CN108365151A - A kind of polyimide high temperature-resistant lithium battery diaphragm and preparation method thereof - Google Patents
A kind of polyimide high temperature-resistant lithium battery diaphragm and preparation method thereof Download PDFInfo
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- CN108365151A CN108365151A CN201810097336.2A CN201810097336A CN108365151A CN 108365151 A CN108365151 A CN 108365151A CN 201810097336 A CN201810097336 A CN 201810097336A CN 108365151 A CN108365151 A CN 108365151A
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- lithium battery
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- battery diaphragm
- high temperature
- polyamic acid
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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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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 polyimide high temperature-resistant lithium battery diaphragm of present invention proposition and preparation method thereof, belongs to lithium battery material field, is applicable to a variety of solvable and insoluble polyimides, greatly extend the type and application field of polyimide porous membrane.Phase inversion method film forming and three step of hot imidization is caused to obtain the preparation method of polyimide high temperature-resistant lithium battery diaphragm by the synthesis of polyamic acid, non-solvent the present solution provides a kind of.The present invention can be applied in the application field of polyimide porous membrane.
Description
Technical field
The invention belongs to lithium battery material field more particularly to a kind of polyimide high temperature-resistant lithium battery diaphragm and its preparations
Method.
Background technology
Lithium battery has many advantages, such as that specific capacity is big, has extended cycle life, memory-less effect, can fast charging and discharging, answered extensively
For fields such as portable communication, electric vehicle, aerospaces.Diaphragm as component part important in lithium ion battery,
Its effect played in lithium ion battery is to separate positive and negative electrode, and positive and negative electrode is avoided to contact, and at the same time allows lithium ion logical
It crosses, carries out charge-conduction, therefore the property relationship of diaphragm is to the chemical property and security performance of lithium ion battery, it is electric to improving
Each performance in pond has larger meaning.
The lithium battery diaphragm being commercialized at present is mainly polyolefin (PO) micro-pore septum, including polyethylene (PE) and polypropylene
(PP), polyolefin has many advantages, such as have heat to close performance under low cost, excellent mechanical strength, high temperature.But polyalkene diaphragm
Yielding at high temperature (135 DEG C or so of PE fusing points, 170 DEG C or so of PP fusing points), to the bad the problems such as system of the wellability of electrolyte
About the further development of lithium battery.The high temperature resistance of diaphragm and the wellability to electrolyte are improved, to improving battery peace
It is made great sense in terms of full property and chemical property.
In order to improve comprehensive performance of the conventional polyolefins in lithium ion battery applications, in addition to ceramic coated composite diaphragm
Outside, the new diaphragm material that selection can replace the thermal stability of polyolefin good is another solution route.Polyimides is a kind of high
The high-molecular organic material of performance, the advantages that collecting excellent dielectric properties, high temperature resistance, mechanical performance, chemical stability in
One, is one of the high molecular polymer of most application prospect.At present prepare polyimide diaphragm it is widely used be quiet
The nano fiber diaphragm of electrical spinning method, preparation is heat-resist, but its aperture is excessive, porosity is excessively high, causes using it as diaphragm
Lithium battery spray charging precipitator it is relatively low, often occur short circuit phenomenon, especially battery diaphragm thickness less than 30 μm when, micro-short circuit
The probability that situation occurs is relatively high.Patent application CN 201410339770.9 discloses a kind of high temp resistance lithium ion cell diaphragm
Preparation process, polyimide precursor, calcium carbonate template and organic solvent are mixed, be coated and dried, are heat-treated, is most passed through afterwards
Peracid treatment dissolves out calcium carbonate, obtains porous septum.Template dissolution acid is common acid used by this method, though avoid use
The dangers such as hydrofluoric acid, but process or comparatively laborious.Patent application CN 201610055570.X disclose a kind of polyamide acyl
The preparation method of imines (PAI) lithium battery diaphragm, using non-solvent cause phase inversion be prepared for polyamidoimide lithium battery every
PAI is dissolved in aprotic polar solvent by film, addition pore former obtain coating liquid, then by NIPs methods obtain PAI every
Film, the diaphragm temperature tolerance are greatly improved compared with polyalkene diaphragm.Patent application CN 201610608944.6 discloses a kind of poly-
The polyimides of synthesis and PVDF are dissolved in organic solvent by the lithium ion battery separator of acid imide and PVDF by certain mass ratio
In, casting solution is then coated in progress forming film with phase transformation method on substrate and obtains polyimides/PVDF diaphragms.
However, the method mentioned in above-mentioned patent can only be directed to soluble high polymer, but polyimides type is various, can
Be dissolved in organic solvent is only a few, and most of aromatic polyimide is all insoluble.Therefore, how to provide a kind of poly-
Imide li battery diaphragm preparation method makes it be applicable to a variety of solvable and insoluble polyimides, to extend polyamides Asia
The type and application field of amine perforated membrane will be projects that this field is studied.
Invention content
A kind of polyimide high temperature-resistant lithium battery diaphragm of present invention proposition and preparation method thereof, is applicable to a variety of solvable
With insoluble polyimides, the type and application field of polyimide porous membrane are greatly extended.
In order to achieve the above object, an aspect of of the present present invention provides a kind of system of polyimide high temperature-resistant lithium battery diaphragm
Preparation Method includes the following steps：
The synthesis of polyamic acid：In a nitrogen environment, by described organic acid anhydride or derivatives thereof with organic diamine according to one
Fixed molar ratio is added in reaction vessel, and organic solvent is then added, in ice-water bath after mechanic whirl-nett reaction 12-24h, obtains
Polyamic acid solution；
The preparation of polyamic acid casting solution：According to mass percent concentration 6-20%：2-20%：60-92% is by synthesis
Polyamic acid, pore former, organic solvent mixing stop stirring in 10-30 DEG C of mechanical agitation until pore former is completely dissolved, quiet
Deaeration is set until bubble-free, obtains polyamic acid casting solution；
Non-solvent causes phase inversion method film forming：Polyamide on clean glass plate or stainless steel substrates after appropriate deaeration
Sour casting solution carries out knifing with scraper, stops in air after 5-100s and slowly at the uniform velocity immerses 10-60 DEG C of non-solvent coagulating bath
In form a film, after film surface and it is internal form micropore 1-30min after take the porous basement membrane with polyamic acid off, be placed in from
It is taken out after impregnating 0.5-60min in sub- water；
Hot imidization：Porous basement membrane with polyamic acid is taken out from deionized water, temperature programming solidification is gathered
Acid imide high-temperature-reslithium lithium battery diaphragm.
Preferably, described program elevated cure condition is：0.5-2h is kept the temperature at 70-150 DEG C, then at 180-250 DEG C
0.5-2h is kept the temperature, then keeps the temperature 0.5-1h at 280-350 DEG C.
Preferably, the molar ratio of described organic acid anhydride or derivatives thereof and organic diamine is 0.8-1.2.
Preferably, described organic acid anhydride or derivatives thereof is biphenyltetracarboxylic dianhydride, benzophenone tetracid dianhydride, equal benzene tetramethyl
One kind of two ether dianhydride of acid dianhydride, oxygen biphenyl tetracarboxylic acid anhydrides or bisphenol-A, the organic diamine be 4,4 '-diaminodiphenyl ethers, 3,
One kind of 4 '-diaminodiphenyl ethers, p-phenylenediamine, m-phenylene diamine (MPD), 3,3 '-diphenyl sulphone (DPS) diamines or 4,4 '-diphenyl sulphone (DPS) diamines.
Preferably, the organic solvent is N-2- methyl pyrrolidones, n,N-dimethylacetamide, N, N- dimethyl methyls
The arbitrary proportion mixture of one or both of amide, repefral, dimethyl sulfoxide (DMSO) or tetrahydrofuran.
Preferably, the non-solvent coagulating bath is the mixing of one or both of acetone or alcohol organic solvent and water
Liquid, wherein the concentration of volume percent of organic solvent is 30%-90%.
Preferably, the pore former be inorganic molecules electrolyte for example lithium chloride, sodium chloride, magnesium chloride, calcium carbonate or
Calcium chloride or small molecule organic compound such as methanol, ethyl alcohol, propyl alcohol, glycerine, acetone, acetic acid, tetrahydrofuran, polyvinyl pyrrole
Alkanone, ethyl acetate, petroleum ether or different molecular weight polyethylene glycol in one or more arbitrary proportion mixtures.
Another aspect provides a kind of preparation methods as described in any of the above-described technical solution to be prepared
Polyimide high temperature-resistant lithium battery diaphragm.
Preferably, the thickness of the polyimide high temperature-resistant lithium battery diaphragm is 10-200 μm.
Preferably, polyimides is formed by polyamic acid hot imidization, and molecular weight 10,000-300,000Da.
Compared with prior art, the advantages and positive effects of the present invention are：
1, the preparation method of polyimide high temperature-resistant lithium battery diaphragm provided by the invention can be adapted for a variety of solubilities
With insoluble polyimides, the type and application field of polyimide porous membrane are greatly extended.In addition, this method is optional
The organic/inorganic pore former for selecting a variety of different molecular weights uses the solidification than mixed organic solvent/water mixing with different volumes
Bath, can effectively adjust the process for mutually converting film forming, prepare porosity and the controllable polyimides lithium battery diaphragm of pore size.
2, the polyimides lithium battery diaphragm structure that prepared by the present invention is uniform, and thermal shrinkage is good, in 300 DEG C of baking ovens
After placing 1h, horizontal and vertical Heat Shrinkage value is 0, can improve the security performance of battery well.
3, the polyimides lithium battery diaphragm electrolyte wellability and absorbent that prepared by the present invention are improved, can be effective
Improve the polyolefin problem poor to electrolyte wellability.
Description of the drawings
Fig. 1 is made polyimide high temperature-resistant lithium battery diaphragm scanning electron microscopic picture in the present invention；
Fig. 2 is that Celgard diaphragms test the contact angle of lithium hexafluorophosphate electrolyte solution；
Fig. 3 is that polyimide high temperature-resistant lithium battery diaphragm tests the contact angle of lithium hexafluorophosphate electrolyte solution.
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 preparation methods of polyimide high temperature-resistant lithium battery diaphragm, including following step
Suddenly：
The synthesis of polyamic acid：In a nitrogen environment, by described organic acid anhydride or derivatives thereof with organic diamine according to one
Fixed molar ratio is added in reaction vessel, and organic solvent is then added, in ice-water bath after mechanic whirl-nett reaction 12-24h, obtains
Polyamic acid solution；
The preparation of polyamic acid casting solution：According to mass percent concentration 6-20%：2-20%：60-92% is by synthesis
Polyamic acid, pore former, organic solvent mixing stop stirring in 10-30 DEG C of mechanical agitation until pore former is completely dissolved, quiet
Deaeration is set until bubble-free, obtains polyamic acid casting solution；
Non-solvent causes phase inversion method film forming：Polyamide on clean glass plate or stainless steel substrates after appropriate deaeration
Sour casting solution carries out knifing with scraper, stops in air after 5-100s and slowly at the uniform velocity immerses 10-60 DEG C of non-solvent coagulating bath
In form a film, after film surface and it is internal form micropore 1-30min after take the porous basement membrane with polyamic acid off, be placed in from
It is taken out after impregnating 0.5-60min in sub- water；
Hot imidization：Porous basement membrane with polyamic acid is taken out from deionized water, temperature programming solidification is gathered
Acid imide high-temperature-reslithium lithium battery diaphragm.
In the above-described embodiments, the preparation method for showing in particular polyimide high temperature-resistant lithium battery diaphragm, via above-mentioned
Method is good in conjunction with the thermal shrinkage for the battery diaphragm that specific parameter index is prepared, and can improve the peace of battery well
Full performance, and wellability to lithium hexafluorophosphate electrolyte solution and absorbent also get a promotion, and can be effectively improved polyolefin pair
The poor problem of electrolyte wellability.
The preparation condition for giving polyamic acid casting solution in the above-described embodiments, the casting film being prepared under this condition
Liquid follow-up non-solvent cause phase inversion method film formation step in can get the high performance porous basement membrane with polyamic acid, to for
The follow-up polyimide high temperature-resistant lithium battery diaphragm for obtaining desired effect lays the foundation.
In a preferred embodiment, described program elevated cure condition is：0.5-2h is kept the temperature at 70-150 DEG C, is then existed
180-250 DEG C of heat preservation 0.5-2h, then 0.5-1h is kept the temperature at 280-350 DEG C.It gives in the present embodiment and is risen by polyamic acid program
Warm imidization obtains the condition of polyimides, and under this condition, polyamic acid can the reaction was complete, poly- to effectively be prepared
Acid imide.
In a preferred embodiment, the molar ratio of described organic acid anhydride or derivatives thereof and organic diamine is 0.8-1.2.This
Given in embodiment the synthesis condition of polyamic acid, acid anhydrides and diamines according to set molar ratio organic solvent effect
Under polyamic acid can be prepared.It should be noted that the molar ratio is the molar ratio after optimization, those skilled in the art can root
Factually border response situation is adjusted within this range.
In an alternative embodiment, described organic acid anhydride or derivatives thereof be biphenyltetracarboxylic dianhydride, benzophenone tetracid dianhydride,
One kind of two ether dianhydride of pyromellitic acid anhydride, oxygen biphenyl tetracarboxylic acid anhydrides or bisphenol-A, the organic diamine are 4,4 '-diamino
Diphenyl ether, 3,4 '-diaminodiphenyl ethers, p-phenylenediamine, m-phenylene diamine (MPD), 3,3 '-diphenyl sulphone (DPS) diamines or 4,4 '-diphenyl sulphone (DPS) diamines
It is a kind of.
In an alternative embodiment, the organic solvent is N-2- methyl pyrrolidones, n,N-dimethylacetamide, N, N-
The arbitrary proportion of one or both of dimethylformamide, repefral, dimethyl sulfoxide (DMSO) or tetrahydrofuran is mixed
Close object.
In an alternative embodiment, the non-solvent coagulating bath be one or both of acetone or alcohol organic solvent with
The mixed liquor of water, wherein the concentration of volume percent of organic solvent is 30%-90%.
In an alternative embodiment, the pore former be inorganic molecules electrolyte for example lithium chloride, sodium chloride, magnesium chloride,
Calcium carbonate or calcium chloride or small molecule organic compound such as methanol, propyl alcohol, glycerine, acetone, acetic acid, tetrahydrofuran, gather ethyl alcohol
Vinylpyrrolidone, ethyl acetate, petroleum ether or different molecular weight polyethylene glycol in one or more arbitrary proportions it is mixed
Close object.
In the above-described embodiments, organic acid anhydride or derivatives thereof, organic diamine, organic solvent, pore-forming are specifically enumerated
The specific implementation form of agent and non-solvent coagulating bath, it is to be understood that said components are enumerated, the present embodiment preferably but
It is not limited thereto, can also be the other components well known to those skilled in the art for carrying out equivalence replacement.
The embodiment of the present invention additionally provide a kind of preparation method as described in any of the above-described embodiment be prepared it is poly-
Acid imide high-temperature-reslithium lithium battery diaphragm.The thermal shrinkage of the polyimide high temperature-resistant lithium battery diaphragm is good, in 300 DEG C of baking ovens
After middle placement 1h, horizontal and vertical Heat Shrinkage value is 0, can improve the security performance of battery well, and to hexafluoro phosphorus
The wellability and absorbent of sour lithium electrolyte also get a promotion, and can be effectively improved that polyolefin is poor to electrolyte wellability to ask
Topic.
In a preferred embodiment, the thickness of the polyimide high temperature-resistant lithium battery diaphragm is 10-200 μm.This implementation
In example, specifically define that the thickness of the diaphragm, the diaphragm of the thickness range can meet above-mentioned performance.Further, in above-mentioned choosing
The molecular weight of polyimides can be 10,000-300,000Da in embodiment, and those skilled in the art can be in the molecular weight ranges
Different types of polyimides is selected, to extend the type and application field of polyimide porous membrane.
In order to become apparent from introduce in detail polyimide high temperature-resistant lithium battery diaphragm that the embodiment of the present invention is provided and its
Preparation 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 160mlDMAC and is added in reaction vessel, and mechanical agitation is for 24 hours in ice-water bath；Add 16g pore formers
PEG400 stops stirring, standing and defoaming in polyamic acid casting solution until do not have after stirring under room temperature is until pore former is completely dissolved
There is bubble.Casting solution on clean glass plate after appropriate deaeration, carries out knifing with scraper, stops 30s in air, delays
Slowly it at the uniform velocity immerses in 20 DEG C of ethyl alcohol and impregnates 1min, then be placed in water 30s, the perforated membrane of polyamic acid is taken after taking-up off, 100
1h is kept the temperature at DEG C, and 1h is kept the temperature at 200 DEG C, 1h is kept the temperature at 300 DEG C, obtains polyimide high temperature-resistant lithium battery diaphragm.To being prepared into
The diaphragm arrived carries out the test of thickness, intensity, ventilative value, heat-shrinkable, and test result is shown in Table 1.
Embodiment 2
Under nitrogen environment, 4,4 '-diaminodiphenyl ethers of 8.00g (0.04mol), 8.7g (0.04mol) benzene tetramethyls are weighed
Acid anhydrides measures 160mlDMAC and is added in reaction vessel, and mechanical agitation is for 24 hours in ice-water bath；16g pore former PEG400 are added,
Stirring stops stirring after pore former is completely dissolved under room temperature, and standing and defoaming in polyamic acid casting solution until do not have bubble.
Casting solution on clean glass plate after appropriate deaeration, carries out knifing with scraper, stops 30s in air, slowly at the uniform velocity
It immerses in 20 DEG C of ethyl alcohol and impregnates 1min, then be placed in water 30s, take the perforated membrane of polyamic acid after taking-up off, protected at 100 DEG C
Warm 1h keeps the temperature 1h at 200 DEG C, keeps the temperature 1h at 300 DEG C, obtain polyimide high temperature-resistant lithium battery diaphragm.To be prepared every
Film carries out the test of thickness, intensity, ventilative value, heat-shrinkable, and test result is shown in Table 1.
Embodiment 3
Under nitrogen environment, 4,4 '-diaminodiphenyl ethers of 8.00g (0.04mol), 8.9g (0.0408mol) benzene four are weighed
Formic anhydride measures 160mlDMAC and is added in reaction vessel, and mechanical agitation is for 24 hours in ice-water bath；Add 32g pore formers
PEG400 stops stirring, standing and defoaming in polyamic acid casting solution until do not have after stirring under room temperature is until pore former is completely dissolved
There is bubble.Casting solution on clean glass plate after appropriate deaeration, carries out knifing with scraper, stops 1min in air,
It slowly at the uniform velocity immerses in 40 DEG C of ethyl alcohol and impregnates 1min, then be placed in water 30s, take the perforated membrane of polyamic acid after taking-up off,
1h is kept the temperature at 100 DEG C, and 1h is kept the temperature at 200 DEG C, 1h is kept the temperature at 300 DEG C, obtains polyimide high temperature-resistant lithium battery diaphragm.To preparing
Obtained diaphragm carries out the test of thickness, intensity, ventilative value, heat-shrinkable, and test result is shown in Table 1.
Embodiment 4
Under nitrogen environment, 4,4 '-diaminodiphenyl ethers of 8.00g (0.04mol), 8.9g (0.0408mol) benzene four are weighed
Formic anhydride measures 160mlDMAC and is added in reaction vessel, and mechanical agitation is for 24 hours in ice-water bath；Add 16g pore formers
PEG200 and 16g glycerine stops stirring, standing and defoaming is until polyamic acid after stirring under room temperature is until pore former is completely dissolved
There is no bubble in casting solution.Casting solution on clean glass plate after appropriate deaeration, carries out knifing, in air with scraper
30s is stopped, (volume ratio of ethyl alcohol and water is 1 to the ethanol/water of slowly at the uniform velocity 60 DEG C of immersion:1) 3min is impregnated in, then is placed in water
1min takes the perforated membrane of polyamic acid off after taking-up, 1h is kept the temperature at 100 DEG C, and 1h is kept the temperature at 200 DEG C, 1h is kept the temperature at 300 DEG C,
Obtain polyimide high temperature-resistant lithium battery diaphragm.Thickness, intensity, ventilative value, heat-shrinkable are carried out to the diaphragm that is prepared
Test, test result are shown in Table 1.
Embodiment 5
Under nitrogen environment, 4,4 '-diaminodiphenyl ethers of 8.00g (0.04mol), 8.9g (0.0408mol) benzene four are weighed
Formic anhydride measures 160mlDMAC and is added in reaction vessel, and mechanical agitation is for 24 hours in ice-water bath；Add 16g pore formers
PEG400 stops stirring, standing and defoaming in polyamic acid casting solution until do not have after stirring under room temperature is until pore former is completely dissolved
There is bubble.Casting solution on clean glass plate after appropriate deaeration, carries out knifing with scraper, stops 30s in air, delays
Slowly it at the uniform velocity immerses in 20 DEG C of ethyl alcohol and impregnates 1min, then be placed in water 30s, the perforated membrane of polyamic acid is taken after taking-up off, 120
0.5h is kept the temperature at DEG C, and 1h is kept the temperature at 250 DEG C, 1h is kept the temperature at 350 DEG C, obtains polyimide high temperature-resistant lithium battery diaphragm.To preparing
Obtained diaphragm carries out the test of thickness, intensity, ventilative value, heat-shrinkable, and test result is shown in Table 1.
Comparative example 1
20 μm of PE basement membranes are carried out to the survey of thickness, intensity, ventilative value, heat-shrinkable under the same conditions as example 1
Examination, test result are shown in Table 1.
Comparative example 2
20 μm of PP basement membranes are carried out to the survey of thickness, intensity, ventilative value, heat-shrinkable under the same conditions as example 1
Examination, test result are shown in Table 1.
Comparative example 3
20 μm of Celgard basement membranes are subjected to thickness, intensity, ventilative value, heat-shrinkable under the same conditions as in example 1
Test, test result is shown in Table 1.
The testing performance index result for the battery diaphragm that table 1 above-described embodiment 1-5 and comparative example 1-3 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.Specifically, as shown in Figure 1, polyimides lithium battery diaphragm tool prepared by the present invention
Have uniform porous structure, allow lithium ion by while, imbibition ability also has prodigious improvement compared with polyalkene diaphragm.
In addition, as shown in Figures 2 and 3, Celgard diaphragms are 51.4 ° to the contact angle of electrolyte, and polyimide diaphragm is to electrolyte
Contact angle is 25.5 °, is substantially improved compared with polyalkene diaphragm to the wellability of electrolyte.In conclusion the present invention uses NIPs systems
Standby polyimide high temperature-resistant lithium battery diaphragm have preferable thermal stability, the good wellability to electrolyte, using its as
The lithium battery of diaphragm has preferable cycle performance of battery.
Claims (10)
1. a kind of preparation method of polyimide high temperature-resistant lithium battery diaphragm, which is characterized in that include the following steps：
The synthesis of polyamic acid：In a nitrogen environment, by described organic acid anhydride or derivatives thereof with organic diamine according to certain
Molar ratio is added in reaction vessel, and organic solvent is then added, in ice-water bath after mechanic whirl-nett reaction 12-24h, obtains polyamides
Amino acid solution；
The preparation of polyamic acid casting solution：According to mass percent concentration 6-20%：2-20%：60-92% is by the polyamides of synthesis
Amino acid, pore former, organic solvent mixing stop stirring in 10-30 DEG C of mechanical agitation until pore former is completely dissolved, and stand de-
Bubble obtains polyamic acid casting solution until bubble-free；
Non-solvent causes phase inversion method film forming：Polyamic acid casting on clean glass plate or stainless steel substrates after appropriate deaeration
Film liquid carries out knifing with scraper, stop in air after 5-100s slowly at the uniform velocity immerse in 10-60 DEG C of non-solvent coagulating bath into
Row film forming takes the porous basement membrane with polyamic acid off after film surface and internal formation micropore 1-30min, is placed in deionized water
It is taken out after middle immersion 0.5-60min；
Hot imidization：Porous basement membrane with polyamic acid is taken out from deionized water, temperature programming solidification obtains polyamides Asia
Amine high-temperature-reslithium lithium battery diaphragm.
2. preparation method according to claim 1, which is characterized in that described program elevated cure condition is：In 70-150
DEG C heat preservation 0.5-2h, then at 180-250 DEG C keep the temperature 0.5-2h, then at 280-350 DEG C keep the temperature 0.5-1h.
3. preparation method according to claim 1, which is characterized in that described organic acid anhydride or derivatives thereof and organic diamine
Molar ratio be 0.8-1.2.
4. preparation method according to claim 1, which is characterized in that described organic acid anhydride or derivatives thereof is biphenyl tetracid
One kind of dianhydride, benzophenone tetracid dianhydride, two ether dianhydride of pyromellitic acid anhydride, oxygen biphenyl tetracarboxylic acid anhydrides or bisphenol-A, it is described to have
Machine diamines is 4,4 '-diaminodiphenyl ethers, 3,4 '-diaminodiphenyl ethers, p-phenylenediamine, m-phenylene diamine (MPD), 3,3 '-diphenyl sulphone (DPS) diamines
Or 4,4 '-diphenyl sulphone (DPS) diamines one kind.
5. preparation method according to claim 1, which is characterized in that the organic solvent be N-2- methyl pyrrolidones,
One in DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, repefral, dimethyl sulfoxide (DMSO) or tetrahydrofuran
Kind or two kinds of arbitrary proportion mixture.
6. preparation method according to claim 1, which is characterized in that the non-solvent coagulating bath is in acetone or alcohol
The mixed liquor of one or two kinds of organic solvents and water, wherein the concentration of volume percent of organic solvent is 30%-90%.
7. preparation method according to claim 1, which is characterized in that the pore former is inorganic molecules electrolyte such as chlorine
Change lithium, sodium chloride, magnesium chloride, calcium carbonate or calcium chloride or small molecule organic compound such as methanol, ethyl alcohol, propyl alcohol, glycerine, third
Ketone, acetic acid, tetrahydrofuran, polyvinylpyrrolidone, ethyl acetate, petroleum ether or different molecular weight polyethylene glycol in one kind
Or a variety of arbitrary proportion mixture.
8. a kind of polyimide high temperature-resistant lithium battery being prepared such as claim 1-7 any one of them preparation methods every
Film.
9. polyimide high temperature-resistant lithium battery diaphragm according to claim 8, which is characterized in that the resistance to height of polyimides
The thickness of warm lithium battery diaphragm is 10-200 μm.
10. polyimide high temperature-resistant lithium battery diaphragm according to claim 8, which is characterized in that polyimides is by polyamides
Amino acid hot imidization forms, molecular weight 10,000-300,000Da.
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| CN110256717A (en) * | 2019-07-03 | 2019-09-20 | 西安交通大学 | A kind of porous polyimide film and its preparation method and application |
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| CN110845731A (en) * | 2019-11-01 | 2020-02-28 | 北京化工大学 | Method for preparing insoluble infusible polyimide film with full sponge pore structure |
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| CN110880574A (en) * | 2019-11-28 | 2020-03-13 | 衡阳市鑫晟新能源有限公司 | Lithium battery isolation film and preparation method thereof |
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| CN112062989A (en) * | 2020-08-10 | 2020-12-11 | 航天特种材料及工艺技术研究所 | Polyimide aerogel lithium battery diaphragm and preparation method thereof |
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| CN112876717A (en) * | 2021-01-25 | 2021-06-01 | 四川大学 | High-dielectric-constant polyamide 1 material and preparation method thereof |
| 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 |
| CN113668093A (en) * | 2021-09-10 | 2021-11-19 | 陕西科技大学 | Polyimide nano spider-web fiber filtering membrane and preparation method thereof |
| CN115133218A (en) * | 2022-03-09 | 2022-09-30 | 哈尔滨工业大学 | Ultrathin composite diaphragm of lithium ion battery and preparation method thereof |
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