation process of new energy lithium ion battery diaphragm |
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| CN201910205183.3A CN109873107B (en) | 2019-03-18 | 2019-03-18 | Preparation process of new energy lithium ion battery diaphragm |
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| CN109873107A true CN109873107A (en) | 2019-06-11 |
| CN109873107B CN109873107B (en) | 2022-09-20 |
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| CN109873107B (en) | 2022-09-20 |
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