CN101656306B - Composite membrane and preparation method thereof and battery comprising composite membrane - Google Patents
Composite membrane and preparation method thereof and battery comprising composite membrane Download PDFInfo
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- CN101656306B CN101656306B CN200810145795XA CN200810145795A CN101656306B CN 101656306 B CN101656306 B CN 101656306B CN 200810145795X A CN200810145795X A CN 200810145795XA CN 200810145795 A CN200810145795 A CN 200810145795A CN 101656306 B CN101656306 B CN 101656306B
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- Prior art keywords
- porous membrane
- acid
- composite diaphragm
- polyimide porous
- pore
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- 239000012528 membrane Substances 0.000 title claims abstract description 154
- 239000002131 composite material Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229920001721 polyimide Polymers 0.000 claims abstract description 152
- 239000004642 Polyimide Substances 0.000 claims abstract description 143
- 238000000034 method Methods 0.000 claims abstract description 62
- 239000011148 porous material Substances 0.000 claims abstract description 62
- 229920000098 polyolefin Polymers 0.000 claims abstract description 41
- 238000009826 distribution Methods 0.000 claims abstract description 19
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims description 68
- 229920005575 poly(amic acid) Polymers 0.000 claims description 61
- 239000004952 Polyamide Substances 0.000 claims description 55
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- 239000000853 adhesive Substances 0.000 claims description 52
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- 239000002904 solvent Substances 0.000 claims description 30
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- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 25
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
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- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009165 saligot Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
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Images
Classifications
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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
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a composite membrane and a preparation method thereof and a battery comprising the composite membrane. The composite membrane comprises a polyolefin porous membrane layer and a polyimide porous membrane layer, wherein the composite membrane also comprises an adhesive layer; the adhesive layer is positioned between the polyimide porous membrane layer and the polyolefin porous membrane layer and tightly attached to the polyolefin porous membrane layer and the polyimide porous membrane layer; and the pore diameter distribution of a polyimide porous membrane comprises that: the pore volume of pores of which pore diameters are 50 to 300 nanometers accounts for over 75 percent of the total pore volume, and the pore volume of pores of which pore diameters are less than 50 nanometers and more than 300 nanometers accounts for less than 25 percent of the total pore volume, and the pore diameter is measured by adopting a mercury intrusion method. A lithium ion battery manufactured by using the composite membrane as a battery membrane has improved service life and improved processing yield. Moreover, the composite membrane also has high thermal stability, and greatly improves the safety performance of the battery.
Description
Technical field
The present invention relates to the preparation method of a kind of composite diaphragm and this composite diaphragm, also relate to the battery that comprises this composite diaphragm.
Background technology
So far, use the lithium rechargeable battery of liquid electrolyte to be widely used.Yet; Because liquid electrolyte need be packaged in the metal-back of sealing, under the situation of some improper use, outside heat was delivered to inside battery through metal shell when for example battery was worked under hot environment; Inside battery heat release when perhaps discharging current is big; Inside battery or outside are understood overheated and inner pressure of battery are increased considerably, thereby blast owing to the liquid electrolyte thermally labile makes battery, therefore use the lithium rechargeable battery of liquid electrolyte to have potential safety hazard; Limit further developing of liquid electrolyte lithium rechargeable battery, therefore improved the key that lithium ion battery security is the research and development lithium rechargeable battery.
One of Security Countermeasures of lithium rechargeable battery are to make the electric current blocking; Wherein battery diaphragm plays important effect; Barrier film with polymer of loose structure melts under higher temperature; Thereby cause loose structure to be closed, impedance increases sharply and make electric current blocking, this temperature is called blocking (Shut-Down) temperature, claims self-closing temperature again.In addition, behind the bore closure of barrier film, if battery temperature continues to raise, when surpassing the heat resisting temperature of barrier film, barrier film can take place to melt fully, destroy, and causes positive pole, negative pole directly to contact and short circuit, and this temperature is called film destroy (break-out) temperature.(the self-closing temperature like the PE barrier film is 130-140 ℃ because fusion temperature is lower than 200 ℃ for battery diaphragm commonly used now such as polyethylene (PE), polypropylene (PP); The self-closing temperature of PP barrier film is about 170 ℃); In some cases; For example external temperature is too high, discharging current is excessive or electrolyte receives under the situation of the thermal inertia in the thermal process, even electric current is interdicted, the temperature of battery also possibly continue to raise; Therefore barrier film possibly be destroyed fully and cause battery short circuit, thereby causes battery explosion or catch fire.Therefore, adopt the fail safe of PE barrier film and PP barrier film lower.
Along with the development of lithium rechargeable battery in recent years; The requirement of high-capacity battery is increasing, and when using high-capacity battery, needs to reduce the internal resistance of cell; Thereby the factor that the inside battery heat is increased increases, and the security performance that therefore improves battery becomes even more important.
CN1725524A discloses a kind of separator for non-aqueous electrolyte battery; It is characterized in that; This barrier film is the separator for non-aqueous electrolyte battery that the micro-porous film by range upon range of polyolefin layer and refractory layer constitutes; Said refractory layer is to be that polyamide, polyimides or polyamidoimide more than 180 ℃ forms by fusing point, and its thickness is the 1-4 micron, and the air permeability of said barrier film is below 200 seconds.This invents the preparation method that said refractory layer is the micro-porous film of polyimides; Can only be used for soluble polyimide; And the dissolution conditions of soluble polyimide is comparatively harsh, thus greatly limited the range of application of polyimides, and be difficult to obtain the uniform polyimide composite film in aperture.
Summary of the invention
The objective of the invention is to overcome the uneven shortcoming of pore size of polyimide porous membrane in the composite diaphragm of prior art, provide a kind of by pore size evenly and the film formed composite diaphragm of the good polyimides of gas permeability and preparation method thereof and comprise the battery of this composite diaphragm.
The invention provides a kind of composite diaphragm; This composite diaphragm comprises polyolefin porous rete and polyimide porous membrane layer; Wherein, said composite diaphragm also comprises adhesive phase, and said adhesive phase is between polyimide porous membrane layer and polyolefin porous rete and polyolefin porous rete and polyimide porous membrane layer are fitted tightly; The pore-size distribution of said polyimide porous membrane does; Bore dia is that the pore volume in the hole of 50-300 nanometer accounts for more than 75% of total pore volume, and bore dia accounts for below 25% of total pore volume less than 50 nanometers and bore dia greater than the pore volume in the hole of 300 nanometers, and said bore dia adopts mercury injection method to record.
The present invention also provides a kind of preparation method of composite diaphragm; Wherein, This method is included between polyolefin porous rete and the polyimide porous membrane layer and forms adhesive phase; And polyolefin porous rete and polyimide porous membrane layer are fitted tightly, the pore-size distribution of said polyimide porous membrane is that bore dia is that the pore volume in the hole of 50-300 nanometer accounts for more than 75% of total pore volume; Bore dia accounts for below 25% of total pore volume less than 50 nanometers and bore dia greater than the pore volume in the hole of 300 nanometers, and said bore dia adopts mercury injection method to record.
The present invention also provides a kind of lithium rechargeable battery; This battery comprises this electrode group and nonaqueous electrolytic solution, and said electrode group and nonaqueous electrolytic solution are sealed in the battery container, and said electrode group comprises positive pole, negative pole and barrier film; Wherein, said barrier film is a composite diaphragm provided by the invention.
The pore diameter distribution of polyimide porous membrane is even in the composite diaphragm provided by the invention, thereby improved the useful life of the lithium ion battery that the composite diaphragm that made by this polyimide porous membrane processes as battery diaphragm; Make the gas permeability of this composite diaphragm fine, thereby can make the security performance of the lithium ion battery of processing as battery diaphragm by this perforated membrane good; Also make this composite diaphragm have higher mechanical strength, thereby the processed finished products rate of the lithium ion battery of being processed as battery diaphragm by this composite membrane is improved.Have higher thermal stability in addition, improved the security performance of battery greatly.
Description of drawings
The electron scanning micrograph that the amplification of the polyimide porous membrane that Fig. 1 makes for the embodiment of the invention 1 is 5000 times.
Embodiment
According to the present invention; Said composite diaphragm comprises polyolefin porous rete and polyimide porous membrane layer; Wherein, Said composite diaphragm also comprises adhesive phase, and said adhesive phase is between polyimide porous membrane layer and polyolefin porous rete and polyolefin porous rete and polyimide porous membrane layer are fitted tightly, and the pore-size distribution of said polyimide porous membrane does; Bore dia is that the pore volume in the hole of 50-300 nanometer accounts for more than 75% of total pore volume, and bore dia accounts for below 25% of total pore volume less than 50 nanometers and bore dia greater than the pore volume in the hole of 300 nanometers.The measurement of above-mentioned bore dia all adopts mercury injection method to carry out, and concrete method of measurement is conventionally known to one of skill in the art.
The uniformity in the hole of polyimide porous membrane is fine in the composite diaphragm provided by the invention, and gas permeability is fine, can make the composite diaphragm that made by this polyimide porous membrane have higher security performance as the lithium ion battery of battery diaphragm.
According to composite diaphragm provided by the invention, when composite diaphragm of the present invention is used for battery diaphragm, be that wherein, the average pore diameter of said polyimide porous membrane is the 0.01-5 micron, is preferably the 0.05-2 micron to the requirement of battery diaphragm; Porosity is 10-60 volume %, is preferably 25-45 volume %; Thickness is the 5-35 micron, be preferably the 12-25 micron; Gas permeability is 10-200 second/100cc, be preferably 20-180 second/100cc.Said polyolefin porous membrane can be for well known to a person skilled in the art various polyolefin porous membranes; When composite diaphragm of the present invention is used for battery diaphragm, to the requirement of battery diaphragm be, wherein; The average pore diameter of said polyolefin porous membrane is the 0.01-5 micron, is preferably the 0.05-2 micron; Porosity is 10-60 volume %, is preferably 25-45 volume %.Said porosity is meant that the cumulative volume of polyimide porous membrane mesopore accounts for the percentage of the volume of polyimide porous membrane.Said porosity adopts mercury injection method to measure.The pore structure of polyimide film is more even in the composite diaphragm of the present invention.
According to the present invention, the number of plies of said composite diaphragm is at least three layers, and promptly the intermediate layer is an adhesive phase, and the both sides of adhesive phase are respectively polyolefin porous rete and polyimide porous membrane layer.Under the preferable case; In order to improve the battery diaphragm security performance, the number of plies of said composite diaphragm is five layers, and the intermediate layer of said composite diaphragm is the polyolefin porous rete; Adhesive phase lays respectively at the both sides of this polyolefin porous rete, and outermost layer is the polyimide porous membrane layer; Perhaps, the intermediate layer of said composite diaphragm is the polyimide porous membrane layer, and adhesive phase lays respectively at the both sides of this polyimide porous membrane layer, and outermost layer is the polyolefin porous rete.The number of plies of said composite diaphragm also can be more than five layers; Wherein, Polyimide porous membrane layer and polyolefin porous rete are arranged in order, and have adhesive phase between adjacent polyimide porous membrane layer and the polyolefin porous membrane, when using this composite diaphragm in the battery; The gross thickness of the composite diaphragm that should guarantee finally to obtain is the 5-35 micron, is preferably the 12-25 micron.
According to composite diaphragm provided by the invention; Wherein, The preparation method of said polyimide porous membrane comprises the mixture formation polyamide acid film that contains polyamic acid, pore-forming material and solvent, this polyamide acid film is contacted with solidification liquid, and carry out imidization; Said solvent is for dissolving polyamic acid but slightly soluble or do not dissolve the solvent of pore shaping object matter, and said solidification liquid is for dissolving pore-forming material but slightly soluble or the insoluble liquid of separating polyamic acid.Described " slightly soluble " expression solubility is less than the 1g/100g solvent and greater than the 0.01g/100g solvent; " do not dissolve " expression solubility less than the 0.01g/100g solvent.
According to the present invention; Under the preferable case, the weight ratio of said pore-forming material and said polyamic acid is 0.01-0.3: 1, and the weight ratio of polyamic acid and said solvent is 1: 4.5-10; The weight ratio of polyamic acid and said solidification liquid is 1: 20-200 is preferably 1: 40-50.
The said mode that polyamide acid film is contacted with solidification liquid is for to be immersed in polyamide acid film in the solidification liquid, and the temperature of said solidification liquid is 0-50 ℃, and the time of said polyamide acid film being immersed said solidification liquid is 20-120 minute.At this moment, this polyamide acid film solidifies and removes the pore-forming material, has formed the perforated membrane of polyamic acid.
The pore-forming principle of this polyamic acid perforated membrane has following two kinds; A kind ofly be; Pore-forming material and polyamic acid are immiscible, can produce reaction with the pore-forming material but do not remove the pore-forming material with the material of polyamic acid reaction through using, thereby in polyamide acid film, form micropore; Another kind is that pore-forming material and polyamic acid are immiscible, can dissolve the pore-forming material but slightly soluble or the insoluble material of separating polyamic acid through adopting, and with the pore-forming substance dissolves, thereby in polyamide acid film, form micropore.
According to preparation method provided by the invention; According to above-mentioned first kind of pore-forming principle; Said pore-forming material is selected from one or more in hydroxide, aluminium hydroxide, alkali-metal phosphate and the sodium phosphate trimer of alkali earth metal, and particle mean size is the 0.01-2 micron.Wherein, the hydroxide of said alkali earth metal is magnesium hydroxide and/or calcium hydroxide; Said alkali-metal phosphate is tertiary sodium phosphate and tripotassium phosphate.Said solidification liquid is one or more in hydrochloric acid, sulfuric acid and the phosphoric acid.Experiment showed, that in hydrochloric acid, sulfuric acid and the phosphoric acid one or more all are not more than 1% (w/w) to one or more the 25 ℃ of solubility in the above-mentioned hydroxide that is selected from alkali earth metal as the pore-forming material, aluminium hydroxide, alkali-metal phosphate and the sodium phosphate trimer.
According to the present invention, the concentration of said hydrochloric acid is 5-35 weight %, and the concentration of said aqueous sulfuric acid is 5-98 weight %, and the concentration of said phosphate aqueous solution is 5-98 weight %.
According to the present invention; According to above-mentioned second kind of pore-forming principle, it is the phthalic acid dialkyl of 13-30 and in the methylin acetate one or more that said pore-forming material is selected from saturated carboxylic acid, benzoic acid polyol ester, carbon number that carbon number is 5-1 5; Said solidification liquid is one or more in methyl alcohol, ethanol, methyl ether, ether, acetone and the methyl propanediol.Wherein, said carbon number is that the saturated carboxylic acid of 5-10 is one or more in valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid and their isomers; Said benzoic acid polyol ester is benzoic acid one condensed ethandiol ester and/or benzoic acid one propylene glycol ester that contracts; Said carbon number is that the phthalic acid dialkyl of 13-30 is one or more in terephthalic acid (TPA) diamyl ester, M-phthalic acid two capronates and the dinonyl phthalate; Said methylin acetate is 1-Methoxy-2-propyl acetate and/or glycol methyl ether acetate.Experiment showed, that in methyl alcohol, ethanol, methyl ether, ether, acetone and the methyl propanediol one or more are that the phthalic acid dialkyl of 13-30 and one or more the 25 ℃ of solubility in the methylin acetate all are not more than 1% (w/w) to above-mentioned be selected from saturated carboxylic acid, benzoic acid polyol ester, carbon number that carbon number is 5-15 as the pore-forming material.
According to the present invention; Said solvent can be the various solvents that can dissolve polyamic acid; The example of this solvent comprises N-2-methyl pyrrolidone (NMP), N; N-dimethylacetylamide (DMAc), oxolane (THF), N, one or more in dinethylformamide (DMF), m-cresol, dimethyl sulfoxide (DMSO) (DMSO) and the methyl alcohol.Experiment showed, that above-mentioned solvent all is not more than 1% (w/w) to 25 ℃ of solubility of aforementioned pore-forming material.
According to the present invention, said polyamic acid can be purchased acquisition, also can obtain through tetracarboxylic dianhydride and organic diamine are reacted in solvent.When adopting tetracarboxylic dianhydride and organic diamine in solvent during the prepared in reaction polyamic acid solution; Said pore-forming material can be before reaction, any stage after the reaction neutralization reaction adds; The pore-forming material is mixed with polyamic acid solution more equably, and the present invention adds the pore-forming material before being chosen in reaction.The preparation method who is said polyamic acid solution comprises tetracarboxylic dianhydride, organic diamine, pore-forming material and solvent; Obtain uniform mixture; This mixture is formed polyamide acid film; And be lower than drying under the vitrification point of polyamic acid, and dried said polyamide acid film is immersed in the solidification liquid remove the pore-forming material, then carry out imidization.
According to the present invention; Under preferable case; The mol ratio of said tetracarboxylic dianhydride and organic diamine is 0.8-1.2; 1.00-1.02 more preferably, the weight ratio of the total amount of tetracarboxylic dianhydride and organic diamine and pore-forming material is 1: 0.01-0.3, the total amount of tetracarboxylic dianhydride and organic diamine and the weight ratio of said solvent are 1: 4.5-10.
According to preparation method provided by the invention, under preferable case, the temperature of tetracarboxylic dianhydride, organic diamine, pore-forming material and solvent being carried out condensation reaction is 20-70 ℃, and the time of contact is 3-15 hour.
According to the present invention, can utilize various technology well known in the art to make polyamic acid solution form polyamide acid film, for example; Can the mixture that contain polyamic acid, pore-forming material and solvent be coated on the supporter; Drying is removed supporter after removing and desolvating, and can obtain polyamide acid film.The polyamide acid film that obtain this moment is the low-down film of porosity of non-porous film or film, is not the perforated membrane on the ordinary meaning, can not satisfy the requirement of battery diaphragm to porosity, aperture and pore size distribution.
The step that polyamic acid solution is coated on the supporter is that 10-40 ℃, relative humidity are to carry out under the condition of 20-80% in temperature preferably.
The method that applies can be a whole bag of tricks well known in the art, for example spin-coating method, knife coating, The tape casting, dip coating etc.The amount that applies depend on thickness or the thickness of polyimide film and the concentration of polyamic acid solution of the polyamide acid film that will obtain.Generally speaking, to make the thickness of final gained polyimide porous membrane be the 5-35 micron to the amount of coating.Experiment showed, THICKNESS CONTROL with the polyamide acid film that forms in the 30-500 micrometer range, the thickness that can make final gained polyimide porous membrane is the 5-35 micron.Under the situation that thickness is confirmed and polyamic acid solution concentration is known, those skilled in the art are easy to grasp the coated weight of polyamic acid solution.
Said supporter can be selected from a kind of in corrosion resistant plate, polyethylene film, polypropylene film, polyester film, Copper Foil and the aluminium foil.
Removing the method for desolvating can be for well known to a person skilled in the art the whole bag of tricks, and like methods such as air dry, heat drying, vacuumizes, dry condition comprises that temperature can be 20-150 ℃, and the time can be 5-20 minute.
Thereby improve the quality of the final polyimide porous membrane that obtains for the quality that further improves polyamide acid film; Under the preferable case, the polyamic acid solution described in the method provided by the invention is the polyamic acid solution of process at 15-40 ℃ of following vacuum degassing 1-12 hour preferred 1-2 hour.In other words, under the preferable case, method provided by the invention also is included in before the polyamic acid solution film forming, earlier with polyamic acid solution at 15-40 ℃ of following vacuum degassing 1-12 hour, preferred 1-2 hour, to remove the bubble that possibly exist in the solution.The vacuum degree of said vacuum degassing can guarantee the non-volatile or a small amount of volatilization of polyamic acid solution, and under the preferable case, said vacuum degree is the 0.001-0.1 MPa.
According to the present invention; In order further to improve the quality of polyimide porous membrane; Prevent that solidification liquid from causing adverse effect to polyimide porous membrane, under the preferable case, method provided by the invention comprises that also the polyamide acid film with the porous that obtains cleans with cleaning agent.Said cleaning agent can be that carbon number is alcohol and/or the ketone of 2-8, is preferably ethanol, acetone or the mixture of the two.Clean temperature 0-60 ℃, be preferably 20-50 ℃.The mode of said cleaning can be with cleaning agent the polyamide acid film of porous to be carried out drip washing and/or dipping.The number of times of drip washing is preferably 3-5 time, and the time of dipping can be 3-6 hour.Ultrasonic wave capable of using is auxiliary during dipping cleans.
Among the present invention; The condition that the polyamide acid film of porous is carried out imidizate can be the condition of conventional amic acid imidizate; Concrete method of operation also has been conventionally known to one of skill in the art; For example, can realize in 2-7 hour through polyamide acid film heating under 70-400 ℃ porous.
Can directly heat up and also can adopt program mode to heat up to raise the temperature to 70-400 ℃, the present invention preferably adopts with 4-8 ℃/minute heating rate temperature programming to 70-400 ℃, so that the abundant imidizate of polyamic acid generates required polyimides.Further preferably make the polyamide acid film of porous be 70-200 ℃ of maintenance 0.5-4 hour down, keep realizing in 0.5-3 hour imidizate down at 200 ℃-400 ℃ in temperature through programmed temperature method.The experiment proof; The reaction that the amic acid dehydration generates polyimides only takes place under this condition; Can't cause the distribution in above-mentioned in type hole, the variation of size, thereby the polyimide film that obtains still keeps the loose structure in the polyamide acid film of porous, become polyimide porous membrane.
Can improve the conversion ratio that polyamic acid is converted into polyimides through raising reaction temperature, prolongation reaction time.Under the above-mentioned condition of the present invention; Polyamic acid is converted into the conversion ratio of polyimides greater than 99%; And owing to the present invention improves the pore-forming mode of polyimide porous membrane; The mode that is transformed into polyimides by polyamic acid then adopts usual manner, therefore in the specific embodiment of the invention, the amount of polyamic acid is not made special demands.In addition, the existence of a small amount of polyamic acid does not have much affect to thermal endurance, gas permeability and the percent thermal shrinkage of polyimide porous membrane, has the polyamic acid below 2% in the polyimide porous membrane that therefore allows to obtain.
Preferably adopt binary organic acid acid anhydride and organic diamine to carry out condensation reaction in the specific embodiment of the invention and prepare polyamic acid.The example of said binary organic acid acid anhydride includes but not limited to like BPDA (s-BPDA), benzophenone tetracarboxylic dianhydride (BTDA), pyromellitic acid anhydride (PMDA), oxygen biphenyl tetracarboxylic acid anhydrides (ODPA) and bisphenol-A two ether dianhydrides (BPADA).The example of said organic diamine includes but not limited to 4,4 '-diaminodiphenyl ether (4,4 '-ODA), 3,4 '-diaminodiphenyl ether (3,4 '-ODA), p-phenylenediamine (PPD) (PDA), m-phenylene diamine (MPD) (mDA), 3,3 '-diphenyl sulphone (DPS) diamines, 4,4 '-diphenyl sulphone (DPS) diamines.
The mol ratio of said polynary organic carboxyl acid or derivatives thereof and organic diamine is preferably 0.8-1.2, more preferably 1.00-1.02.Under the preferable case, the weight ratio of total feeding quantity of the feeding quantity of said solvent and polynary organic carboxyl acid or derivatives thereof and organic diamine is 4.5-10.The temperature of condensation reaction is preferably 20-70 ℃, and the time is preferably 3-15 hour.
Among the present invention, said polyimides can be the polymer that contains imide group in the conventional various repetitives in this area, and under the preferable case, said polyimides is the polyimides with following structural formula.
Wherein, wherein, A
1Be preferably the aryl of following structure:
Said diamines can be to have NH
2-A
2-NH
2The diamines of the structure of expression, A
2Can be the aryl of following structure:
Polymerization degree n is 50-10000, and heat decomposition temperature is more than 420 ℃.
One skilled in the art will appreciate that because general polyimides (PI) is a kind of insoluble high molecular polymer its degree of polymerization is difficult to accurately measure, and the inherent viscosity of another the physical parameter polyamic acid directly related with the degree of polymerization is closely related.Polyamic acid is by the intermediate in acid dianhydride and the amine prepared in reaction polyimides course of reaction; Discover; Through control polyamic acid inherent viscosity within the specific limits; Can obtain the polyimides of the required degree of polymerization or desired physical properties, and inherent viscosity be one with the irrelevant physical parameter that can objectively respond the polyamic acid degree of polymerization of measuring condition, so this area uses the inherent viscosity of polyamic acid to represent the degree of polymerization of polyamic acid and polyimides usually.The present invention continues to use the degree of polymerization that said method characterizes polyimide film at this.Inventor of the present invention discovers; As long as being controlled at 100-200 milliliter/gram, the inherent viscosity of polyamic acid that will be corresponding with this polyimides preferably can realize the object of the invention at 140-190 milliliter/gram; Therefore; Among the present invention, be that 100-200 milliliter/gram is preferably 140-190 milliliter/gram as long as make the inherent viscosity of the polyamic acid corresponding with this polyimides.
Under the preferable case, said polyimides for the PMMI corresponding with tetracarboxylic dianhydride and diamines, gather the biphenyl tetracarboxylic acid imide, gather in the benzophenone tetramethyl acid imide one or more.Preferred said PMMI is selected from and gathers the equal diimides of N-phenyl, gathers the equal diimides of N-xenyl, gathers in the equal diimides of N-hexichol ether one or more; The said biphenyl tetracarboxylic acid imide that gathers is selected from and gathers N-phenyl biphenyl tetracarboxylic acid imide, gathers N-xenyl biphenyl tetracarboxylic acid imide, gathers in the N-hexichol ether biphenyl tetracarboxylic acid imide one or more; The said benzophenone tetramethyl acid imide that gathers is selected from and gathers N-phenyl benzophenone tetramethyl acid imide, gathers N-xenyl benzophenone tetramethyl acid imide, gathers in the N-hexichol ether benzophenone tetramethyl acid imide one or more.
A preferred embodiment of the invention, the preparation method of polyimide porous membrane of the present invention comprises the steps:
(1) with tetracarboxylic dianhydride and organic diamine according to mol ratio 0.8-1.2: 1 ratio adds in the solvent; It is 5-40 weight % that the consumption of solvent makes the concentration of the polyamic acid that obtains; After 20-70 ℃ of following stirring reaction 3-15 hour; Add the pore-forming material, the pore-forming material is 0.01-0.3 with the weight ratio of the polyamic acid that obtains: 1; Under uniform temp, obtained polyamic acid solution in vacuum degassing 1-12 hour;
(2) be that 10-40 ℃, relative humidity are under the 20-80% condition in temperature, above-mentioned polyamic acid solution be coated on stainless steel or the glass support, 20-200 ℃ dry down, remove the polyamide acid film that obtains the 5-50 micron after desolvating;
(3) supporter of above-mentioned polyamide acid film is put into 10-50 ℃ solidification liquid dipping 20-120 minute, obtained the polyamide acid film of porous;
(4) with the polyamide acid film of the above-mentioned porous that obtains in 10-50 ℃ cleaning agent soaking and washing 3-6 hour; The progressively mode of imidization of gradient increased temperature is adopted in dry back; Heating is converted into polyimides with polyamic acid under nitrogen, argon gas or vacuum, obtains polyimide porous membrane.The temperature of heating is 100-200 ℃ and keeps down 0.5-1.5 hour, 180-250 ℃ to keep 0.5-1.5 hour, 230-280 ℃ to keep 0.5-1.5 hour, 260-350 ℃ to keep 0.5-1.5 hour down down down.
Method provided by the invention can be qualitatively judged according to the ABC of organic synthesis and polyimide film can be accessed.Certainly, also can carry out qualitative sign according to infrared spectrum.1720cm in the infrared spectrum
-1Near strong peak is a C=O stretching vibration absworption peak, 1380cm
-1Strong peak is a C-N stretching vibration absworption peak in neighbouring.If occur above-mentioned peak in the infrared spectrum, then can explain to have obtained polyimides.Said infrared spectrum spectrogram can adopt the U.S. NEXUS470 of Nicolet company type fourier transform infrared spectroscopy, KBr coating to obtain.The said determination method has been conventionally known to one of skill in the art, repeats no more at this.Owing to adopt very ripe method synthesis of polyimides among the present invention, just the pore-forming mode is improved, so especially the structure of polyimide film is not characterized in an embodiment.
Size, porosity and the gas permeability in the formed polyimides of the present invention hole all has relation with polyamic acid solution concentration, solidification liquid, film-forming temperature, humidity, can realize the control to the polyimide porous membrane quality through regulating these parameters.
Method provided by the invention is included between polyolefin porous rete and the polyimide porous membrane layer and forms adhesive phase; And polyolefin porous rete and polyimide porous membrane layer are fitted tightly, said polyimide porous membrane is the polyimide porous membrane described in the present invention.
According to method of the present invention; Adopt adhesive that polyolefin porous membrane and polyimide porous membrane of the present invention are fitted tightly and obtain composite diaphragm; The kind of said adhesive and consumption are conventionally known to one of skill in the art; For example; Said adhesive can be selected from the copolymer of Kynoar, polyvinyl chloride, polytetrafluoroethylene, tetrafluoroethylene/hexafluoropropylene, the copolymer of tetrafluoroethylene/perfluoro alkyl vinyl ether, the copolymer, 1 of ethylene/tetrafluoroethylene; In the copolymer of 1-difluoroethylene/hexafluoroethylene, polyimides, polyamic acid, polyurethane, phenolic resins, polyethylene and the polypropylene one or more, said adhesive consumption make that usually the thickness of adhesive layer is the 0.5-20 micron.
According to the present invention; This method also is included between polyolefin porous rete and the polyimide porous membrane layer and forms adhesive phase; And making the drying steps after polyolefin porous rete and polyimide porous membrane layer fit tightly, the method for said drying and condition are conventionally known to one of skill in the art, for example; Dry temperature can be 40-140 ℃, and the dry time can be 2-180 minute.
Under the preferable case; Can also contain additive in the adhesive according to the invention, and the composite diaphragm that obtains after bonding was flooded in solvent 1-60 minute, dry then; Said additive can play the effect of pore-forming; The solvent of dipping can still can't impact the structure of composite diaphragm by solubilising additive, can play the effect that makes the adhesive phase pore-forming, is beneficial to reach the purpose that is communicated with hole between polyolefin porous rete and the polyimide porous membrane layer.Said additive can be selected from silicon dioxide, magnesium hydroxide, aluminium hydroxide, benzoic acid one condensed ethandiol ester, dinonyl phthalate, 1-Methoxy-2-propyl acetate, certain herbaceous plants with big flowers acid, calcium hydroxide, magnesium sulfate, tertiary sodium phosphate, sodium phosphate trimer, tripotassium phosphate, N; Dinethylformamide, N; N-DEF, N; N-dimethylacetylamide, N, one or more in N-diethyl acetamide, dimethyl sulfoxide (DMSO), dimethyl sulfone, N-methyl pyrrolidone, N-cyclohexyl-2-Pyrrolidone, trimethyl urea, hexamethyl phosphoramide, diethylene glycol dimethyl ether, pyridine and the picoline.The adjustable extent broad of the weight ratio of said additive and adhesive is preferably 0.1-3: 1.
Said dipping can be selected from hydrochloric acid, sulfuric acid, phosphoric acid, ethanol, acetone, butanone, methyl ether, ether and the methyl propanediol one or more with solvent.Dry method and condition are conventionally known to one of skill in the art, and like air dry, vacuumize and forced air drying etc., dry temperature can be-100 ℃ of room temperatures (25 ℃), and the dry time can be 10-180 minute.
The present invention also provides a kind of lithium rechargeable battery; This battery comprises this electrode group and nonaqueous electrolytic solution, and said electrode group and nonaqueous electrolytic solution are sealed in the battery container, and said electrode group comprises positive pole, negative pole and barrier film; Wherein, said barrier film is a composite diaphragm provided by the invention.
Lithium ion battery provided by the invention comprises battery case and the electrode group and the electrolyte that are encapsulated in this enclosure, and said electrode group comprises reels or stacked positive pole, barrier film and negative pole successively, and wherein, said barrier film is a composite diaphragm provided by the invention.
Because the present invention only relates to useful life and the security performance that lithium rechargeable battery is provided through the improvement to battery diaphragm; According to lithium ion battery provided by the invention; The positive pole of said battery, negative pole and electrolyte all can adopt and well known to a person skilled in the art various positive poles, negative pole and electrolyte, and specifically prescription and preparation method repeat no more at this.
Following embodiment will do further description to the present invention.In an embodiment, among the embodiment there be used primary raw material:
Pyromellitic acid anhydride: SHANGHAI RESEARCH INSTITUTE OF SYNTHETIC RESINS;
Benzophenone tetracarboxylic dianhydride (BTDA): SHANGHAI RESEARCH INSTITUTE OF SYNTHETIC RESINS;
Bisphenol-A two ether dianhydrides: Shanghai synthetic resin research institute;
Oxygen bibenzene tetracarboxylic dianhydride: Shanghai chemical reagents corporation;
P-phenylenediamine (PPD): chemical reagent purchase and supply 5-linked chemical plant, Shanghai;
N, N-dimethylacetylamide, N-methyl pyrrolidone: Shanghai chemical reagent work.
Embodiment 1
Present embodiment is explained the preparation of composite diaphragm provided by the invention
(1) with 4; 4 '-diaminodiphenyl ether and pyromellitic acid anhydride join 300 milliliters N with 1: 1 mol ratio; In the N-dimethylacetylamide, wherein solid content (weight of the polyamic acid that solid content refers to generate in the system accounts for the mass percent of mixture total weight amount) is 10 weight %.25 ℃ of following stirring reactions 8 hours, add 3 gram 1-Methoxy-2-propyl acetates then, and vacuum degassing 1 hour under this temperature, obtain thick mixture, the inherent viscosity η of this mixture
Int=150 milliliters/gram (condition determination: Ubbelohde viscometer, 30 ℃ of constant temperature, mixture diluted is 0.005 grams per milliliter to solid content);
(2) be that 10 ℃, relative humidity are under 50% condition in temperature, said mixture is coated on the corrosion resistant plate, remove after dry 20 minutes down at 100 ℃ and desolvate, obtain polyamide acid film;
(3) the above-mentioned corrosion resistant plate that has polyamide acid film was flooded 60 minutes down at 20 ℃ in 100 milliliters of solidification liquids of being made up of ethanol, ether and acetone (volume ratio of ethanol, ether and acetone is 3: 2: 1); Be cured, pore-forming, 40 ℃ dry 20 hours down; Ultrasonic cleaning 1 hour in 25 ℃ water then; Descended dry 20 hours at 40 ℃ afterwards, obtain the polyamide acid film of porous;
(4) adopt the progressively mode of imidizate of gradient increased temperature, the polyamide acid film of above-mentioned porous is heated in nitrogen carry out imidizate, obtain thickness and be 33 microns polyimide porous membrane.The mode of heating is to keep 1 hour down at 150 ℃, and 200 ℃ kept 1 hour down, and 250 ℃ kept 1 hour down, and 320 ℃ kept 1 hour down.
Adopt sem observation to observe the pore size distribution of the above-mentioned polyimide porous membrane that obtains, resultant electron scanning micrograph is as shown in Figure 1.Can find out that from this figure polyimide porous membrane is a three-dimensional net structure, i.e. the surface of film and inner crisscross a large amount of hole that distributing; Hole is circular or oval, and is tortuous circuitous, communicates with each other; And the distribution in hole and aperture are all comparatively even, and the pattern in hole is better.
Adopt mercury injection method to measure the pore volume of bore dia and account for 93% of total pore volume in the hole of 110-130 nanometer.The pore-size distribution that this polyimide porous membrane is described is very even.
(5) be that 1: 0.25 mixed obtains adhesive with polyimides adhesive and silicon dioxide according to weight ratio;
(6) adhesive that step (5) is obtained is coated on the polyimide porous membrane that step (4) obtains; The amount that applies makes that the thickness of adhesive phase is 2 microns, and with thickness be that 18 microns polypropylene porous film (U.S. CE LGARD) is bonding, 120 ℃ dry 0.5 hour down; In hydrochloric acid, flooded 60 minutes then; After the taking-up,, obtain the composite diaphragm of polyimide porous membrane/polypropylene porous film 40 ℃ of dryings 1 hour.
Embodiment 2
Present embodiment is explained the preparation of composite diaphragm provided by the invention
Method according to embodiment 1 prepares composite diaphragm, and different is that when the preparation polyimide porous membrane, the amount of the pore-forming material 1-Methoxy-2-propyl acetate that in step (1), adds is 6 grams, obtains thick mixture, the inherent viscosity η of this mixture
Int=180 milliliters/gram (condition determination: Ubbelohde viscometer, 30 ℃ of constant temperature, mixture diluted is 0.005 grams per milliliter to solid content).Finally obtain thickness and be 19 microns polyimide porous membrane.
Adopt mercury injection method to measure the pore volume of aperture and account for 78% of total pore volume in the hole of 160-190 nanometer.The pore-size distribution that this polyimide porous membrane is described is very even.
Embodiment 3
Present embodiment is explained the preparation of composite diaphragm provided by the invention
Method according to embodiment 1 prepares composite diaphragm, and different is that when the preparation polyimide porous membrane, the amount of the pore-forming material 1-Methoxy-2-propyl acetate that in step (1), adds is 5 grams, obtains thick mixture, the inherent viscosity η of this mixture
Int=160 milliliters/gram (condition determination: Ubbelohde viscometer, 30 ℃ of constant temperature, mixture diluted is 0.005 grams per milliliter to solid content).Finally obtain thickness and be 14 microns polyimide porous membrane.
Adopt mercury injection method to measure the pore volume of aperture and account for 88% of total pore volume in the hole of 160-210 nanometer.The pore-size distribution that this polyimide porous membrane is described is very even.
Embodiment 4
Present embodiment is explained the preparation of composite diaphragm provided by the invention
(1) with 4,4 '-diaminodiphenyl ether and benzophenone tetracarboxylic dianhydride (BTDA) join 300 milliliters of N with 1: 1 mol ratio, and in the N-dimethylacetylamide, wherein solid content is 12 weight %.40 ℃ of following stirring reactions 10 hours, add 4 gram capric acid then, and back vacuum degassing 1 hour under this temperature, obtain thick mixture, the inherent viscosity η of this mixture
Int=188 milliliters/gram (condition determination: Ubbelohde viscometer, 30 ℃ of constant temperature, mixture diluted is 0.005 grams per milliliter to solid content);
(2) be that 20 ℃, relative humidity are under 60% condition in temperature, said mixture is coated on the corrosion resistant plate, obtain polyamide acid film after dry 10 minutes down at 120 ℃;
(3) the above-mentioned corrosion resistant plate that has polyamide acid film was flooded 60 minutes down at 25 ℃ in 500 milliliters of solidification liquids of being made up of ethanol and ether (volume ratio of ethanol and ether is 2: 1); Be cured, pore-forming, 40 ℃ dry 5 hours down; Ultrasonic cleaning 1 hour in 25 ℃ of water then; Descended dry 20 hours at 40 ℃ afterwards, obtain the polyamide acid film of porous;
(4) adopt the progressively mode of imidizate of gradient increased temperature, the polyamide acid film of above-mentioned porous is heated in nitrogen carry out imidizate, obtain thickness and be 26 microns polyimide porous membrane.The mode of heating is to keep 1 hour down at 160 ℃, and 210 ℃ kept 0.8 hour down, and 230 ℃ kept 1.2 hours down, and 320 ℃ kept 1 hour down.
Adopt mercury injection method to measure the pore volume of aperture and account for 87% of total pore volume in the hole of 275-300 nanometer.The pore-size distribution that this polyimide porous membrane is described is very even.
(5) be that 1: 0.4 mixed obtains adhesive with synvaren and benzoic acid one condensed ethandiol ester according to weight ratio;
(6) adhesive that step (5) is obtained is coated on the polyimide porous membrane that step (4) obtains; The amount that applies makes that the thickness of adhesive phase is 5 microns; And with thickness be that 16 microns polyethylene porous membrane (Japanese Asahi Chemical Industry) is bonding, 70 ℃ dry 1.5 hours down, dipping 30 minutes in ethanol then; 70 ℃ of dryings 1 hour, obtain the composite diaphragm of polyimide porous membrane/polyethylene porous membrane.
Embodiment 5
Present embodiment is explained the preparation of composite diaphragm provided by the invention
(1) with 4,4 '-diaminodiphenyl ether and pyromellitic acid anhydride join among 300 milliliters of NMP with 1: 1 mol ratio, and wherein solid content is 12 weight %., add 1 gram magnesium hydroxide and 1.5 gram aluminium hydroxides then, and obtain thick mixture, the inherent viscosity η of this mixture after 15 hours at 25 ℃ of following stirring reactions
Int=143 milliliters/gram (condition determination: Ubbelohde viscometer, 30 ℃ of constant temperature, mixture diluted is 0.005 grams per milliliter to solid content);
(2) be that 30 ℃, relative humidity are under 80% condition in temperature, said mixture is coated on the corrosion resistant plate, dry naturally after 10 minutes and obtain polyamide acid film;
(3) the above-mentioned corrosion resistant plate that has polyamide acid film was flooded 80 minutes down at 25 ℃ in 600 milliliters of solidification liquids of being made up of hydrochloric acid and phosphoric acid (volume ratio of hydrochloric acid and phosphoric acid is 2: 1); Be cured, pore-forming, in 25 ℃ water, cleaned 10 hours; Descended dry 10 hours at 40 ℃ afterwards, obtain the polyamide acid film of porous;
(4) adopt the progressively mode of imidizate of gradient increased temperature, the polyamide acid film of above-mentioned porous is heated in nitrogen carry out imidizate, obtain thickness and be 35 microns polyimide porous membrane.The mode of heating is to keep 1 hour down at 80 ℃, and 120 ℃ kept 1 hour down, and 180 ℃ kept 1 hour down, and 250 ℃ kept 1 hour down, and 300 ℃ kept 1 hour down, and 350 ℃ kept 1 hour down.
Adopt mercury injection method to measure the pore volume of aperture and account for 80% of total pore volume in the hole of 75-120 nanometer.The pore-size distribution that this polyimide porous membrane is described is very even.
(5) be that 1: 0.5 mixed obtains adhesive with polyurethane adhesive and benzoic acid one condensed ethandiol ester according to weight ratio;
(6) adhesive that step (5) is obtained is coated on the polyimide porous membrane that step (4) obtains; It is 6 microns that the amount that applies makes the thickness of adhesive phase; And with thickness be that 16 microns polyethylene porous membrane (Japanese Asahi Chemical Industry) is bonding, 70 ℃ of following dry 2 times, dipping 20 minutes in the mixed solution of butanone and ethanol (volume ratio is 1: 1) then; Drying is 2 hours under 40 ℃, obtains the composite diaphragm of polyimide porous membrane/polyethylene porous membrane.
Embodiment 6
Present embodiment is explained the preparation of composite diaphragm provided by the invention
(1) with 4,4 '-diaminodiphenyl ether and bibenzene tetracarboxylic dianhydride join among 300 milliliters of NMP with 1: 1 mol ratio, and wherein solid content is 12 weight %.55 ℃ of following stirring reactions 8 hours; The mixture (volume ratio is 4: 3: 1) that adds 1 gram phthalic acid fat in two ninth of the ten Heavenly Stems, capric acid and o-phthalic acid dibutyl ester then; And vacuum degassing 2 hours under this temperature, obtain thick mixture, the inherent viscosity η of this mixture
Int=145 milliliters/gram (condition determination: Ubbelohde viscometer, 30 ℃ of constant temperature, mixture diluted is 0.005 grams per milliliter to solid content);
(2) be that 30 ℃, relative humidity are under 70% condition in temperature, said mixture is coated on the corrosion resistant plate, obtain polyamide acid film after dry 10 minutes down at 100 ℃;
(3) with the above-mentioned corrosion resistant plate that has a polyamide acid film in 1000 milliliters of acetone at 25 ℃ of dippings 30 minutes down, be cured, pore-forming, 40 ℃ dry 10 hours down, obtain the polyamide acid film of porous;
(4) adopt the progressively mode of imidizate of gradient increased temperature, the polyamide acid film of above-mentioned porous is heated in nitrogen carry out imidizate, obtain thickness and be 23 microns polyimide porous membrane.The mode of heating is to keep 1 hour down at 150 ℃, and 200 ℃ kept 1 hour down, and 250 ℃ kept 1 hour down, and 300 ℃ kept 1 hour down.
Adopt mercury injection method to measure the pore volume of aperture and account for 79% of total pore volume in the hole of 50-80 nanometer.The pore-size distribution that this polyimide porous membrane is described is very even.
(5) polyurethane adhesive is coated on the polyimide porous membrane that step (4) obtains; It is 5 microns that the amount that applies makes the thickness of adhesive phase; And with thickness be that 16 microns polyethylene porous membrane (Japanese Asahi Chemical Industry) is bonding; Drying is 1.5 hours under 40 ℃, obtains the composite diaphragm of polyimide porous membrane/polyethylene porous membrane.
Embodiment 7
Present embodiment is explained the preparation of composite diaphragm provided by the invention
(1) with 4,4 '-diaminodiphenyl ether and bibenzene tetracarboxylic dianhydride join among 300 milliliters of DMF with 1: 1 mol ratio, and wherein solid content is 15 weight %.20 ℃ of following stirring reactions 8 hours, add 3 gram phthalic acid fat in two ninth of the ten Heavenly Stems then, and, obtain thick mixture, the inherent viscosity η of this mixture 15 ℃ of following vacuum degassings 2 hours
Int=166 milliliters/gram (condition determination: Ubbelohde viscometer, 30 ℃ of constant temperature, mixture diluted is 0.005 grams per milliliter to solid content);
(2) be that 30 ℃, relative humidity are under 40% condition in temperature, said mixture is coated on the corrosion resistant plate, dry naturally after 60 minutes and obtain polyamide acid film;
(3) with the above-mentioned corrosion resistant plate that has a polyamide acid film in 500 milliliters of ethanol at 25 ℃ of dippings 60 minutes down, be cured, pore-forming, 40 ℃ dry 10 hours down, obtain the polyamide acid film of porous;
(4) adopt the progressively mode of imidizate of gradient increased temperature, the polyamide acid film of above-mentioned porous is heated in nitrogen carry out imidizate, obtain thickness and be 45 microns polyimide porous membrane.The mode of heating is to keep 1 hour down at 150 ℃, and 200 ℃ kept 1 hour down, and 250 ℃ kept 1 hour down, and 320 ℃ kept 1 hour down.
Adopt mercury injection method to measure the pore volume of aperture and account for 85% of total pore volume in the hole of 80-110 nanometer.The pore-size distribution that this polyimide porous membrane is described is very even.
(5) be that 1: 1.5 mixed obtains adhesive with polyurethane adhesive and benzoic acid one condensed ethandiol ester according to weight ratio;
(6) adhesive that step (5) is obtained is coated on the both sides of the polyimide porous membrane that step (4) obtains; It is 7 microns that the amount that applies makes the thickness of every layer of adhesive phase; And be that 16 microns polyethylene porous membrane (Japanese Asahi Chemical Industry) is bonded in respectively on the both side surface of polyimide porous membrane with thickness; Drying is 30 minutes under 50 ℃; In the mixed solution of butanone and ethanol (volume ratio is 1: 1), flooded 20 minutes then, drying is 1 hour under 50 ℃, obtains the composite diaphragm of polyethylene porous membrane/polyimide porous membrane/polyethylene porous membrane.
Embodiment 8
Present embodiment is explained the preparation of composite diaphragm provided by the invention
(1) with 4,4 '-diaminodiphenyl ether and bibenzene tetracarboxylic dianhydride join 300 milliliters of N with 1: 1 mol ratio, in the N-dimethylacetylamide (DMAc); Solid content is 10 weight %; 20 ℃ of following stirring reactions 4 hours, add 2.5 gram benzoic acid, one condensed ethandiol fat then, and 15 ℃ of following vacuum degassings 2 hours; Obtain thick mixture, the inherent viscosity η of this mixture
Int=178 milliliters/gram (condition determination: Ubbelohde viscometer, 30 ℃ of constant temperature, mixture diluted is 0.005 grams per milliliter to solid content);
(2) be that 30 ℃, relative humidity are under 40% condition in temperature, said mixture is coated on the corrosion resistant plate, dry naturally after 60 minutes and obtain polyamide acid film;
(3) with the above-mentioned corrosion resistant plate that has a polyamide acid film in 1000 milliliters of sulfuric acid at 25 ℃ of dippings 45 minutes down, be cured, pore-forming, dipping 10 hours in 30 ℃ acetone then, afterwards 70 ℃ dry 10 hours down, obtain the polyamide acid film of porous;
(4) adopt the progressively mode of imidizate of gradient increased temperature, the polyamide acid film of above-mentioned porous is heated in nitrogen carry out imidizate, obtain thickness and be 18 microns polyimide porous membrane.The mode of heating is to keep 1 hour down at 150 ℃, and 200 ℃ kept 1 hour down, and 250 ℃ kept 1 hour down, and 320 ℃ kept 1.5 hours down.
Adopt mercury injection method to measure the pore volume of aperture and account for 89% of total pore volume in the hole of 195-220 nanometer.The pore-size distribution that this polyimide porous membrane is described is very even.
(5) be that 1: 0.8 mixed obtains adhesive with polyurethane adhesive and benzoic acid one condensed ethandiol ester according to weight ratio;
(6) adhesive that step (5) is obtained is coated in the both sides that thickness is 16 microns polyethylene porous membrane (Japanese Asahi Chemical Industry) respectively; It is 2 microns that the amount that applies makes the thickness of adhesive phase of a side of polyethylene porous membrane layer; And the polyimide porous membrane that step (4) obtains is bonded in respectively on the both sides of polyethylene porous membrane; Placed 2 hours in the ventilation; In the mixed solution of butanone and ethanol (volume ratio is 1: 1), flooded 20 minutes then, drying is 1 hour under 70 ℃, obtains the composite diaphragm of polyimide porous membrane/polyethylene porous membrane/polyimide porous membrane.
Comparative Examples 1
The preparation of this Comparative Examples explanation reference composite diaphragm
Pyromellitic acid anhydride, diaminodiphenyl ether, polymeric chain one end are contained amino polystyrene, and (weight average molecular weight is 15000; Available from Aldrich company) join 100 milliliters of N-2-methyl pyrrolidones (NMP) with 1: 1: 0.008 mol ratio and at room temperature mix; Obtain the solution of homogeneous; The solid content of this solution is 10 weight %, films with the I-shaped spreader of filming then, obtains thickness and be 0.5 millimeter film.
This film was removed solvent in 2 hours 120 ℃ of heating; ℃ carried out imidizate 3 hours with 5 ℃ of/minute temperature programmings to 300 then, be warmed up to 350 ℃ again and kept 1.5 hours, be cooled to 120 ℃ at last and carry out biaxial stretching simultaneously and handle; Draw speed 10 mm/min; Draw ratio vertically (MD) is 2 times, and laterally (TD) is 2 times, obtains battery diaphragm of the present invention thus.
Wherein there is 1720cm in the fourier-transform infrared spectrogram
-1Near strong peak is C=O stretching vibration absworption peak, 1380cm
-1Strong peak is a C-N stretching vibration absworption peak in neighbouring, and explaining has imide group in the product, has 1600 centimetres in the spectrogram
-1, 1575 centimetres
-1, 1490 centimetres
-1, 1450 centimetres
-1Absworption peak (phenyl ring characteristic peak), explain to have phenyl ring in the product.
Adopt mercury injection method to measure the pore volume of aperture and account for 45% of total pore volume in the hole of 30-65 nanometer.The aperture that this polyimide porous membrane is described is inhomogeneous.
Method according to embodiment 1 prepares composite diaphragm, and different is that used polyimide film is the polyimide film that Comparative Examples 1 prepares.
Comparative Examples 2
The preparation of this Comparative Examples explanation reference composite diaphragm
Prepare composite diaphragm according to the CN1725524A disclosed method.
Performance test
1, film properties test
(1) thickness of test membrane
Adopt measured film thickness appearance (Shanghai six water chestnut instrument plants;
type) measures polyimide film sample thickness in the composite diaphragm; Choose 5 point measurements on the membrane sample arbitrarily, and average.
(2) porosity of test membrane and average pore size
Adopt mercury injection apparatus (DEMO AutoPore 9500, the U.S.) to measure the porosity and the average pore size of polyimides membrane sample in the composite diaphragm, method of testing is conventionally known to one of skill in the art.
(3) hot strength of test membrane and percentage elongation
Come the hot strength and the percentage elongation of polyimides membrane sample in the test compound barrier film according to the plastic tensile test method of GB1040-79.
(4) testing air permeable property
Measure the gas permeability of polyimides membrane sample in the composite diaphragm according to the method for describing among the JIS P8117.
According to above-mentioned method of testing polyimide porous membrane in the prepared composite diaphragm among embodiment 1-8 and the Comparative Examples 1-2 is carried out performance test, gained is the result be shown in Table 1.
Table 1
Can find out that from the result of table 1 average pore size of polyimide porous membrane that adopts method provided by the invention preparation is between 68 to 290 nanometers, porosity, gas permeability and mechanical strength are all very good, meet the requirement of lithium ion battery separator to the aperture.From Comparative Examples 1 and 2 and the comparison of the test data of embodiment 8 can find out; The porosity of the polyimide porous membrane that Comparative Examples 1 obtains, gas permeability and mechanical strength are all relatively poor; The polyimide porous membrane that Comparative Examples 2 obtains does not have gas permeability, can not use as battery diaphragm.
2, test battery performance
(1) preparation of positive pole
With 100 gram positive active material LiCoO
2, 2 gram adhesive vinylidene fluorides (PVDF), 3 gram conductive agent acetylene blacks mixture join in the 40 gram N-N-methyl-2-2-pyrrolidone N-s (NMP), in de-airing mixer, stir then and form uniform anode sizing agent.
This slurry is coated on the aluminium foil equably, 150 ℃ of following oven dry, roll-ins then, cuts to make and be of a size of 390 millimeters * 40 millimeters * positive pole of 18 microns (thick), wherein contain 5.8 gram active component LiCoO
2
(2) preparation of negative pole
The mixture of 100 gram negative electrode active material native graphites, 1.5 gram adhesive polytetrafluoroethylene (PTFE)s and 1.5 gram carboxymethyl celluloses (CMC) is joined in the 100 gram water, in de-airing mixer, stir then and form uniform cathode size.
This cathode size is coated on equably on the both sides of Copper Foil,, roll-in, cuts to make and be of a size of 395 millimeters * 41 millimeters * negative pole of 12 microns (thick), wherein contain 2.6 gram active component native graphites then 90 ℃ of down oven dry.
(3) with composite diaphragm manufacture batteries of the present invention
With including in after the above-mentioned positive pole that obtains, negative pole and barrier film lamination successively and the winding in 4.0 millimeters * 34 millimeters * 46 millimeters the square aluminum hull.Said barrier film is respectively the composite diaphragm that makes by in embodiment 1-8 and the Comparative Examples 1.
To in solvent (ethylene carbonate: Methylethyl carbonic ester: diethyl carbonate (EC/EMC/DEC) volume ratio is 1: 1: 1), contain 1 mole lithium hexafluoro phosphate (LiPF
6) about 2.4 grams of electrolyte inject above-mentioned battery, and ageing in a conventional manner, the sealed cell aluminum hull promptly obtains lithium rechargeable battery.The design capacity of this battery is 750 MAHs.
(4) battery resistance to elevated temperatures test
Method of testing is following: battery is carried out 1C be charged to 100% Charging state, be placed in the baking oven, oven temperature is elevated to 150 ℃ and 180 ℃ with 5 ℃/minute from room temperature, and wherein cell voltage falls greater than 0.2 volt and is regarded as short circuit.
(5) battery life test
Method of testing is following: under 25 ℃ ± 5 ℃, battery is carried out cycle charge-discharge 500 times, the record dump energy.Dump energy is high more, and battery life is long more.
The battery that to use composite diaphragm made in embodiment 1-8 and the Comparative Examples 1 to make carries out battery resistance to elevated temperatures and life test according to above-mentioned method of testing, and resulting result lists in the table 2.
Table 2
Can find out that from the result of table 2 lithium rechargeable battery for preparing with composite diaphragm provided by the invention has better fail safe and longer useful life.
Claims (23)
1. composite diaphragm; This composite diaphragm comprises polyolefin porous rete and polyimide porous membrane layer; It is characterized in that said composite diaphragm also comprises adhesive phase, said adhesive phase is between polyimide porous membrane layer and polyolefin porous rete and polyolefin porous rete and polyimide porous membrane layer are fitted tightly; The pore-size distribution of said polyimide porous membrane does; Bore dia is that the pore volume in the hole of 50-300 nanometer accounts for more than 75% of total pore volume, and bore dia accounts for below 25% of total pore volume less than 50 nanometers and bore dia greater than the pore volume in the hole of 300 nanometers, and said bore dia adopts mercury injection method to record.
2. composite diaphragm according to claim 1; Wherein, the number of plies of said composite diaphragm is five layers, and the intermediate layer of said composite diaphragm is the polyolefin porous rete; Adhesive phase lays respectively at the both sides of this polyolefin porous rete, and outermost layer is the polyimide porous membrane layer.
3. composite diaphragm according to claim 1; Wherein, the number of plies of said composite diaphragm is five layers, and the intermediate layer of said composite diaphragm is the polyimide porous membrane layer; Adhesive phase lays respectively at the both sides of this polyimide porous membrane layer, and outermost layer is the polyolefin porous rete.
4. according to any described composite diaphragm among the claim 1-3, wherein, the gas permeability of said polyimide porous membrane layer is 10-200 second/100cc.
5. composite diaphragm according to claim 4, wherein, the gas permeability of said polyimide porous membrane layer is 20-180 second/100cc.
6. according to any described composite diaphragm among the claim 1-3, wherein, the thickness of said polyimide porous membrane layer is the 5-35 micron.
7. according to any described composite diaphragm among the claim 1-3; Wherein, The polyolefin porous membrane of said formation polyolefin porous rete is selected from one or more in polyethylene porous membrane, polypropylene porous film and the polyvinylidene fluoride porous film, and the thickness of said polyolefin porous rete is the 10-35 micron; The adhesive of said formation adhesive phase is selected from the copolymer of Kynoar, polyvinyl chloride, polytetrafluoroethylene, tetrafluoroethylene/hexafluoropropylene, the copolymer of tetrafluoroethylene/perfluoro alkyl vinyl ether, the copolymer, 1 of ethylene/tetrafluoroethylene; In the copolymer of 1-difluoroethylene/hexafluoroethylene, polyimides, polyamic acid, polyurethane, phenolic resins, polyethylene and the polypropylene one or more, the thickness of said adhesive phase are the 0.5-20 micron.
8. the preparation method of the said composite diaphragm of claim 1; It is characterized in that; This method is included between polyolefin porous rete and the polyimide porous membrane layer and forms adhesive phase; And polyolefin porous rete and polyimide porous membrane layer are fitted tightly, the pore-size distribution of said polyimide porous membrane is that bore dia is that the pore volume in the hole of 50-300 nanometer accounts for more than 75% of total pore volume; Bore dia accounts for below 25% of total pore volume less than 50 nanometers and bore dia greater than the pore volume in the hole of 300 nanometers, and said bore dia adopts mercury injection method to record.
9. method according to claim 8, wherein, the number of plies of said composite diaphragm is five layers, and the intermediate layer of said composite diaphragm is the polyolefin porous rete, and adhesive phase lays respectively at the both sides of this polyolefin porous rete, and outermost layer is the polyimide porous membrane layer.
10. method according to claim 8; Wherein, the number of plies of said composite diaphragm is five layers, and the intermediate layer of said composite diaphragm is the polyimide porous membrane layer; Adhesive phase lays respectively at the both sides of this polyimide porous membrane layer, and outermost layer is the polyolefin porous rete.
11. method according to claim 8, wherein, the gas permeability of said polyimide porous membrane is 10-200 second/100cc.
12. method according to claim 11, wherein, the gas permeability of said polyimide porous membrane is 20-180 second/100cc.
13. method according to claim 8, wherein, the thickness of said polyimide porous membrane layer is the 5-35 micron.
14. method according to claim 8; Wherein, The preparation method of said polyimide porous membrane comprises the mixture formation polyamide acid film that contains polyamic acid, pore-forming material and solvent, this polyamide acid film is contacted with solidification liquid, and carry out imidizate; Said solvent is for dissolving polyamic acid but slightly soluble or do not dissolve the solvent of pore shaping object matter, and said solidification liquid is for dissolving pore-forming material or with the pore shaping object qualitative response but slightly soluble or the insoluble liquid of separating polyamic acid.
15. method according to claim 14; Wherein, The weight ratio of said pore-forming material and said polyamic acid is 0.01-0.3: 1, and the weight ratio of polyamic acid and said solvent is 1: 4.5-10, the weight ratio of polyamic acid and said solidification liquid is 1: 20-200.
16. according to claim 14 or 15 described methods, wherein, said pore-forming material is selected from one or more in hydroxide, aluminium hydroxide, alkali-metal phosphate and the sodium phosphate trimer of alkali earth metal, particle mean size is the 0.01-2 micron; Said solidification liquid is one or more in hydrochloric acid, aqueous sulfuric acid and the phosphate aqueous solution.
17. method according to claim 16, wherein, the hydroxide of said alkali earth metal is magnesium hydroxide and/or calcium hydroxide; Said alkali-metal phosphate is tertiary sodium phosphate and/or tripotassium phosphate.
18. method according to claim 16, wherein, the concentration of said hydrochloric acid is 5-35 weight %, and the concentration of said aqueous sulfuric acid is 5-98 weight %, and the concentration of said phosphate aqueous solution is 5-98 weight %.
19. according to claim 14 or 15 described methods; Wherein, to be selected from saturated carboxylic acid, benzoic acid polyol ester, carbon number that carbon number is 5-15 be the phthalic acid dialkyl of 13-30 and in the methylin acetate one or more to said pore-forming material; Said solidification liquid is one or more in methyl alcohol, ethanol, methyl ether, ether, acetone and the methyl propanediol; Said polyamic acid is to gather equal benzene tetramethyl amic acid, gather the biphenyl tetracarboxylic amic acid and gather in the benzophenone tetramethyl amic acid one or more; Said solvent is N-2-methyl pyrrolidone, N, N-dimethylacetylamide, oxolane, N, one or more in dinethylformamide, m-cresol, dimethyl sulfoxide (DMSO) and the methyl alcohol.
20. method according to claim 19, wherein, said carbon number is that the saturated carboxylic acid of 5-15 is one or more in valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid and their isomers; Said benzoic acid polyol ester is benzoic acid one condensed ethandiol ester and/or benzoic acid one propylene glycol ester that contracts; Said carbon number is that the phthalic acid dialkyl of 13-30 is one or more in terephthalic acid (TPA) diamyl ester, M-phthalic acid two capronates and the dinonyl phthalate; Said methylin acetate is 1-Methoxy-2-propyl acetate and/or glycol methyl ether acetate.
21. method according to claim 14, wherein, the said mode that polyamide acid film is contacted with solidification liquid is for to be immersed in polyamide acid film in the solidification liquid, and the temperature of said solidification liquid is 0-50 ℃, and the time of dipping is 20-120 minute.
22. method according to claim 14, wherein, the method for said imidizate be included in keep under 70-200 ℃ the temperature 0.5-4 hour, under 200-400 ℃ temperature, kept 0.5-3 hour.
23. lithium rechargeable battery; This battery comprises this electrode group and nonaqueous electrolytic solution; Said electrode group and nonaqueous electrolytic solution are sealed in the battery container; Said electrode group comprises positive pole, negative pole and barrier film, it is characterized in that, said barrier film is any described composite diaphragm among the claim 1-7.
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| CN101872853B (en) * | 2010-04-21 | 2013-03-20 | 东莞新能源电子科技有限公司 | Polymer lithium ion secondary battery and isolating membrane thereof |
| JP2013051180A (en) * | 2011-08-31 | 2013-03-14 | Dexerials Corp | Separator sheet for battery, and battery |
| JP5800268B2 (en) * | 2011-12-09 | 2015-10-28 | 公立大学法人首都大学東京 | Separator for lithium secondary battery and manufacturing method thereof |
| CN102522528B (en) * | 2011-12-31 | 2014-08-27 | 宁波长阳科技有限公司 | Preparation method of battery diaphragm |
| KR20130099546A (en) * | 2012-02-29 | 2013-09-06 | 제일모직주식회사 | Separator comprising organic and inorganic mixture coating layer containing soluble polyimide and battery using the separator |
| CN103028535A (en) * | 2012-12-11 | 2013-04-10 | 天津力神电池股份有限公司 | Membrane gluing method |
| CN109608682A (en) * | 2013-04-22 | 2019-04-12 | 东京应化工业株式会社 | Manufacturing method, porous polyimide film and the partition for having used the porous polyimide film of porous polyimide film |
| CN103219483B (en) * | 2013-04-27 | 2015-05-27 | 中材科技股份有限公司 | Composite lithium battery diaphragm and preparation method thereof |
| JP6213506B2 (en) * | 2015-03-18 | 2017-10-18 | トヨタ自動車株式会社 | Nonaqueous electrolyte secondary battery |
| JP6905308B2 (en) * | 2015-06-16 | 2021-07-21 | 川崎重工業株式会社 | Alkaline water electrolysis diaphragm and its manufacturing method |
| EP3316346B1 (en) * | 2015-07-10 | 2019-02-27 | LG Chem, Ltd. | Separator and electrochemical device comprising same |
| CN105576176B (en) * | 2016-01-29 | 2018-01-30 | 中南大学 | A kind of preparation method of high security lithium ion battery diaphragm |
| CN107195838B (en) * | 2017-05-02 | 2020-03-17 | 佛山市金辉高科光电材料有限公司 | Heat-resistant coating with uniform and ordered pore diameter for lithium ion battery diaphragm and preparation method thereof |
| AU2018305973B2 (en) | 2017-07-26 | 2023-07-13 | Nippon Shokubai Co., Ltd. | Diaphragm for alkaline water electrolysis, method for producing same, and method for producing inorganic-organic composite membrane |
| CN111916622A (en) * | 2020-08-19 | 2020-11-10 | 北京宇程科技有限公司 | Multifunctional double-sided heterogeneous Janus diaphragm for lithium ion battery and preparation method thereof |
| CN112387135B (en) * | 2020-10-29 | 2022-05-17 | 江苏厚生新能源科技有限公司 | Water filtration composite membrane and preparation method thereof |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1355940A (en) * | 1999-04-09 | 2002-06-26 | Basf公司 | Composite bodies used as separators in electrochemical cells |
| CN1725524A (en) * | 2004-07-21 | 2006-01-25 | 三洋电机株式会社 | Separator for non-aqueous electrolyte battery and non-aqueous electrolyte battery |
-
2008
- 2008-08-22 CN CN200810145795XA patent/CN101656306B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1355940A (en) * | 1999-04-09 | 2002-06-26 | Basf公司 | Composite bodies used as separators in electrochemical cells |
| CN1725524A (en) * | 2004-07-21 | 2006-01-25 | 三洋电机株式会社 | Separator for non-aqueous electrolyte battery and non-aqueous electrolyte battery |
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