CN108346765A - A kind of composite lithium ion cell diaphragm and preparation method thereof - Google Patents
A kind of composite lithium ion cell diaphragm and preparation method thereof Download PDFInfo
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- CN108346765A CN108346765A CN201810095512.9A CN201810095512A CN108346765A CN 108346765 A CN108346765 A CN 108346765A CN 201810095512 A CN201810095512 A CN 201810095512A CN 108346765 A CN108346765 A CN 108346765A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of composite lithium ion cell diaphragm of present invention proposition and preparation method thereof, belong to field of lithium ion battery material, the lithium ion battery separator improves the compatibility and bonding force of polyolefin basic layer diaphragm and coat, can effectively improve the cycle performance of ionic conductivity and lithium ion battery.The composite lithium ion cell diaphragm includes porous base's diaphragm and is coated on the polyimide coating of porous base's diaphragm unilateral side.The present invention can be applied in the key link of lithium ion battery development and application.
Description
Technical field
The invention belongs to field of lithium ion battery material more particularly to a kind of composite lithium ion cell diaphragm and its preparation sides
Method.
Background technology
As lithium ion battery (LIB) is led to power such as electric vehicle, aerospace, large-scale instrument instrument and energy storages
The development in domain, to the comprehensive performance of battery, more stringent requirements are proposed, and the safety issue of lithium ion battery is particularly important,
Especially internal short-circuit of battery problem.Diaphragm is component part indispensable in lithium ion battery, effect be prevent it is positive and negative
Short circuit occurs for pole contact, and is migrated in the electrolytic solution for lithium ion and provide channel.
Most widely used LIB diaphragms are traditional polyalkene diaphragms currently on the market.Although it is good with mechanical performance
Well, the advantages that chemical stability is good and cheap, but its poor thermal stability can influence the isolation between positive and negative electrode, very
The generation of safety accident can extremely be caused.Also, that there is also porositys is low for traditional polyalkene diaphragm, electrolyte wellability is insufficient
The problems such as, become one of the main factor for influencing high-temperature lithium ion battery security performance and high-rate discharge ability, is to restrict
The key link of lithium ion battery development and application.
In order to improve comprehensive performance of traditional polyalkene diaphragm in lithium ion battery applications, researcher has developed
Inorganic (ceramics) the composite lithium ion cell diaphragm of machine-, such diaphragm preparation process is simple, combine polyolefine material flexibility and
The advantages that absorbency of inorganic material, high temperature resistant, can avoid battery short circuit, explosion accident generation, to improving lithium-ion electric
The safety in pond has certain effect.But the binding force between the ceramic layer and basement membrane of Ceramic Composite diaphragm is weaker, easily makes pottery
Enamel coating obscission, therefore, patent application CN 201610024165.1 disclose a kind of functional coating diaphragm, in polyolefin
The slurry being made of Kynoar, inorganic nano ceramic particle and water is coated on base material, so that slurry and diaphragm is had more excellent
Caking property and heat resistance.If however, used under long-time service or high intensity environment, inorganic ceramic material and polyolefin-based
The stress generated between film still can be such that ceramic powder falls off.Therefore, this preparation method is obviously also required to addition adhesive
Improve the bonding force of ceramic layer and base, but effect is not long-acting.
Polyimides (PI) is a kind of high performance high-molecular organic material, collect excellent dielectric properties, high temperature resistance,
The advantages that mechanical performance, chemical stability is one of the high molecular polymer of most application prospect in one.Patent application CN
201610055570.X discloses a kind of preparation method of polyamidoimide lithium ion battery separator, causes phase to turn using non-solvent
Change method is prepared for polyamide-imide LIB diaphragms, which is greatly improved compared with polyalkene diaphragm, but tensile strength and
Puncture strength is relatively low.Therefore, the preferable compound LIB diaphragms of a kind of mechanical performance and high temperature resistance, which how will be prepared, to be
The important topic that this field is studied.
Invention content
A kind of composite lithium ion cell diaphragm of present invention proposition and preparation method thereof, which improves poly-
The compatibility and bonding force of alkene base diaphragm and coat can effectively improve ionic conductivity and the cycle of lithium ion battery
Performance.
In order to achieve the above object, an aspect of of the present present invention provides a kind of composite lithium ion cell diaphragm, the diaphragm
Including porous base's diaphragm and the polyimide coating for being coated on porous base's diaphragm unilateral side.
Preferably, porous base's diaphragm is thickness：5-40 μm, porosity：The polyalkene diaphragm of 30-80%.
Preferably, the polyalkene diaphragm is selected from polyethylene lithium battery diaphragm, polypropylene lithium battery diaphragm or by poly- second
One kind in the composite diaphragm of alkene lithium battery diaphragm and spaced three layers of polypropylene lithium battery diaphragm or more.
Preferably, the thickness of the polyimide coating is 1-10 μm, polyimide content is in the battery diaphragm
1-10%.
Another aspect provides a kind of composite lithium ion cell as described in any of the above-described technical solution every
The preparation method of film, includes the following steps：
The synthesis of polyimides：In a nitrogen environment, by dianhydride and diamines, reaction vessel is added in 0.8-1.2 in molar ratio
It is interior, organic solvent is then added, obtains polyamic acid solution after mechanic whirl-nett reaction 12-24h in ice-water bath, second is then added
Acid anhydride and triethylamine carry out chemical imidization, after reacting 24-48h, with ethanol precipitation resulting polymers, are filled through ethyl alcohol and deionized water
After dividing washing, it is placed in drying box, is dried overnight at 60-120 DEG C；It is dried in vacuo 12-48h at 120-150 DEG C again, is obtained
Polyimides；
The preparation of polyimide dope liquid：According to mass percent concentration 1-10%：2-20%：70-97% is by synthesis
Polyimides, pore former, organic solvent mixing, mechanical agitation is carried out in 50-100 DEG C of oil bath, until being uniformly mixed, has been dissolved
Entirely, polyimide dope liquid is obtained；
The preparation of composite lithium ion cell diaphragm：Gained polyimide dope liquid is stood into 12- in 50-100 DEG C of oil bath
It for 24 hours after deaeration, is coated on porous base's diaphragm, with scraper knifing, stops in air after 3-300s slowly at the uniform velocity into entering the room
Temperature is solidified in the coagulating bath containing solvent and non-solvent, and the film water after solidification is washed, and the dry 3-10h at 40-80 DEG C, is waited for
Moisture evaporation is complete, obtains composite lithium ion cell diaphragm.
Preferably, in the preparation process of polyimide dope liquid, according to mass percent concentration 4-8%：8-12%：
80-88% mixes the polyimides, pore former, organic solvent of synthesis.
Preferably, in the preparation process of composite lithium ion cell diaphragm, the slurry viscosity after deaeration is 40-800 centipoises,
Preferably 60-600 centipoises.
Preferably, the coagulating bath be one or more organic solvents in DMAc, NMP, DMF, DMP or ethyl alcohol with it is non-
The mixed liquor of aqueous solvent, wherein the concentration of volume percent of organic solvent is 10-90%, preferably 20-80%.
Preferably, the dianhydride is binary organic acid acid anhydride, the binary organic acid acid anhydride is selected from biphenyltetracarboxylic dianhydride, hexichol
One kind in ketone tetracid dianhydride, two ether dianhydride of pyromellitic acid anhydride, oxygen biphenyl tetracarboxylic acid anhydrides and bisphenol-A；The diamines is to have
Machine diamines, the organic diamine be selected from 4,4 '-diaminodiphenyl ethers, 3,4 '-diaminodiphenyl ethers, p-phenylenediamine, m-phenylene diamine (MPD),
One kind in 3,3 '-diphenyl sulphone (DPS) diamines and 4,4 '-diphenyl sulphone (DPS) diamines.
Preferably, the organic solvent is selected from N-Methyl pyrrolidone, n,N-dimethylacetamide, N, N- dimethyl
One or both of formamide, repefral, dimethyl sulfoxide (DMSO), m-cresol, tetrahydrofuran and methanol are appointed
Meaning scalemic thereof；The pore former be selected from lithium chloride, sodium chloride, magnesium chloride, calcium carbonate, calcium chloride, methanol, ethyl alcohol, propyl alcohol,
Glycerine, acetone, acetic acid, tetrahydrofuran, the polyethylene glycol of different molecular weight and different molecular weight polyvinylpyrrolidone in
It is one or more.
Compared with prior art, the advantages and positive effects of the present invention are：
1, the compound lithium ion battery diaphragm tensile strength and puncture strength that the present invention prepares are larger, high mechanical strength,
Be conducive to lithium ion battery assembling and improve the security performance of lithium ion battery.
2, the compound lithium ion battery diaphragm high temperature resistance that the present invention prepares is good, at relatively high temperatures diaphragm micro-hole knot
Structure will not destroy, and after placing 1h such as in 130 DEG C of baking ovens, membrane surface pore structure is not destroyed substantially.
3, the compound lithium ion battery diaphragm that the present invention prepares is without adding adhesive that can improve polyolefin base membrane and painting
The compatibility of coating improves the bonding force of polyolefin basic layer diaphragm and coat.
4, the electrolyte wellability for the compound lithium ion battery diaphragm that the present invention prepares is effectively improved, can be effective
Improving problem of the polyolefin to electrolyte wellability difference, imbibition rate is 150% after 6h is impregnated in lithium hexafluorophosphate electrolyte solution,
Lithium ion battery capacity retention ratio and cycle life can be effectively improved.
Description of the drawings
Fig. 1 is the PI product pictures synthesized in the present invention；
Fig. 2 is Celgrad polypropylene LIB diaphragms and electrolyte contacts angle picture；
Fig. 3 is the made compound LIB diaphragms of PI and electrolyte contacts angle picture in embodiment 1 in the present invention；
Fig. 4 is after PE basement membranes place 1h under 90 DEG C (left sides) and 130 DEG C (right side) in the present invention, with scanning electron microscope (SEM) table
The membrane surface pattern picture of sign；
Fig. 5 is after the made compound LIB diaphragms of PI place 1h under 90 DEG C (left sides) and 130 DEG C (right side) in the present invention, with scanning
The membrane surface pattern picture of Electronic Speculum (SEM) characterization.
Specific implementation mode
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
The every other embodiment that technical staff is obtained without making creative work belongs to the model that the present invention protects
It encloses.
An embodiment of the present invention provides a kind of composite lithium ion cell diaphragm, the diaphragm includes porous base's diaphragm and painting
Polyimide coating of the cloth in porous base's diaphragm unilateral side.A kind of composite lithium ion cell diaphragm is present embodiments provided,
It is combined by porous base's diaphragm and polyimide coating, the advantages of combining two kinds of materials of polyolefin and polyimides,
The compatibility for not only improving polyolefin basic layer diaphragm and coat improves the bonding of polyolefin basic layer diaphragm and coat
Power makes electrolyte wellability be improved, and the interface performance being effectively improved between positive and negative electrode and diaphragm improves ionic conductance
The cycle performance of rate and LIB batteries, meanwhile, the good mechanical property of composite lithium ion cell diaphragm substantially increases lithium ion
The high temperature resistance of battery diaphragm.
In a preferred embodiment, porous base's diaphragm is thickness：5-40 μm, porosity：The polyolefin of 30-80%
Diaphragm.In the present embodiment, it is enumerated the specific requirement realized to porous base's diaphragm, wherein being carried out to thickness, porosity
It limits, thus the polyalkene diaphragm with polyimide coating of form carry out compound, can effectively obtain the complex lithium electricity of desired effect
Sub- battery diaphragm.In an alternative embodiment, also the specific implementation form of polyalkene diaphragm is enumerated, as it can be selected from
Polyethylene lithium battery diaphragm, polypropylene lithium battery diaphragm or by polyethylene lithium battery diaphragm and polypropylene lithium battery diaphragm interval
One kind in three layers or more of the composite diaphragm of (PP/PE/PP) is set.
In a preferred embodiment, the thickness of the polyimide coating is 1-10 μm, and polyamides is sub- in the battery diaphragm
Amine content is 1-10%.The thickness of polyimide coating and its shared content in battery diaphragm are defined in the present embodiment, with
Ensure that obtained battery diaphragm all has good performance in terms of thickness, intensity, ventilative value, heat-shrinkable.One
The molecular weight in alternative embodiment, specifically defining the thickness of the coating, and further defining polyimides is 10,000-
300,000Da.Using under this condition polyimide coating and above-mentioned porous base's diaphragm carry out compound, desired effect can be obtained
Lithium ion battery diaphragm.
The embodiment of the present invention additionally provides a kind of composite lithium ion cell diaphragm as described in any of the above-described embodiment
Preparation method includes the following steps：
The synthesis of polyimides：In a nitrogen environment, by dianhydride and diamines, reaction vessel is added in 0.8-1.2 in molar ratio
It is interior, organic solvent is then added, obtains polyamic acid solution after mechanic whirl-nett reaction 12-24h in ice-water bath, second is then added
Acid anhydride and triethylamine carry out chemical imidization, after reacting 24-48h, with ethanol precipitation resulting polymers, are filled through ethyl alcohol and deionized water
After dividing washing, it is placed in drying box, is dried overnight at 60-120 DEG C；It is dried in vacuo 12-48h at 120-150 DEG C again, is obtained
Polyimides；
The preparation of polyimide dope liquid：According to mass percent concentration 1-10%：2-20%：70-97% is by synthesis
Polyimides, pore former, organic solvent mixing, mechanical agitation is carried out in 50-100 DEG C of oil bath, until being uniformly mixed, has been dissolved
Entirely, polyimide dope liquid is obtained；
The preparation of composite lithium ion cell diaphragm：Gained polyimide dope liquid is stood into 12- in 50-100 DEG C of oil bath
It for 24 hours after deaeration, is coated on porous base's diaphragm, with scraper knifing, stops in air after 3-300s slowly at the uniform velocity into entering the room
Temperature is solidified in the coagulating bath containing solvent and non-solvent, and the film water after solidification is washed, and the dry 3-10h at 40-80 DEG C, is waited for
Moisture evaporation is complete, obtains composite lithium ion cell diaphragm.
In the above-described embodiments, the preparation method for showing in particular composite lithium ion cell diaphragm, via above method knot
The compatibility of polyolefin basic layer diaphragm and coat can be improved by closing the battery diaphragm that specific parameter index is prepared, and be improved
The bonding force of polyolefin basic layer diaphragm and coat makes electrolyte wellability be improved, be effectively improved positive and negative electrode and diaphragm it
Between interface performance, improve the cycle performance of ionic conductivity and LIB batteries, meanwhile, the composite lithium ion cell diaphragm
Good mechanical property, substantially increase the high temperature resistance of lithium ion battery separator.
It, can be in the above method in order to which performance further more preferably battery diaphragm is prepared in an alternative embodiment
Some design parameters optimize, can be according to mass percent concentration for example, in the preparation process of polyimide dope liquid
4-8%：8-12%：80-88% mixes the polyimides, pore former, organic solvent of synthesis.For example, in compound lithium ion electricity
In the preparation process of pond diaphragm, the slurry viscosity after deaeration is 40-800 centipoises, preferably 60-600 centipoises.In another example will
When polyimide dope liquid is coated on porous base's diaphragm, Best-Effort request film, spin-coating, leaching may be used in coating method
Painting, scraper, coating bar and dimple roller coating apply etc..
In an alternative embodiment, the dianhydride is binary organic acid acid anhydride, and the binary organic acid acid anhydride is selected from biphenyl tetracid
One kind in dianhydride, benzophenone tetracid dianhydride, two ether dianhydride of pyromellitic acid anhydride, oxygen biphenyl tetracarboxylic acid anhydrides and bisphenol-A；It is described
Diamines is organic diamine, the organic diamine be selected from 4,4 '-diaminodiphenyl ethers, 3,4 '-diaminodiphenyl ethers, p-phenylenediamine,
One kind in m-phenylene diamine (MPD), 3,3 '-diphenyl sulphone (DPS) diamines and 4,4 '-diphenyl sulphone (DPS) diamines.
In an alternative embodiment, the organic solvent be selected from N-Methyl pyrrolidone, n,N-dimethylacetamide, N,
One kind in dinethylformamide, repefral, dimethyl sulfoxide (DMSO), m-cresol, tetrahydrofuran and methanol or
Two kinds of arbitrary proportion mixture；The pore former is selected from lithium chloride, sodium chloride, magnesium chloride, calcium carbonate, calcium chloride, methanol, second
Polyethylene glycol (the molecular weight of alcohol, propyl alcohol, glycerine, acetone, acetic acid, tetrahydrofuran, different molecular weight:200-4000Da) and not
With one or more in the polyvinylpyrrolidone of molecular weight.
In an alternative embodiment, the coagulating bath is DMAc, NMP, DMF, DMP or ethyl alcohol its one or more organic
The mixed liquor of solvent and non-solvent water, wherein the concentration of volume percent of organic solvent is 10-90%, preferably 20-80%.
In the above-described embodiments, specifically it is enumerated the specific of dianhydride, diamines, organic solvent, pore former and coagulating bath
Way of realization, it is to be understood that said components are enumerated, preferably however, it is not limited to this for the present embodiment, can also be this
The other components of equivalence replacement can be carried out known to field technology personnel.
The composite lithium ion cell diaphragm and its preparation side that the embodiment of the present invention is provided are introduced in detail in order to become apparent from
Method is described below in conjunction with specific embodiment.
Embodiment 1
Under nitrogen environment, 4,4 '-diaminodiphenyl ethers of 8.00g (0.04mol), 8.9g (0.0408mol) benzene four are weighed
Formic anhydride measures 160mL DMAC and is added in reaction vessel, and mechanical agitation is for 24 hours in ice-water bath；It is separately added into 17.6mL second again
Acid anhydride and 24mL triethylamines carry out chemical imidization.It is abundant through ethyl alcohol and deionized water with ethanol precipitation resulting polymers after 48h
It after washing, is placed in drying box and is dried overnight at 100 DEG C, be dried in vacuo at 150 DEG C for 24 hours to get light yellow PI products, such as
Shown in Fig. 1.
By 0.5g solid polyimides obtained above, 2.5g PEG2000,2.5g polyvinylpyrrolidones (PVP),
44.5g DMAc mixing carries out mechanical agitation until polyimides and pore former dissolving completely, obtain PI in 80 DEG C of oil bath
Casting solution.After stopping stirring, the deaeration 60min in 80 DEG C of oil baths.It is smooth on clean glass plate to complete 16 μm of PE bases
Film, the polyimide dope liquid on PE basement membranes after appropriate deaeration carry out knifing with scraper, delay after stopping 1min in air
Slowly at the uniform velocity immersing room temperature DMAc coagulating baths, (volume ratio of DMAc and water is 3:2) NIPs film forming is carried out in, is taken off and is carried after 3min
The PE films of polyimides are placed in water after impregnating 12h and take out.Polyimide content is 1% in made battery diaphragm.It is right after drying
Prepared composite lithium ion cell diaphragm carries out thickness, intensity, ventilative value, heat-shrinkable etc. and is tested, and the results are shown in Table 1.
Embodiment 2
Material therefor type, dosage and technological process with embodiment 1, unlike：
1g solid polyimides obtained above, 2.5g PEG2000,2.5g PVP, 43g DMAc are mixed, at 80 DEG C
Oil bath in carry out mechanical agitation until PI and organic pore former be uniformly mixed, dissolving it is complete, obtain the casting solution of P I.Stop
After stirring, the deaeration 60mi n in 80 DEG C of oil baths.It is smooth on clean glass plate to complete 16 μm of PE basement membranes, in PE basement membranes
On polyimide dope liquid after appropriate deaeration, carry out knifing with scraper, slowly at the uniform velocity immersed after stopping 1min in air
(volume ratio of DMAc and water is 3 for room temperature DMAc coagulating baths:2) NIPs film forming is carried out in, and polyimide coating is taken off after 3min
PE basement membranes are placed in deionized water after impregnating 12h and take out.Polyimide content is 2% in made battery diaphragm.To what is be prepared into
Composite lithium ion cell diaphragm carries out the tests such as thickness, intensity, ventilative value, heat-shrinkable, the results are shown in Table 1.
Embodiment 3
Material therefor type, dosage and technological process with embodiment 1, unlike：
5g solid polyimides obtained above, 2.5g PEG2000,2.5g PVP, 40g DMAc are mixed, at 80 DEG C
Oil bath in carry out mechanical agitation until PI and organic pore former be uniformly mixed, dissolving it is complete, obtain the casting solution of PI.Stopping is stirred
After mixing, the deaeration 60min in 80 DEG C of oil baths.It is smooth on clean glass plate to complete 16 μm of PE basement membranes, it is fallen on PE basement membranes
Polyimide dope liquid after appropriate deaeration, knifing is carried out with scraper, slowly at the uniform velocity immerses room temperature after stopping 1min in air
(volume ratio of DMAc and water is 3 for DMAc coagulating baths:2) NIPs film forming is carried out in, takes the PE bases of polyimide coating after 3min off
Film is placed in deionized water after impregnating 12h and takes out.Polyimide content is 10% in made battery diaphragm.It answers what is be prepared into
It closes lithium ion battery separator and carries out the tests such as thickness, intensity, ventilative value, heat-shrinkable, the results are shown in Table 1.
Embodiment 4
Material therefor type, dosage and technological process with embodiment 1, unlike：
1g solid polyimides obtained above, 5.0g glycerine, 44g DMAc are mixed, machine is carried out in 80 DEG C of oil bath
Tool stirring until PI and organic molecule pore former be uniformly mixed, dissolving it is complete, obtain PI casting solutions.After stopping stirring, 80
Standing and defoaming 60min in DEG C oil bath.It is smooth on clean glass plate to complete 16 μm of PE basement membranes, it is appropriate on PE basement membranes
Polyimide dope liquid after deaeration carries out knifing with scraper, slowly at the uniform velocity immerses room temperature DMAc after stopping 1min in air
(volume of DMAc and water point is than being 3 for coagulating bath:2) NIPs film forming is carried out in, takes the PE basement membranes of polyimide coating after 3min off,
It is placed in deionized water after impregnating 12h and takes out.Polyimide content is 2% in made battery diaphragm.To the complex lithium being prepared into
Ion battery diaphragm carries out the tests such as thickness, intensity, ventilative value, heat-shrinkable, the results are shown in Table 1.
Embodiment 5
Material therefor type, dosage and technological process with embodiment 1, unlike：
1g solid polyimides obtained above, 2.5g PEG2000,2.5g PVP, 44g DMAc are mixed, at 80 DEG C
Oil bath in carry out mechanical agitation until polyimides and pore former be uniformly mixed, dissolving it is complete, obtain polyimide dope liquid.
After stopping stirring, the deaeration 60min in 80 DEG C of oil baths.It is smooth on clean glass plate to complete 16 μm of PE basement membranes, in PE bases
Casting solution on film after appropriate deaeration carries out knifing with scraper, in air stop 1min after slowly, at the uniform velocity immerse room temperature
(volume ratio of DMAc and water is 2 for DMAc coagulating baths:3) it forms a film in, takes the PE films of polyimide coating after 3min off, be placed in
It is taken out after impregnating 12h in water.Polyimide content is 2% in made battery diaphragm.To the composite lithium ion cell that is prepared into every
Film carries out the tests such as thickness, intensity, ventilative value, heat-shrinkable, the results are shown in Table 1.
Embodiment 6
Material therefor type, dosage and technological process with embodiment 1, unlike：
1g solid polyimides obtained above, 2.5g PEG2000,2.5g PVP, 44g DMAc are mixed, at 80 DEG C
Oil bath in carry out mechanical agitation until polyimides and pore former dissolving are complete, obtain PI casting solutions.After stopping stirring, 80
Standing and defoaming 60min in DEG C oil bath.It is smooth on clean glass plate to complete 16 μm of PE basement membranes, it is appropriate on PE basement membranes
Polyimide dope liquid after deaeration carries out knifing with scraper, stops slow, at the uniform velocity immersion room temperature DMAc after 30s in air
(volume ratio of DMAc and water is 2 for coagulating bath:3) it forms a film in, takes the PE films of polyimide coating after 1min off, be soaked in certainly
Overflow is taken out afterwards for 24 hours in water.Polyimide content is 2% in made battery diaphragm.To the composite lithium ion cell being prepared into
Diaphragm carries out the tests such as thickness, intensity, ventilative value, heat-shrinkable, the results are shown in Table 1.
Comparative example 1
Identical as 1 technological process of embodiment, difference lies in battery diaphragms to be only made of 12 μm of PE basement membranes, then carries out thick
The test of degree, intensity, ventilative value, heat-shrinkable, the results are shown in Table 1.
Comparative example 2
Identical as 1 technological process of embodiment, difference lies in battery diaphragms to be only made of 18 μm of celgard basement membranes, then into
The test of row thickness, intensity, ventilative value, heat-shrinkable, the results are shown in Table 1.
Comparative example 3
Identical as 1 technological process of embodiment, difference lies in battery diaphragms to be only made of 22 μm of PP basement membranes, then carries out thick
The test of degree, intensity, ventilative value, heat-shrinkable, the results are shown in Table 1.
Comparative example 4
It is identical as 1 material therefor type of embodiment, dosage and technological process, and under the same conditions carry out thickness,
The test of intensity, ventilative value, heat-shrinkable the results are shown in Table 1 the difference is that 18 μm of celgard used are basement membrane.
Comparative example 5
It is identical as 1 material therefor type of embodiment, dosage and technological process, and under the same conditions carry out thickness,
The test of intensity, ventilative value, heat-shrinkable the results are shown in Table 1 the difference is that 22 μm of PP used are basement membrane.
The testing performance index result for the battery diaphragm that table 1 above-described embodiment 1-6 and comparative example 1-5 is provided
From the data in table 1, it can be seen that the thickness of composite lithium ion cell diaphragm provided herein, tensile strength, ventilative value,
Heat-shrinkable etc. has superperformance, such as Fig. 4, Fig. 5 it is found that the compound LIB diaphragms of PI prepared by the present invention be placed in 90 DEG C or
At 130 DEG C after 1h, pore structure does not change substantially；And PE basement membranes are placed at 90 DEG C after 1h, surface pore structure is not destroyed；But
It is placed at 130 DEG C after 1h, significant change has had occurred in diaphragm pore structure, and closed pore phenomenon occurs in significant portion hole.Meanwhile this
Battery diaphragm in application also has smaller contact angle, and as shown in Figure 2 and Figure 3, Celgard polypropylene LIB diaphragms are to electrolyte
Contact angle be 51.4 °, coat solid content 2% polyimides after compound LIB diaphragms the contact angle of electrolyte is reduced to
29.1°.Compared with polyolefin base membrane, surface coating PI prepared by compound LIB diaphragms to the wellability of electrolyte have compared with
It is big to improve.In conclusion the compound LIB diaphragms of PI that the present invention is prepared using NIPs have preferable thermal stability, to electrolyte
Good wellability, should have preferable cycle performance of battery using it as the LIB of diaphragm.
Claims (10)
1. a kind of composite lithium ion cell diaphragm, which is characterized in that the diaphragm includes porous base's diaphragm and is coated on described
The polyimide coating of porous base's diaphragm unilateral side.
2. composite lithium ion cell diaphragm according to claim 1, which is characterized in that porous base's diaphragm is thickness
Degree：5-40 μm, porosity：The polyalkene diaphragm of 30-80%.
3. composite lithium ion cell diaphragm according to claim 2, which is characterized in that the polyalkene diaphragm is selected from poly- second
Alkene lithium battery diaphragm, polypropylene lithium battery diaphragm are arranged by polyethylene lithium battery diaphragm and polypropylene lithium battery diaphragm interval
Three layers or more of composite diaphragm in one kind.
4. composite lithium ion cell diaphragm according to claim 1, which is characterized in that the thickness of the polyimide coating
It it is 1-10 μm, polyimide content is 1-10% in the battery diaphragm.
5. a kind of preparation method of composite lithium ion cell diaphragm according to any one of claims 1-4, which is characterized in that packet
Include following steps：
The synthesis of polyimides：In a nitrogen environment, by dianhydride and diamines, 0.8-1.2 is added in reaction vessel in molar ratio, so
After organic solvent is added, obtain polyamic acid solution after mechanic whirl-nett reaction 12-24h in ice-water bath, then be added acetic anhydride and
Triethylamine carries out chemical imidization, after reacting 24-48h, with ethanol precipitation resulting polymers, is fully washed through ethyl alcohol and deionized water
It after washing, is placed in drying box, is dried overnight at 60-120 DEG C；It is dried in vacuo 12-48h at 120-150 DEG C again, obtains polyamides
Imines；
The preparation of polyimide dope liquid：According to mass percent concentration 1-10%：2-20%：70-97% is by the polyamides of synthesis
Imines, pore former, organic solvent mixing, carry out mechanical agitation in 50-100 DEG C of oil bath, until being uniformly mixed, dissolving is complete,
Obtain polyimide dope liquid；
The preparation of composite lithium ion cell diaphragm：Gained polyimide dope liquid is stood 12-24h to take off in 50-100 DEG C of oil bath
It after bubble, is coated on porous base's diaphragm, with scraper knifing, stops in air after 3-300s and slowly at the uniform velocity enter room temperature containing molten
It is solidified in agent and the coagulating bath of non-solvent, the film water after solidification is washed, and the dry 3-10h at 40-80 DEG C, wait for that moisture is waved
It distributes entirely, obtains composite lithium ion cell diaphragm.
6. preparation method according to claim 5, which is characterized in that in the preparation process of polyimide dope liquid, according to
Mass percent concentration 4-8%：8-12%：80-88% mixes the polyimides, pore former, organic solvent of synthesis.
7. preparation method according to claim 5, which is characterized in that in the preparation process of composite lithium ion cell diaphragm,
Slurry viscosity after deaeration is 40-800 centipoises, preferably 60-600 centipoises.
8. preparation method according to claim 5, which is characterized in that the coagulating bath is DMAc, NMP, DMF, DMP or second
The mixed liquor of one or more organic solvents and non-solvent water in alcohol, wherein the concentration of volume percent of organic solvent is 10-
90%, preferably 20-80%.
9. preparation method according to claim 5, which is characterized in that the dianhydride is binary organic acid acid anhydride, the binary
Organic acid anhydride is selected from biphenyltetracarboxylic dianhydride, benzophenone tetracid dianhydride, pyromellitic acid anhydride, oxygen biphenyl tetracarboxylic acid anhydrides and bisphenol-A
One kind in two ether dianhydrides；The diamines is organic diamine, and the organic diamine is selected from 4,4 '-diaminodiphenyl ethers, 3,4 '-two
One kind in amino-diphenylethers, p-phenylenediamine, m-phenylene diamine (MPD), 3,3 '-diphenyl sulphone (DPS) diamines and 4,4 '-diphenyl sulphone (DPS) diamines.
10. preparation method according to claim 5, which is characterized in that the organic solvent is selected from N- crassitudes
Ketone, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, repefral, dimethyl sulfoxide (DMSO), m-cresol, four
The arbitrary proportion mixture of one or both of hydrogen furans and methanol；The pore former is selected from lithium chloride, sodium chloride, chlorination
The poly- second two of magnesium, calcium carbonate, calcium chloride, methanol, ethyl alcohol, propyl alcohol, glycerine, acetone, acetic acid, tetrahydrofuran, different molecular weight
It is one or more in the polyvinylpyrrolidone of alcohol and different molecular weight.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109004165A (en) * | 2018-08-01 | 2018-12-14 | 上海钱丰纺织品有限公司 | Heat-resisting lithium ion battery separator and preparation method thereof |
| CN109817870A (en) * | 2018-12-29 | 2019-05-28 | 东莞东阳光科研发有限公司 | Polyimide microsphere slurry, composite diaphragm and lithium ion battery |
| CN110142189A (en) * | 2019-04-08 | 2019-08-20 | 深圳市劢全新材料科技有限责任公司 | A kind of coating method and its application in high-temperaure coating coating |
| CN110474009A (en) * | 2019-07-12 | 2019-11-19 | 大连恒超锂业科技有限公司 | A kind of lithium ion battery nonwoven fabric base composite diaphragm and preparation method thereof |
| CN110911615A (en) * | 2019-11-20 | 2020-03-24 | 芜湖天弋能源科技有限公司 | High-temperature-resistant lithium ion battery diaphragm, preparation method thereof and lithium ion battery prepared from high-temperature-resistant lithium ion battery diaphragm |
| CN111063852A (en) * | 2019-09-17 | 2020-04-24 | 宁德时代新能源科技股份有限公司 | Separator, method for producing same, lithium ion secondary battery, and device |
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| CN112803118A (en) * | 2021-01-13 | 2021-05-14 | 山东工业陶瓷研究设计院有限公司 | Battery separator, preparation method and polyimide porous membrane impregnation equipment |
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| CN113488739A (en) * | 2021-08-03 | 2021-10-08 | 广东工业大学 | Three-layer porous diaphragm combining electrostatic spinning and phase separation methods and preparation method and application thereof |
| CN113508494A (en) * | 2019-01-04 | 2021-10-15 | 赛尔格有限责任公司 | Polyimide coated separator for lithium battery or capacitor |
| CN114204210A (en) * | 2021-11-05 | 2022-03-18 | 东方电气集团科学技术研究院有限公司 | Preparation method of novel sodium-ion battery diaphragm |
| CN114709558A (en) * | 2022-03-25 | 2022-07-05 | 中材锂膜有限公司 | High-heat-resistance polyamide-imide composite diaphragm and preparation method thereof |
| CN115332722A (en) * | 2022-08-16 | 2022-11-11 | 合肥国轩高科动力能源有限公司 | Modified high-heat-resistance polyamide coating diaphragm and preparation method and application thereof |
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| CN109004165A (en) * | 2018-08-01 | 2018-12-14 | 上海钱丰纺织品有限公司 | Heat-resisting lithium ion battery separator and preparation method thereof |
| CN109817870A (en) * | 2018-12-29 | 2019-05-28 | 东莞东阳光科研发有限公司 | Polyimide microsphere slurry, composite diaphragm and lithium ion battery |
| CN109817870B (en) * | 2018-12-29 | 2020-06-05 | 东莞东阳光科研发有限公司 | Polyimide microsphere slurry, composite diaphragm and lithium ion battery |
| CN113508494A (en) * | 2019-01-04 | 2021-10-15 | 赛尔格有限责任公司 | Polyimide coated separator for lithium battery or capacitor |
| CN110142189A (en) * | 2019-04-08 | 2019-08-20 | 深圳市劢全新材料科技有限责任公司 | A kind of coating method and its application in high-temperaure coating coating |
| CN110474009A (en) * | 2019-07-12 | 2019-11-19 | 大连恒超锂业科技有限公司 | A kind of lithium ion battery nonwoven fabric base composite diaphragm and preparation method thereof |
| CN111063852A (en) * | 2019-09-17 | 2020-04-24 | 宁德时代新能源科技股份有限公司 | Separator, method for producing same, lithium ion secondary battery, and device |
| CN110911615A (en) * | 2019-11-20 | 2020-03-24 | 芜湖天弋能源科技有限公司 | High-temperature-resistant lithium ion battery diaphragm, preparation method thereof and lithium ion battery prepared from high-temperature-resistant lithium ion battery diaphragm |
| CN113131089A (en) * | 2019-12-30 | 2021-07-16 | 深圳市研一新材料有限责任公司 | Spider-web structure lithium ion battery diaphragm and preparation method thereof |
| CN111234224A (en) * | 2020-01-16 | 2020-06-05 | 青岛蓝科途膜材料有限公司 | Modified aramid polymer with polyimide structure, aramid film casting liquid, lithium battery diaphragm, preparation method of lithium battery diaphragm and lithium battery |
| CN112803118A (en) * | 2021-01-13 | 2021-05-14 | 山东工业陶瓷研究设计院有限公司 | Battery separator, preparation method and polyimide porous membrane impregnation equipment |
| CN112803118B (en) * | 2021-01-13 | 2022-09-09 | 山东工业陶瓷研究设计院有限公司 | Battery separator, preparation method and polyimide porous membrane impregnation equipment |
| CN113488739A (en) * | 2021-08-03 | 2021-10-08 | 广东工业大学 | Three-layer porous diaphragm combining electrostatic spinning and phase separation methods and preparation method and application thereof |
| CN114204210A (en) * | 2021-11-05 | 2022-03-18 | 东方电气集团科学技术研究院有限公司 | Preparation method of novel sodium-ion battery diaphragm |
| CN114204210B (en) * | 2021-11-05 | 2024-01-05 | 东方电气集团科学技术研究院有限公司 | Preparation method of sodium ion battery diaphragm |
| CN114709558A (en) * | 2022-03-25 | 2022-07-05 | 中材锂膜有限公司 | High-heat-resistance polyamide-imide composite diaphragm and preparation method thereof |
| CN115332722A (en) * | 2022-08-16 | 2022-11-11 | 合肥国轩高科动力能源有限公司 | Modified high-heat-resistance polyamide coating diaphragm and preparation method and application thereof |
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