CN102522528A - Battery diaphragm and preparation method thereof - Google Patents
Battery diaphragm and preparation method thereof Download PDFInfo
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- CN102522528A CN102522528A CN2011104580464A CN201110458046A CN102522528A CN 102522528 A CN102522528 A CN 102522528A CN 2011104580464 A CN2011104580464 A CN 2011104580464A CN 201110458046 A CN201110458046 A CN 201110458046A CN 102522528 A CN102522528 A CN 102522528A
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Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a battery diaphragm and a preparation method thereof. The invention provides a battery diaphragm, aiming at overcoming the defects of weak adhesion force and low transmittance between composite layers of the battery diaphragm in the prior art. The battery diaphragm comprises a polyimide porous membrane layer and a polyolefin porous membrane layer, wherein the polyolefin porous membrane layer is bonded on the polyimide porous membrane layer; the battery diaphragm is provided with a through hole, the aperture of the through hole is 60-250 nanometers, and the porosity is 30-60%. The thickness of the battery diaphragm is 30-50 microns, and the thickness of the polyimide porous membrane layer is 20-40 microns. Compared with the prior art, the battery diaphragm provided by the invention has strong bonding force between layers and high transmittance. The invention also provides a preparation method of the battery diaphragm, which comprises a coating process, and is simple in process and easy to operate. The battery diaphragm provided by the invention can be widely applied to lithium ion batteries.
Description
Technical field
The present invention relates to technical field of lithium ion, relate in particular to a kind of battery diaphragm and preparation method thereof.
Background technology
Development along with information technology; We also increase the demand of portable power source fast, simultaneously, compare with conventional batteries; Transformation has also taken place the direction of demand: energy is high, volume is little, in light weight, security performance is high, has become the new direction of portable power source development.Lithium ion battery since its energy density high, have extended cycle life, safety nuisance free, the performance of impulse electricity fast, become the first-selection of numerous mancarried electronic aids and electric automobile.
The part of ion battery comprises: electrode, electrolyte, membrane for polymer (battery diaphragm) etc.; Wherein the barrier film between two electrodes has played very important effect; It not only will play and separate the two poles of the earth, makes battery be unlikely to the effect of internal short-circuit, also will play the effect through ion; Certain porosity can guarantee that battery diaphragm having under the prerequisite of good transmitance, can also guarantee outstanding mechanical performance.In the battery use, inevitably can produce a part of heat, if fault has taken place, temperature can rise always, causes inner pressure of battery significantly to increase, and blasts easily.This potential safety hazard can be got rid of through battery diaphragm to a certain extent, has the battery diaphragm of loose structure, when temperature is higher, can melt, and causes closing of hole, increases impedance, and breaking current reaches safing effect.Yet common battery diaphragm material is selected polyethylene (PE) for use, and polypropylene (PP), fusing point be all below 200 ℃, also lower (130～140 ℃ of the self-closing temperature of PE of self-closing temperature; About 170 ℃ of the self-closing temperature of PP), higher in battery operated ambient temperature, when perhaps discharging current is excessive; Because electrolytical thermal inertia effect, temperature also can continue to raise behind the barrier film breaking current, when reaching the film destroy temperature; Barrier film can destroy fully, causes the internal short-circuit of battery temperature to continue to raise, thereby causes battery explosion.Therefore we need a kind of battery diaphragm of exotic material to ensure the safety of battery under higher temperature, have good permeability and insulating properties again simultaneously, and polyimide film just become one of ideal material of battery diaphragm in the lithium ion battery.
The application number of Biyadi Co Ltd is a 200610170396.X (publication No.: CN101212035B; Date of publication: Chinese patent on July 2nd, 2008) has been reported a kind of battery diaphragm and preparation method thereof; Its feature is; On the polyimide porous membrane for preparing, apply polyolefin, heating in vacuum makes and contains polyolefinic polyimide film in the hole.Though this method is through using polyimide material as battery diaphragm; Utilized its resistant to elevated temperatures characteristic, but, be unfavorable for that ion sees through owing to filled polyolefin in the polyimides fenestra; Cause the transmitance of battery diaphragm to descend the impedance that has improved battery diaphragm; And at high temperature polyolefin can melt destruction, the effect of the closed pore that can't reach a high temperature down protection.
The application number of Biyadi Co Ltd is 200810145795.X (publication No. CN101656306A; Date of publication: one Chinese patent application on July 2nd, 2008) has been reported a kind of composite diaphragm and preparation method thereof and the battery that comprises this composite diaphragm; Its feature is; Preparation polyimides and polyolefinic perforated membrane, bonding through adhesive layer, in solution, soak.Remove the pore-forming material in the adhesive layer, obtain polyimides and polyolefinic composite battery separator film.Though this method has been utilized the heat-resisting quantity and the polyolefinic closed pore defencive function of polyimides simultaneously; But remove the pore-forming material owing to just in solution, soaking after bonding through adhesive layer, can cause like this removing the pore-forming material in the adhesive layer fully, the porosity of adhesive layer is descended; Cause the both sides of composite membrane well not to be communicated with; Thereby reduced the whole transmitance of composite membrane, increased impedance, reduced battery efficiency.
The application number of Liang Jin is 200810067765.1 (publication No.: CN101304082A; Date of publication: one Chinese patent application on November 12nd, 2008) has been reported a kind of lithium ion secondary battery membrane compound film and manufacturing process thereof; Its feature is to use multi-layer polyolefin perforated membrane and the range upon range of preparation battery diaphragm of polyimide porous membrane.Its shortcoming is that the interlayer adhesion is not strong, comes off easily between the stacked film, reduces ion transmission, increases impedance.
Summary of the invention
In order to overcome in the prior art a little less than each compound ply adhesion of battery diaphragm and the low shortcoming of transmitance, the present invention provides a kind of cohesive force strong, battery diaphragm that transmitance is high and preparation method thereof.Compared with prior art, cohesive force is strong between the layer of battery diaphragm provided by the invention and the layer, and transmitance is high, has good temperature resistance and closed pore defencive function.The present invention also provides the preparation method of battery diaphragm, and this method technology is simple, easy operating.
In order to solve the problems of the technologies described above, the present invention provides following technical proposals:
A kind of battery diaphragm, its feature be, said battery diaphragm comprises polyimide porous membrane layer and polyolefin porous rete, and said polyolefin porous rete is bonded on the polyimide porous membrane layer; Said battery diaphragm is provided with through hole, and the aperture of said through hole is the 60-250 nanometer, and porosity is 30-60%, and air penetrability is 80-450s/100cc.Said air penetrability is preferably 200-300s/100cc.
Further, the thickness of said battery diaphragm is the 30-50 micron, and the thickness of said polyimide porous membrane layer is the 20-40 micron.The thickness that the thickness of battery diaphragm deducts the polyimide porous membrane layer promptly is the thickness of polyolefin porous rete, and the thickness of polyolefin porous rete is 4 microns at least.
Further, the thickness of said battery diaphragm is the 35-45 micron, and the thickness of said polyimide porous membrane layer is the 25-35 micron.
Further, the aperture of said through hole is the 90-200 nanometer, and porosity is 35-55%.
Further, the thickness of said battery diaphragm is the 30-40 micron, and the thickness of said polyimide porous membrane layer is the 20-30 micron.
Further, the thickness of said battery diaphragm is the 40-50 micron, and the thickness of said polyimide porous membrane layer is the 30-40 micron.
The present invention also provides a kind of preparation method of battery diaphragm, and its feature is that said preparation method comprises the steps:
(1) mixture with polyamic acid, pore-forming material and solvent is coated on the supporter (like glass plate, corrosion resistant plate); Except that after desolvating; Obtain the polyamic acid non-porous film, be lower than drying under the vitrification point of polyamide acid film, preferably dry under 100 ℃-150 ℃ condition; And carry out imidization, obtain the polyimides non-porous film; The inherent viscosity of said mixture [η]=100-200 milliliter/gram.
(2) will contain the polyolefin master batch fusion of pore-forming material, be coated on the polyimides non-porous film of step (1) gained, after leaving standstill, obtain compound non-porous film;
(3) the compound non-porous film with step (2) gained contacts with solidification liquid, removes the pore-forming material, obtains comprising the battery diaphragm of polyimide porous membrane layer and polyolefin porous rete.
Wherein, Pore-forming material in the said polyolefin master batch is identical with pore-forming material in the polyimides non-porous film; 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 not for reacting the solution of while and pore shaping object qualitative response with polyimides and polyolefin.Said solidification liquid is used for removing the pore-forming material.
In the step (1), the preferred temperature of coating is 30-65 ℃, and the method for coating can be used the whole bag of tricks well known in the art; For example: spin-coating method, knife coating, The tape casting or dip coating etc., according to requirement to film thickness, the adjustment coated weight; Finally make the polyimides non-porous film reach thickness requirement; Experiment showed, the thickness that will make the polyimides non-porous film at the 20-40 micron, the thickness of polyamide acid film is preferably at the 200-400 micron; Thickness after the polyamide acid film imidization can attenuation.The method that can adopt heating is except that desolvating, and heating-up temperature is 30-130 ℃, and the time is 5-10 minute.
The imidization of polyamic acid non-porous film is through keeping down realizing in 3-9 hour at 80-350 ℃; Heating mode can be selected direct intensification; Preferred 5-10 ℃/minute heating rate; Most preferably use the mode of gradient increased temperature: polyamide acid film kept 1-4 hour down at 80-200 ℃, kept 2-5 hour down to realize imidization at 200-350 ℃.Under described reaction condition, the conversion ratio of polyamic acid is more than 99%, and a spot of polyamic acid does not have much affect to performance of polyimide, therefore allows to exist in the polyimide film polyamic acid less than 3%.
In the step (2), the thickness of the coat after the said polyolefin fusion is preferably the 30-100 micron, and said coat is leaving standstill back thickness meeting attenuation.In the step (3), the mode that said compound non-porous film contacts with solidification liquid is immersed in compound non-porous film in the solidification liquid for dipping; Pore-forming material and solidification liquid are reacted; Remove the pore-forming material, make the position of original pore-forming material become micropore, micropore is interconnected and has formed through hole.The solidification liquid temperature is 0-50 ℃, and the time of said compound non-porous film being immersed said solidification liquid is 30-180 minute.Can pass through electron microscopic observation micropore distribution situation, the ion that equally distributed micropore helps the battery diaphragm both sides passes through, and reduces impedance.Micropore on the above-mentioned battery diaphragm distributes more even.
Further, the weight ratio of said pore-forming material and said polyamic acid is 0.02-0.2: 1, and the weight ratio of said polyamic acid and said solvent is 1: 4-9; Said pore-forming material and said polyolefinic weight ratio are 0.01-0.1: 1; The weight ratio of said compound non-porous film and said solidification liquid is 1: 10-150 is preferably 1: 35-45.
Further, said polyamic acid carries out condensation reaction through binary organic acid acid anhydride and organic diamine and obtains, and the mol ratio of said binary organic acid acid anhydride and organic diamine is 0.7-1.4: 1; Said polyolefin is a polarity enhancement mode polyolefin.
Wherein, said pore-forming material can be before condensation reaction, and in the reaction or reaction back any stage adds, and adds before the preferred reaction.The preparation method who is said polyamic acid coating solution comprises: with binary organic acid acid anhydride, organic diamine, pore-forming material and solvent; Obtain uniform mixture, this mixture forms polyamide acid film through condensation reaction; The preferred temperature of condensation is 30-60 ℃, and be 4-20 hour time of contact.The mol ratio of said binary organic acid acid anhydride and organic diamine is preferably 1.10-1.13: 1.Said polarity enhancement mode polyolefin; Be to have strengthened polyolefinic polarity through the method with polarity unit and polyolefin graft copolymerization, said polarity unit comprises acrylic acid, methacrylic acid; Fumaric acid; Maleic acids etc. make polyolefin layer on polyimide layer, have good adhesive force, have strengthened the composite diaphragm interlayer adhesion.
Further, said pore-forming material comprises the hydroxide of alkaline-earth metal, alkali-metal phosphate or sodium phosphate trimer; Said pore-forming material particle mean size is the 0.03-3 micron; Said solvent comprises N-2-methyl pyrrolidone, N, the combination of a kind of in N-dimethylacetylamide, oxolane or the m-cresol or at least two kinds; Said solidification liquid comprises the combination of a kind of in hydrochloric acid, sulfuric acid or the phosphoric acid or at least two kinds.
Experiment showed, that above-mentioned solvent all is not more than 1wt% to 25 ℃ of solubility of above-mentioned pore-forming material; Above-mentioned solidification liquid concentration is respectively: hydrochloric acid (3-40wt%), and aqueous sulfuric acid (3-98wt%), phosphate aqueous solution (3-98wt%), preferred version is: hydrochloric acid (10-15wt%), aqueous sulfuric acid (20-30wt%), phosphate aqueous solution (20-30wt%).In solidification liquid, the solubility of pore-forming material under 25 ℃ is all greater than 1wt% (parts by weight).
A kind of preparation method of battery diaphragm, its feature are that said preparation method comprises the steps:
(1) with binary organic acid acid anhydride and organic diamine with 0.7-1.4: it is in binary organic acid acid anhydride and the organic diamine gross mass 4-9 solvent doubly that 1 mol ratio joins quality; Adding quality simultaneously is binary organic acid acid anhydride and organic diamine gross mass 0.02-0.2 pore-forming material doubly; Stirred 4-20 hour down at 30-60 ℃; Obtain thick mixture, the inherent viscosity of this mixture [η]=100-200 milliliter/gram;
(2) under 30-65 ℃, the mixture of step (1) gained is coated on the supporter (like glass plate, corrosion resistant plate), coat thickness is the 100-550 micron; Preferred 200-400 micron; Under 30-130 ℃ of condition, obtained polyamide acid film except that desolvating in dry 5-10 minute then;
(3) adopt the mode of gradient increased temperature, the polyamide acid film of step (2) gained is heated in nitrogen carry out imidization, obtain the polyimide film that thickness is the 20-40 micron;
(4) will contain the polypropylene agglomerate fusion of pore-forming material after, be coated on the polyimide film of step (3) gained, coat thickness is the 30-100 micron, places at normal temperatures after 1 hour and obtains compound non-porous film; In the said polypropylene agglomerate, the weight ratio of said polypropylene and pore-forming material is 1: 0.01-0.1;
(5) with the compound non-porous film of step (4) gained under 0-50 ℃; Be immersed in fully in the solidification liquid, soaked 30-180 minute, the weight ratio of said compound non-porous film and said solidification liquid is 1: 10-150; Take out after removing the pore-forming material fully, obtain said battery diaphragm.
Because polyimides is a kind of insoluble high molecular polymer, the degree of polymerization is difficult to measure, but through discovering; Control inherent viscosity (the intrinsic viscosity of polyamic acid within the specific limits; Abbreviation [η]), can regulate and control the degree of polymerization of polyimides, the experiment proof; The inherent viscosity of polyamic acid is controlled at 100-200 milliliter/gram, and the preferred conversion ratio that the 150-190 milliliter/gram can be realized polyamic acid is more than 99%.Use Ubbelohde viscometer, in 25 ℃ of following test characteristic viscosity of constant temperature, mixture diluted is 0.005 grams per milliliter to solid content during test.
The present invention also provides a kind of battery, comprises battery diaphragm, and its feature is that said battery diaphragm is made by above-mentioned preparation method.Perhaps, said battery diaphragm is above-mentioned battery diaphragm.
Compared with prior art, battery diaphragm provided by the invention only has double-layer structure, and the polyolefin porous rete is bonded on the polyimide porous membrane layer; Have very strong interlayer adhesion, and can utilize the heat-resisting quantity and the polyolefinic closed pore defencive function of polyimides simultaneously, when temperature raises; The polyolefin porous rete plays the effect of breaking current; The polyimide porous membrane layer can also effectively intercept both positive and negative polarity simultaneously, prevents short circuit, has improved the security performance of battery greatly.Owing to remove the pore-forming material in polyolefin layer and the polyimide layer simultaneously, make pore shaping object mass-energy remove enough completely, the micropore of every layer of battery diaphragm can both be evenly distributed, improved its transmitance, reduce impedance; Preparation method's technology of battery diaphragm provided by the invention is simple, easy operating; The battery safety that contains battery diaphragm of the present invention is better, and useful life is long.Battery diaphragm provided by the invention extensively model is applied to battery, especially lithium ion battery.
Description of drawings
Fig. 1 is the generalized section of battery diaphragm provided by the invention;
Wherein, 1 is the polyimide porous membrane layer, and 2 is the polyolefin porous rete, and 3 is through hole.
Embodiment
As shown in Figure 1, battery diaphragm provided by the invention comprises polyimide porous membrane layer 1 and polyolefin porous rete 2, and said polyolefin porous rete 2 is bonded on the polyimide porous membrane layer 1; Also be provided with through hole 3 on the said battery diaphragm, the aperture of said through hole 3 is the 60-250 nanometer.
Material therefor of the present invention and equipment are existing material and facility, all can on market, buy.As; Bibenzene tetracarboxylic dianhydride (Shanghai enlightening cypress chemicals technology Co., Ltd produces), 4; 4 '-diaminodiphenyl ether (Lu, Shanghai peaking worker Co., Ltd), N-2-methyl pyrrolidone (Shenzhen China prosperous chemical industry Co., Ltd), calcium hydroxide (the strong forever calcium industry in Xinxiang City Co., Ltd), (mean molecule quantity is 35000 in the modified polypropene section; Guangzhou Keyuan New Materials Co., Ltd), N; N '-dimethylacetylamide (emerging commerce and trade Co., Ltd of Shanghai section), magnesium hydroxide (Shandong, Shandong China chemical industry Co., Ltd), tertiary sodium phosphate (Jiaozuo City letter Dehua worker Co., Ltd) oxolane (Shanghai De-Nol chemical industry Co., Ltd), hydrochloric acid (Weifang Heng Feng chemical industry Co., Ltd), phosphoric acid, sulfuric acid (western Gansu Province chemical industry), other materials such as polyamic acid, magnesium hydroxide also are product sold on the market.Polyethylene or polypropylene (Guangzhou Keyuan New Materials Co., Ltd) through the graft modification enhanced polarity.
Each item performance that the present invention adopts following common method and testing of equipment prepared cell barrier film and contains the battery of this battery diaphragm.
Average pore size: the instrument of measuring average pore size is AutoPore IV 9500 full-automatic mercury injection apparatuses (Shanghai experimental facilities Co., Ltd in the future produces), adopts the method for testing test of GB/T21650.
Membrane thicknesses: measure with digimatic micrometer.
Resistance to elevated temperatures: battery diaphragm is positioned in 400 degrees centigrade of baking ovens, is incubated after 1 hour and takes out, observe battery diaphragm and whether break.
Porosity is the percentage that the cumulative volume of finger-hole accounts for the battery diaphragm cumulative volume, and the test porosity adopts the conventional method of testing test in this area, from the square sample of microporous barrier cutting-out certain-length, measures its volume (cm
3) and weight (g), calculate by following formula: porosity (%)=100 * (1-weight/(resin density * volume)).
Gas permeability: adopt the gas permeability of the method test battery barrier film of JIS P8117, used instrument is the TQD-G1 air permeability tester that Labthink Instruments Co., Ltd. produces.
Peel strength: adopt the peel strength of the method test battery barrier film of GB/T8808-88, used instrument is the GP-6017 peel test force appearance that Suzhou your detecting instrument Co., Ltd of high article produces.Peel strength is high more, and the cohesive force between layer and the layer is strong more.
Percent thermal shrinkage: with lateral length is L
0Battery diaphragm be placed on naturally in 400 ℃ the baking oven and kept respectively 1 hour, measure lateral length L then
1, then
Percentage elongation: adopt the percentage elongation of the method for testing test battery barrier film of GB1040-79, used instrument is the JB-117B electronic universal material testing machine that shore of a specified duration, Shanghai Instr Ltd. produces.
Polyamic acid inherent viscosity: use Ubbelohde viscometer; Test the polyamic acid inherent viscosity down for 25 ℃ at constant temperature; Mixture diluted is 0.005 grams per milliliter to solid content during test, and the inherent viscosity of polyamic acid is controlled at 100-200 milliliter/gram, preferred 150-190 milliliter/gram.
The battery that will contain battery diaphragm according to the invention carries out security performance test and test in useful life; Wherein, Battery safety test: the battery that will use the prepared battery diaphragm of this patent; To be placed on temperature be to carry out discharge test in 400 ℃ the baking oven in charging under 1800mA, press 1C (1800mA) discharge insulation and take out observation battery outward appearance after 30 minutes.
The battery life test: at normal temperatures, with the battery that uses battery diaphragm of the present invention, cycle charge-discharge 500 times, the record dump energy is tested its useful life.Dump energy is high more, and useful life is long more.
The preparation method of battery diaphragm provided by the invention comprises the steps:
(1) with binary organic acid acid anhydride and organic diamine with 0.7-1.4: it is in binary organic acid acid anhydride and the organic diamine gross mass 4-9 solvent doubly that 1 mol ratio joins quality; Adding quality simultaneously is binary organic acid acid anhydride and organic diamine gross mass 0.02-0.2 pore-forming material doubly; Stirred 4-20 hour down at 30-60 ℃; Obtain thick mixture, the inherent viscosity of this mixture [η]=100-200 milliliter/gram;
(2) under 30-65 ℃, the mixture of step (1) gained is coated on the corrosion resistant plate, coat thickness is the 200-400 micron, then under 30-130 ℃ of condition, removes in dry 5-10 minute and to desolvate, and obtains polyamide acid film;
(3) adopt the mode of gradient increased temperature, the polyamide acid film of step (2) gained is heated in nitrogen carry out imidization, obtain the polyimide film of 20-40 micron;
(4) will contain the polypropylene agglomerate fusion of pore-forming material after, be coated on the polyimide film of step (3) gained, coat thickness is the 30-100 micron, places at normal temperatures after 1 hour and obtains compound non-porous film; The weight ratio of polypropylene and pore-forming material is 1 in the said polypropylene agglomerate: 0.01-0.1;
(5) with the compound non-porous film of step (4) gained under 0-50 ℃; Be immersed in fully in the solidification liquid, soaked 30-180 minute, the weight ratio of said compound non-porous film and said solidification liquid is 1: 10-150; Take out after removing the pore-forming material fully, obtain said battery diaphragm.
Among the embodiment, the coating thickness of polyamide acid film is about the 200-400 micron, and after the said polyamide acid film imidization, thickness can attenuation.The thickness of polyimide porous membrane layer is the 20-40 micron among the embodiment; This thickness receives the restriction of polyamide acid film coating thickness in the above-mentioned steps (2); The inherent viscosity of products therefrom in the step (1); The factors such as addition of pore-forming material also can have certain influence to the thickness of polyimide porous membrane layer, and those skilled in the art can confirm the coating thickness of the polyamide acid film in the embodiment according to the thickness of the polyimide porous membrane layer that finally will obtain.Polyolefin described in the embodiment is through the polyethylene of graft modification enhanced polarity or polypropylene; Coat in the above-mentioned steps (4) behind the polypropylene fusion places at normal temperatures that thickness also can attenuation after 1 hour.
Among the following embodiment; The preparation method of battery diaphragm is identical with above-mentioned preparation method; Just material mixture ratio is different; With aforementioned method of testing the battery diaphragm of following embodiment gained and the battery that contains this battery diaphragm are tested respectively, it is as shown in the table for the test result of its average pore size, porosity, gas permeability, interlaminar strength, percent thermal shrinkage, percentage elongation, resistance to elevated temperatures, closed pore temperature, broken film temperature, battery safety and dump energy.
(1) with bibenzene tetracarboxylic dianhydride and 4; It is bibenzene tetracarboxylic dianhydride and 4 that 4 '-diaminodiphenyl ether joins quality with 1.1: 1 mol ratio, and in the N-2-methyl pyrrolidone that 4 '-diaminodiphenyl ether gross mass is 4 times, adding quality simultaneously is bibenzene tetracarboxylic dianhydride and 4; The calcium hydroxide that 4 '-diaminodiphenyl ether gross mass is 0.02 times (particle mean size is 1.5 microns); Stirred 6 hours down at 35 ℃, obtain thick mixture, the inherent viscosity of this mixture [η]=150 milliliter/gram;
(2) under 30 ℃, the mixture of step (1) gained is coated on the corrosion resistant plate, coat thickness is 350 microns, then under 120 ℃ of conditions, removes in dry 5 minutes and to desolvate, and obtains polyamide acid film;
(3) polyamide acid film that adopts the mode of gradient increased temperature that step (2) is obtained heats in nitrogen and carries out imidization; Obtain 38 microns polyimides non-porous film, mode of heating is: kept 3 hours down at 180 ℃, 220 ℃ kept 3 hours down; 260 ℃ kept 2 hours down, and 300 ℃ kept 1 hour down.
(4) will contain the polypropylene agglomerate fusion of calcium hydroxide after; Be coated on the polyimides non-porous film that step (3) obtains, coat thickness is 50 microns, place 1 hour at normal temperatures after; Obtain compound non-porous film, the weight ratio of polypropylene and calcium hydroxide is 10: 1 in the said polypropylene agglomerate;
(5) the compound non-porous film that step (4) is obtained immerses under 30 ℃ in the hydrochloric acid of concentration 15% fully, soaks 120 minutes, takes out after removing calcium hydroxide fully, obtains thickness and be 44 microns battery diaphragm.
Prepare battery diaphragm like embodiment 1 said method; Wherein, The quality of calcium hydroxide (granularity is 1.5 microns) is bibenzene tetracarboxylic dianhydride and 4 in the step (1), 0.04 times of 4 '-diaminodiphenyl ether gross mass, and the inherent viscosity of the viscous mixture of gained be [η]=160 milliliter/restrain; The coat thickness of adjustment polyamide acid film, the thickness of the polyimides non-porous film of gained is 30 microns, the thickness of the battery diaphragm that finally obtains is 36 microns.
Prepare battery diaphragm like embodiment 1 said method; Wherein, The quality of calcium hydroxide (granularity is 1.5 microns) is bibenzene tetracarboxylic dianhydride and 4 in the step (1), 0.06 times of 4 '-diaminodiphenyl ether gross mass, and the inherent viscosity of the viscous mixture of gained be [η]=170 milliliter/restrain; The coat thickness of adjustment polyamide acid film, the coat thickness after the fusion of adjustment polypropylene agglomerate, the thickness of the polyimides non-porous film of gained is 24 microns, the thickness of the battery diaphragm that finally obtains is 35 microns.
Embodiment 4
(1) with bibenzene tetracarboxylic dianhydride and 4, it is bibenzene tetracarboxylic dianhydride and 4 that 4 '-diaminodiphenyl ether joins quality with 1.1: 1 mol ratio, the N that 4 '-diaminodiphenyl ether gross mass is 4 times; In the N-dimethylacetylamide; Adding quality simultaneously is bibenzene tetracarboxylic dianhydride and 4, and the tertiary sodium phosphate that 4 '-diaminodiphenyl ether gross mass is 0.02 times (particle mean size is 1.5 microns) stirred 5 hours down at 40 ℃; Obtain thick mixture, the inherent viscosity of this mixture [η]=155 milliliter/gram;
(2) under 30 ℃, the mixture of step (1) gained is coated on the corrosion resistant plate, coat thickness is 340 microns, under 110 ℃ of conditions, removes in dry 10 minutes then and desolvates, and obtains polyamide acid film;
(3) mode of employing gradient increased temperature; The polyamide acid film that step (2) is obtained heats in nitrogen and carries out imidization; Obtain 34 microns polyimides non-porous film, mode of heating is: kept 3 hours down at 200 ℃, 240 ℃ kept 3 hours down; 280 ℃ kept 2 hours down, and 320 ℃ kept 1 hour down.
(4) will contain the polypropylene agglomerate fusion of tertiary sodium phosphate after; Be coated on the polyimides non-porous film that step (3) obtains; Coat thickness is 50 microns, places at normal temperatures after 1 hour and obtains compound non-porous film, and the weight ratio of polypropylene and calcium hydroxide is 8: 1 in the said polypropylene agglomerate;
(5) the compound non-porous film that step (4) is obtained immerses under 30 ℃ in the aqueous sulfuric acid of concentration 25% fully, soaks 120 minutes, takes out after removing tertiary sodium phosphate fully, obtains thickness and be 40 microns battery diaphragm.
Embodiment 5
(1) with bibenzene tetracarboxylic dianhydride and 4; It is bibenzene tetracarboxylic dianhydride and 4 that 4 '-diaminodiphenyl ether joins quality with 1.1: 1 mol ratio, and in the oxolane that 4 '-diaminodiphenyl ether gross mass is 5 times, adding quality simultaneously is bibenzene tetracarboxylic dianhydride and 4; The magnesium hydroxide that 4 '-diaminodiphenyl ether gross mass is 0.1 times (particle mean size is 1.5 microns); Stirred 8 hours down at 50 ℃, obtain thick mixture, the inherent viscosity of this mixture [η]=185 milliliter/gram;
(2) under 30 ℃, the mixture of step (1) gained is coated on the corrosion resistant plate, coat thickness is 250 microns, under 110 ℃ of conditions, removes in dry 10 minutes then and desolvates, and obtains polyamide acid film;
(3) mode of employing gradient increased temperature; The polyamide acid film that step (2) is obtained heats in nitrogen and carries out imidization; Obtain 26 microns polyimides non-porous film, mode of heating is: kept 3 hours down at 200 ℃, 240 ℃ kept 3 hours down; 280 ℃ kept 2 hours down, and 320 ℃ kept 1 hour down.
(4) will contain the polypropylene agglomerate fusion of magnesium hydroxide after; Be coated on the polyimide film that step (3) obtains; Coat thickness is 90 microns, places at normal temperatures after 1 hour and obtains compound non-porous film, and the weight ratio of polypropylene and calcium hydroxide is 7: 1 in the said polypropylene agglomerate;
(5) the compound non-porous film that step (4) is obtained immerses under 30 ℃ in the phosphate aqueous solution of concentration 25% fully, soaks 120 minutes, takes out after removing magnesium hydroxide fully, obtains thickness and be 35 microns battery diaphragm.
Embodiment 6
(1) with bibenzene tetracarboxylic dianhydride and 4; It is bibenzene tetracarboxylic dianhydride and 4 that 4 '-diaminodiphenyl ether joins quality with 1.1: 1 mol ratio, and in the oxolane that 4 '-diaminodiphenyl ether gross mass is 7 times, adding quality simultaneously is bibenzene tetracarboxylic dianhydride and 4; The magnesium hydroxide that 4 '-diaminodiphenyl ether gross mass is 0.15 times (particle mean size is 1.5 microns); Stirred 8 hours down at 50 ℃, obtain thick mixture, the inherent viscosity of this mixture [η]=190 milliliter/gram;
(2) under 30 ℃, the mixture of step (1) gained is coated on the corrosion resistant plate, coat thickness is 200 microns, under 110 ℃ of conditions, removes in dry 10 minutes then and desolvates, and obtains polyamide acid film;
(3) mode of employing gradient increased temperature; The polyamide acid film that step (2) is obtained heats in nitrogen and carries out imidization; Obtain 22 microns polyimides non-porous film, mode of heating is: kept 3 hours down at 200 ℃, 240 ℃ kept 3 hours down; 280 ℃ kept 2 hours down, and 320 ℃ kept 1 hour down.
(4) will contain the polypropylene agglomerate fusion of magnesium hydroxide after; Be coated on the polyimide film that step (3) obtains; Coat thickness is 100 microns, places at normal temperatures after 1 hour and obtains compound non-porous film, and the weight ratio of polypropylene and calcium hydroxide is 5: 1 in the said polypropylene agglomerate;
(5) the compound non-porous film that step (4) is obtained immerses under 30 ℃ in the hydrochloric acid of concentration 25% fully, soaks 180 minutes, takes out after removing magnesium hydroxide fully, obtains thickness and be 33 microns battery diaphragm.
Table 1
Gas permeability numerical value in the table is low more, and the transmitance of battery diaphragm is high more.
Embodiment 7
(1) with bibenzene tetracarboxylic dianhydride and 4; It is bibenzene tetracarboxylic dianhydride and 4 that 4 '-diaminodiphenyl ether joins quality with 0.7: 1 mol ratio, and in the N-2-methyl pyrrolidone that 4 '-diaminodiphenyl ether gross mass is 4 times, adding quality simultaneously is bibenzene tetracarboxylic dianhydride and 4; The calcium hydroxide that 4 '-diaminodiphenyl ether gross mass is 0.02 times; Stirred 6 hours down at 35 ℃, obtain thick mixture, the inherent viscosity of this mixture [η]=150 milliliter/gram;
(2) under 30 ℃, the mixture of step (1) gained is coated on the corrosion resistant plate, then under 120 ℃ of conditions, removed in dry 5 minutes and to desolvate, obtain polyamide acid film;
(3) polyamide acid film that adopts the mode of gradient increased temperature that step (2) is obtained heats in nitrogen and carries out imidization; Obtain 20 microns polyimides non-porous film, mode of heating is: kept 2 hours down at 100 ℃, 200 ℃ kept 2 hours down; 260 ℃ kept 2 hours down, and 300 ℃ kept 2 hours down.
(4) will contain the polypropylene agglomerate fusion of calcium hydroxide after, be coated on the polyimides non-porous film that step (3) obtains, place 1 hour at normal temperatures after, obtain compound non-porous film, the weight ratio of polypropylene and calcium hydroxide is 1: 0.1 in the said polypropylene agglomerate;
(5) the compound non-porous film that step (4) is obtained immerses in the hydrochloric acid of concentration 10% under 30 ℃ fully; Soaked 120 minutes; The weight ratio of said compound non-porous film and said solidification liquid is 1: 120, takes out after removing calcium hydroxide fully, obtains thickness and be 30 microns battery diaphragm.
Embodiment 8
(1) with bibenzene tetracarboxylic dianhydride and 4, it is bibenzene tetracarboxylic dianhydride and 4 that 4 '-diaminodiphenyl ether joins quality with 1.4: 1 mol ratio, the N that 4 '-diaminodiphenyl ether gross mass is 9 times; In the N-dimethylacetylamide; Adding quality simultaneously is bibenzene tetracarboxylic dianhydride and 4, and the calcium hydroxide that 4 '-diaminodiphenyl ether gross mass is 0.2 times stirred 6 hours down at 35 ℃; Obtain thick mixture, the inherent viscosity of this mixture [η]=180 milliliter/gram;
(2) under 30 ℃, the mixture of step (1) gained is coated on the corrosion resistant plate, then under 120 ℃ of conditions, removed in dry 5 minutes and to desolvate, obtain polyamide acid film;
(3) polyamide acid film that adopts the mode of gradient increased temperature that step (2) is obtained heats in nitrogen and carries out imidization; Obtain 40 microns polyimides non-porous film, mode of heating is: kept 2 hours down at 150 ℃, 200 ℃ kept 2 hours down; 260 ℃ kept 2 hours down, and 330 ℃ kept 2 hours down.
(4) will contain the polypropylene agglomerate fusion of calcium hydroxide after, be coated on the polyimides non-porous film that step (3) obtains, place 1 hour at normal temperatures after, obtain compound non-porous film, the weight ratio of polypropylene and calcium hydroxide is 1: 0.01 in the said polypropylene agglomerate;
(5) the compound non-porous film that step (4) is obtained immerses in the aqueous sulfuric acid of concentration 30% under 20 ℃ fully; Soaked 120 minutes; The weight ratio of said compound non-porous film and said solidification liquid is 1: 10, takes out after removing calcium hydroxide fully, obtains thickness and be 50 microns battery diaphragm.
Embodiment 9
(1) with bibenzene tetracarboxylic dianhydride and 4; It is bibenzene tetracarboxylic dianhydride and 4 that 4 '-diaminodiphenyl ether joins quality with 1.05: 1 mol ratio, and in the N-2-methyl pyrrolidone that 4 '-diaminodiphenyl ether gross mass is 6 times, adding quality simultaneously is bibenzene tetracarboxylic dianhydride and 4; The potassium phosphate that 4 '-diaminodiphenyl ether gross mass is 0.1 times; Stirred 6 hours down at 35 ℃, obtain thick mixture, the inherent viscosity of this mixture [η]=130 milliliter/gram;
(2) under 30 ℃, the mixture of step (1) gained is coated on the corrosion resistant plate, coat thickness is 300 microns, then under 120 ℃ of conditions, removes in dry 5 minutes and to desolvate, and obtains polyamide acid film;
(3) polyamide acid film that adopts the mode of gradient increased temperature that step (2) is obtained heats in nitrogen and carries out imidization; Obtain 30 microns polyimides non-porous film, mode of heating is: kept 2 hours down at 150 ℃, 200 ℃ kept 2 hours down; 260 ℃ kept 2 hours down, and 330 ℃ kept 2 hours down.
(4) will contain the polypropylene agglomerate fusion of potassium phosphate after, be coated on the polyimides non-porous film that step (3) obtains, place 1 hour at normal temperatures after, obtain compound non-porous film, the weight ratio of polypropylene and potassium phosphate is 1: 0.03 in the said polypropylene agglomerate;
(5) the compound non-porous film that step (4) is obtained immerses under 10 ℃ in the aqueous sulfuric acid of concentration 20% fully, soaks 120 minutes, takes out after removing potassium phosphate fully, obtains thickness and be 40 microns battery diaphragm.
Embodiment 10
(1) with bibenzene tetracarboxylic dianhydride and 4; It is bibenzene tetracarboxylic dianhydride and 4 that 4 '-diaminodiphenyl ether joins quality with 1.13: 1 mol ratio, and in the m-cresol that 4 '-diaminodiphenyl ether gross mass is 7 times, adding quality simultaneously is bibenzene tetracarboxylic dianhydride and 4; The tertiary sodium phosphate that 4 '-diaminodiphenyl ether gross mass is 0.08 times; Stirred 5 hours down at 40 ℃, obtain thick mixture, the inherent viscosity of this mixture [η]=155 milliliter/gram;
(2) under 30 ℃, the mixture of step (1) gained is coated on the corrosion resistant plate, under 110 ℃ of conditions, removed in dry 10 minutes then and desolvate, obtain polyamide acid film;
(3) mode of employing gradient increased temperature; The polyamide acid film that step (2) is obtained heats in nitrogen and carries out imidization; Obtain 25 microns polyimides non-porous film, mode of heating is: kept 3 hours down at 200 ℃, 240 ℃ kept 3 hours down; 280 ℃ kept 2 hours down, and 320 ℃ kept 1 hour down.
(4) will contain the polypropylene agglomerate fusion of tertiary sodium phosphate after, be coated on the polyimides non-porous film that step (3) obtains, place at normal temperatures after 1 hour and obtain compound non-porous film, the weight ratio of polypropylene and tertiary sodium phosphate is 1: 0.02 in the said polypropylene agglomerate;
(5) the compound non-porous film that step (4) is obtained immerses in the aqueous sulfuric acid of concentration 25% under 50 ℃ fully; Soaked 120 minutes; The weight ratio of compound non-porous film and said solidification liquid is 1: 150, takes out after removing tertiary sodium phosphate fully, obtains thickness and be 35 microns battery diaphragm.
Embodiment 11
(1) with bibenzene tetracarboxylic dianhydride and 4; It is bibenzene tetracarboxylic dianhydride and 4 that 4 '-diaminodiphenyl ether joins quality with 0.8: 1 mol ratio, and in the oxolane that 4 '-diaminodiphenyl ether gross mass is 5 times, adding quality simultaneously is bibenzene tetracarboxylic dianhydride and 4; The magnesium hydroxide that 4 '-diaminodiphenyl ether gross mass is 0.15 times; Stirred 8 hours down at 50 ℃, obtain thick mixture, the inherent viscosity of this mixture [η]=185 milliliter/gram;
(2) under 30 ℃, the mixture of step (1) gained is coated on the corrosion resistant plate, under 110 ℃ of conditions, removed in dry 10 minutes then and desolvate, obtain polyamide acid film;
(3) mode of employing gradient increased temperature; The polyamide acid film that step (2) is obtained heats in nitrogen and carries out imidization; Obtain 28 microns polyimides non-porous film, mode of heating is: kept 3 hours down at 200 ℃, 240 ℃ kept 3 hours down; 280 ℃ kept 2 hours down, and 320 ℃ kept 1 hour down.
(4) will contain the polypropylene agglomerate fusion of magnesium hydroxide after, be coated on the polyimide film that step (3) obtains, place at normal temperatures after 1 hour and obtain compound non-porous film, the weight ratio of polypropylene and calcium hydroxide is 1: 0.05 in the said polypropylene agglomerate;
(5) the compound non-porous film that step (4) is obtained immerses under 8 ℃ in the mixed solution of sulfuric acid and phosphoric acid (volume ratio of sulfuric acid and phosphoric acid is 1: 1) fully, soaks 120 minutes, takes out after removing magnesium hydroxide fully, obtains thickness and be 43 microns battery diaphragm.
Embodiment 12
(1) with bibenzene tetracarboxylic dianhydride and 4; It is bibenzene tetracarboxylic dianhydride and 4 that 4 '-diaminodiphenyl ether joins quality with 1.2: 1 mol ratio, and in the oxolane that 4 '-diaminodiphenyl ether gross mass is 8 times, adding quality simultaneously is bibenzene tetracarboxylic dianhydride and 4; The magnesium hydroxide that 4 '-diaminodiphenyl ether gross mass is 0.13 times (particle mean size is 1.5 microns); Stirred 8 hours down at 50 ℃, obtain thick mixture, the inherent viscosity of this mixture [η]=190 milliliter/gram;
(2) under 30 ℃, the mixture of step (1) gained is coated on the corrosion resistant plate, under 110 ℃ of conditions, removed in dry 10 minutes then and desolvate, obtain polyamide acid film;
(3) mode of employing gradient increased temperature; The polyamide acid film that step (2) is obtained heats in nitrogen and carries out imidization; Obtain 35 microns polyimides non-porous film, mode of heating is: kept 3 hours down at 200 ℃, 240 ℃ kept 3 hours down; 280 ℃ kept 2 hours down, and 320 ℃ kept 1 hour down.
(4) will contain the polypropylene agglomerate fusion of magnesium hydroxide after, be coated on the polyimide film that step (3) obtains, place at normal temperatures after 1 hour and obtain compound non-porous film, the weight ratio of polypropylene and calcium hydroxide is 1: 0.06 in the said polypropylene agglomerate;
(5) the compound non-porous film that step (4) is obtained immerses under 5 ℃ in the hydrochloric acid of concentration 25% fully, soaks 180 minutes, takes out after removing calcium hydroxide fully, obtains thickness and be 45 microns battery diaphragm.
The correlated performance test result of the battery diaphragm of the foregoing description 7-12 gained is as shown in table 2.
Table 2
The foregoing description 7-12, the particle mean size of used pore-forming material is the 0.03-1.5 micron.
Embodiment 13
Prepare battery diaphragm like embodiment 7 said methods; Wherein, The quality of calcium hydroxide (particle mean size is 1.0 microns) is bibenzene tetracarboxylic dianhydride and 4 in the step (1), 0.04 times of 4 '-diaminodiphenyl ether gross mass, and the inherent viscosity of the viscous mixture of gained be [η]=180 milliliter/restrain; The thickness of the polyimides non-porous film of gained is 28 microns, and the thickness of the battery diaphragm that finally obtains is 32 microns.
Embodiment 14
Prepare battery diaphragm like embodiment 12 said methods; Wherein, The quality of magnesium hydroxide (particle mean size is 2.0 microns) is bibenzene tetracarboxylic dianhydride and 4 in the step (1), 0.08 times of 4 '-diaminodiphenyl ether gross mass, and the inherent viscosity of the viscous mixture of gained be [η]=170 milliliter/restrain; The thickness of the polyimides non-porous film of gained is 26 microns, and the thickness of the battery diaphragm that finally obtains is 40 microns.
Embodiment 15
Prepare battery diaphragm like embodiment 1 said method; Wherein, The quality of calcium hydroxide (particle mean size is 1.0 microns) is bibenzene tetracarboxylic dianhydride and 4 in the step (1), 0.05 times of 4 '-diaminodiphenyl ether gross mass, and the inherent viscosity of the viscous mixture of gained be [η]=190 milliliter/restrain institutes; The coat thickness of adjustment polyamide acid film, the coat thickness after the fusion of adjustment polypropylene agglomerate, the thickness of the polyimides non-porous film of gained is 32 microns, the thickness of the battery diaphragm that finally obtains is 45 microns.
Embodiment 16
Prepare battery diaphragm like embodiment 11 said methods; Wherein, The quality of magnesium hydroxide (particle mean size is 2.0 microns) is bibenzene tetracarboxylic dianhydride and 4 in the step (1), 0.08 times of 4 '-diaminodiphenyl ether gross mass, and the inherent viscosity of the viscous mixture of gained be [η]=150 milliliter/restrain; The thickness of the polyimides non-porous film of gained is 30 microns, and the thickness of the battery diaphragm that finally obtains is 42 microns.
Embodiment 17
Prepare battery diaphragm like embodiment 9 said methods; Wherein, The quality of potassium phosphate (particle mean size is 0.5 micron) is bibenzene tetracarboxylic dianhydride and 4 in the step (1), 0.12 times of 4 '-diaminodiphenyl ether gross mass, and the inherent viscosity of the viscous mixture of gained be [η]=180 milliliter/restrain; The coat thickness of adjustment polyamide acid film, the thickness of the polyimides non-porous film of gained is 33 microns, the thickness of the battery diaphragm that finally obtains is 40 microns.
Embodiment 18
Prepare battery diaphragm like embodiment 10 said methods; Wherein, The quality of tertiary sodium phosphate (particle mean size is 1.5 microns) is bibenzene tetracarboxylic dianhydride and 4 in the step (1), 0.15 times of 4 '-diaminodiphenyl ether gross mass, and the inherent viscosity of the viscous mixture of gained be [η]=170 milliliter/restrain; The thickness of the polyimides non-porous film of gained is 26 microns, and the thickness of the battery diaphragm that finally obtains is 38 microns.
The correlated performance test result of the battery diaphragm of the foregoing description 13-18 gained is as shown in table 3.
Table 3
Among the following embodiment 19-24, the polyamic acid of said polyamic acid for using prior art (comprising existing raw material and existing preparation method) to make.
Embodiment 19
(1) be that 1: 0.02 polyamic acid and calcium hydroxide (particle mean size is 1.5 microns) joins in the oxolane that quality is 4 times of polyamic acid quality with mass ratio; Stirred 8 hours down at 50 ℃; Obtain thick mixture, the inherent viscosity of this mixture [η]=150 milliliter/gram;
(2) under 30 ℃, the mixture of step (1) gained is coated on the corrosion resistant plate, under 110 ℃ of conditions, removed in dry 10 minutes then and desolvate, obtain polyamide acid film;
(3) mode of employing gradient increased temperature; The polyamide acid film that step (2) is obtained heats in nitrogen and carries out imidization; Obtain 26 microns polyimides non-porous film, mode of heating is: kept 3 hours down at 200 ℃, 240 ℃ kept 3 hours down; 280 ℃ kept 2 hours down, and 320 ℃ kept 1 hour down.
(4) will contain the polypropylene agglomerate fusion of calcium hydroxide after, be coated on the polyimide film that step (3) obtains, place at normal temperatures after 1 hour and obtain compound non-porous film, the weight ratio of polypropylene and calcium hydroxide is 1: 0.01 in the said polypropylene agglomerate;
(5) the compound non-porous film that step (4) is obtained immerses in the hydrochloric acid of concentration 25% under 15 ℃ fully; Soaked 30 minutes; The weight ratio of compound non-porous film and said solidification liquid is 1: 100, takes out after removing calcium hydroxide fully, obtains thickness and be 35 microns battery diaphragm.
Embodiment 20
(1) be that 1: 0.2 polyamic acid and sodium phosphate trimer (particle mean size is 0.8 micron) joins the N that quality is 9 times of polyamic acid quality with mass ratio; In the N-dimethylacetylamide; Stirred 8 hours down at 50 ℃; Obtain thick mixture, the inherent viscosity of this mixture [η]=100 milliliter/gram;
(2) under 30 ℃, the mixture of step (1) gained is coated on the glass plate, under 110 ℃ of conditions, removed in dry 10 minutes then and desolvate, obtain polyamide acid film;
(3) mode of employing gradient increased temperature; The polyamide acid film that step (2) is obtained heats in nitrogen and carries out imidization; Obtain 30 microns polyimides non-porous film, mode of heating is: kept 3 hours down at 200 ℃, 240 ℃ kept 3 hours down; 280 ℃ kept 2 hours down, and 320 ℃ kept 1 hour down.
(4) will contain the polypropylene agglomerate fusion of sodium phosphate trimer after, be coated on the polyimide film that step (3) obtains, place at normal temperatures after 1 hour and obtain compound non-porous film, the weight ratio of polypropylene and sodium phosphate trimer is 1: 0.1 in the said polypropylene agglomerate;
(5) the compound non-porous film that step (4) is obtained immerses under 0 ℃ in the hydrochloric acid of concentration 25% fully, soaks 180 minutes, takes out after removing sodium phosphate trimer fully, obtains thickness and be 42 microns battery diaphragm.
Embodiment 21
(1) be that 1: 0.1 polyamic acid and tertiary sodium phosphate (particle mean size is 0.5 micron) joins in the m-cresol that quality is 6 times of polyamic acid quality with mass ratio; Stirred 8 hours down at 50 ℃; Obtain thick mixture, the inherent viscosity of this mixture [η]=130 milliliter/gram;
(2) under 30 ℃, the mixture of step (1) gained is coated on the glass plate, under 110 ℃ of conditions, removed in dry 10 minutes then and desolvate, obtain polyamide acid film;
(3) mode of employing gradient increased temperature; The polyamide acid film that step (2) is obtained heats in nitrogen and carries out imidization; Obtain 33 microns polyimides non-porous film, mode of heating is: kept 3 hours down at 200 ℃, 240 ℃ kept 3 hours down; 280 ℃ kept 2 hours down, and 320 ℃ kept 1 hour down.
(4) will contain the polypropylene agglomerate fusion of tertiary sodium phosphate after, be coated on the polyimide film that step (3) obtains, place at normal temperatures after 1 hour and obtain compound non-porous film, the weight ratio of polypropylene and tertiary sodium phosphate is 1: 0.05 in the said polypropylene agglomerate;
(5) the compound non-porous film that step (4) is obtained immerses under 25 ℃ in hydrochloric acid and the phosphoric acid mixed aqueous solution (volume ratio of hydrochloric acid and phosphoric acid is 1: 1) fully; Soaked 120 minutes; The weight ratio of compound non-porous film and said solidification liquid is 1: 50; Take out after removing tertiary sodium phosphate fully, obtain thickness and be 40 microns battery diaphragm.
Embodiment 22
Prepare battery diaphragm like embodiment 19 said methods; Wherein, The mass ratio of polyamic acid and calcium hydroxide (particle mean size is 2.0 microns) is 1: 0.08 in the step (1); The inherent viscosity of the viscous mixture of gained is [η]=150 milliliter/gram, and the thickness of the polyimides non-porous film of gained is 28 microns, and the thickness of the battery diaphragm that finally obtains is 35 microns.
Embodiment 23
(1) be that 1: 0.15 polyamic acid and potassium phosphate (particle mean size is 1.5 microns) joins in the oxolane that quality is 4 times of polyamic acid quality with mass ratio; Stirred 8 hours down at 50 ℃; Obtain thick mixture, the inherent viscosity of this mixture [η]=190 milliliter/gram;
(2) under 30 ℃, the mixture of step (1) gained is coated on the corrosion resistant plate, under 110 ℃ of conditions, removed in dry 10 minutes then and desolvate, obtain polyamide acid film;
(3) mode of employing gradient increased temperature; The polyamide acid film that step (2) is obtained heats in nitrogen and carries out imidization; Obtain 35 microns polyimides non-porous film, mode of heating is: kept 3 hours down at 200 ℃, 240 ℃ kept 3 hours down; 280 ℃ kept 2 hours down, and 320 ℃ kept 1 hour down.
(4) will contain the polypropylene agglomerate fusion of potassium phosphate after, be coated on the polyimide film that step (3) obtains, place at normal temperatures after 1 hour and obtain compound non-porous film, the weight ratio of polypropylene and potassium phosphate is 1: 0.03 in the said polypropylene agglomerate; Said polyolefin is the polypropylene through the graft modification enhanced polarity.
(5) in the hydrochloric acid that the compound non-porous film that step (4) is obtained immerses under 30 ℃ fully and the mixed solution of sulfuric acid (volume ratio of hydrochloric acid and sulfuric acid is 2: 1), soaked 180 minutes, take out after removing potassium phosphate fully, obtain thickness and be 44 microns battery diaphragm.
Embodiment 24
Prepare battery diaphragm like embodiment 19 said methods; Wherein, The mass ratio of polyamic acid and calcium hydroxide is 1: 0.12 in the step (1); The inherent viscosity of the viscous mixture of gained is [η]=200 milliliter/gram, and the thickness of the polyimides non-porous film of gained is 27 microns, and the thickness of the battery diaphragm that finally obtains is 39 microns.Said polyolefin is the polyethylene through the graft modification enhanced polarity.
The correlated performance test result of the battery diaphragm of the foregoing description 19-24 gained is as shown in table 4.
Table 4
The battery that will contain the battery diaphragm of the foregoing description 1-6 gained carries out security performance test and battery life test.The gained result is as described in Table 5.
Table 5
The battery that will contain the battery diaphragm of the foregoing description 7-12 gained carries out security performance test and battery life test.The gained result is as described in Table 6.
Table 6
The battery that will contain the battery diaphragm of the foregoing description 13-18 gained carries out security performance test and battery life test.The gained result is as described in Table 7.
Table 7
The battery that will contain the battery diaphragm of the foregoing description 19-24 gained carries out security performance test and battery life test.The gained result is as described in Table 8.
Table 8
Test data in above-mentioned table 1 to the table 8 shows, the aperture of battery diaphragm provided by the invention, and porosity meets the requirement of lithium ion battery separator, and mechanical performance, resistance to elevated temperatures are also relatively good; Battery safety provided by the invention is good, long service life.
The above is merely preferred embodiment of the present invention, is not to be used to limit protection scope of the present invention.Every equalization that content is done according to the present invention changes and modifies, and all is encompassed in the claim of the present invention.
Claims (10)
1. a battery diaphragm is characterized in that, said battery diaphragm comprises polyimide porous membrane layer and polyolefin porous rete, and said polyolefin porous rete is bonded on the polyimide porous membrane layer; Said battery diaphragm is provided with through hole, and the aperture of said through hole is the 60-250 nanometer, and porosity is 30-60%.
2. a battery diaphragm according to claim 1 is characterized in that the thickness of said battery diaphragm is the 30-50 micron, and the thickness of said polyimide porous membrane layer is the 20-40 micron.
3. a battery diaphragm according to claim 1 is characterized in that the thickness of said battery diaphragm is the 35-45 micron, and the thickness of said polyimide porous membrane layer is the 25-35 micron.
4. a battery diaphragm according to claim 1 is characterized in that the aperture of said through hole is the 90-200 nanometer, and porosity is 35-55%.
5. the preparation method like the said battery diaphragm of one of claim 1 to 4 is characterized in that, said preparation method comprises the steps:
(1) mixture with polyamic acid, pore-forming material and solvent is coated on the supporter, except that after desolvating, obtains the polyamic acid non-porous film, is being lower than drying under the vitrification point of polyamide acid film, and is carrying out imidization, obtains the polyimides non-porous film;
(2) will contain the polyolefin master batch fusion of pore-forming material, be coated on the polyimides non-porous film of step (1) gained, after leaving standstill, obtain compound non-porous film;
(3) the compound non-porous film with step (2) gained contacts with solidification liquid, removes the pore-forming material, obtains comprising the battery diaphragm of polyimide porous membrane and polyolefin porous membrane.
6. one kind like the said preparation method of claim 5, it is characterized in that the weight ratio of said pore-forming material and said polyamic acid is 0.02-0.2: 1, and the weight ratio of said polyamic acid and said solvent is 1: 4-9; In the said polyolefin master batch that contains the pore-forming material, said pore-forming material and said polyolefinic weight ratio are 0.01-0.1: 1; The weight ratio of said compound non-porous film and said solidification liquid is 1: 10-150.
7. one kind like the said preparation method of claim 5, it is characterized in that said polyamic acid carries out condensation reaction through binary organic acid acid anhydride and organic diamine and obtains, and the mol ratio of said binary organic acid acid anhydride and organic diamine is 0.7-1.4: 1; The total weight of said binary organic acid acid anhydride and organic diamine and the weight ratio of said pore-forming material are 1: 0.02-0.2, and the total weight of said binary organic acid acid anhydride and organic diamine and the weight ratio of said solvent are 1: 4-9; In the said polyolefin master batch that contains the pore-forming material, the weight ratio of said polyolefin and said pore-forming material is 1: 0.01-0.1; The weight ratio of said compound non-porous film and said solidification liquid is 1: 10-150.
8. one kind like the said preparation method of claim 7, it is characterized in that said pore-forming material comprises the hydroxide of alkaline-earth metal, alkali-metal phosphate or sodium phosphate trimer; Said pore-forming material particle mean size is the 0.03-3 micron; Said solvent comprises N-2-methyl pyrrolidone, N, the combination of a kind of in N-dimethylacetylamide, oxolane or the m-cresol or at least two kinds; Said solidification liquid comprises the combination of a kind of in hydrochloric acid, sulfuric acid or the phosphoric acid or at least two kinds.
9. the preparation method of a battery diaphragm is characterized in that, said preparation method comprises the steps:
(1) with binary organic acid acid anhydride and organic diamine with 0.7-1.4: it is in binary organic acid acid anhydride and the organic diamine gross mass 4-9 solvent doubly that 1 mol ratio joins quality; Adding quality simultaneously is binary organic acid acid anhydride and organic diamine gross mass 0.02-0.2 pore-forming material doubly; Stirred 4-20 hour down at 30-60 ℃; Obtain thick mixture, the inherent viscosity of this mixture [η]=100-200 milliliter/gram;
(2) under 30-65 ℃, the mixture of step (1) gained is coated on the supporter, coat thickness is the 100-550 micron, then under 30-130 ℃ of condition, removes in dry 5-10 minute and to desolvate, and obtains polyamide acid film;
(3) adopt the mode of gradient increased temperature, the polyamide acid film of step (2) gained is heated in nitrogen carry out imidization, obtain the polyimide film of 20-40 micron;
(4) will contain the polypropylene agglomerate fusion of pore-forming material after, be coated on the polyimide film of step (3) gained, coat thickness is the 30-100 micron, places at normal temperatures after 1 hour and obtains compound non-porous film; The weight ratio of polypropylene and pore-forming material is 1 in the said polypropylene agglomerate: 0.01-0.1;
(5) with the compound non-porous film of step (4) gained under 0-50 ℃, be immersed in fully in the solidification liquid, soaked 30-180 minute, the weight ratio of said compound non-porous film and said solidification liquid is 1: 10-150, take out after removing the pore-forming material, obtain said battery diaphragm.
10. a battery comprises battery diaphragm, it is characterized in that, said battery diaphragm is the described battery diaphragm of one of claim 1 to 4.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103383996A (en) * | 2013-06-27 | 2013-11-06 | 江苏华东锂电技术研究院有限公司 | Preparation method of polyimide micro-pore diaphragm |
| CN104213333A (en) * | 2014-09-05 | 2014-12-17 | 北京化工大学常州先进材料研究院 | Polyimide/polyolefin complex fiber membrane with cross-linked structure and preparation method |
| WO2015003725A1 (en) | 2013-07-09 | 2015-01-15 | Friedrich-Schiller-Universität Jena | Electroactive polymers, manufacturing process thereof, electrode and use thereof |
| CN110286075A (en) * | 2019-06-12 | 2019-09-27 | 河北金力新能源科技股份有限公司 | A kind of test method of lithium ion battery separator closed pore temperature |
| CN111755649A (en) * | 2019-03-28 | 2020-10-09 | 河北金力新能源科技股份有限公司 | PEI coating slurry, diaphragm and preparation method and application thereof |
| CN111816840A (en) * | 2019-04-11 | 2020-10-23 | 宁德时代新能源科技股份有限公司 | Lithium supplement layer, negative pole piece thereof and lithium ion battery |
| CN113809469A (en) * | 2018-07-19 | 2021-12-17 | 河南义腾新能源科技有限公司 | Battery diaphragm casting sheet and manufacturing method thereof, and battery diaphragm and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103383996A (en) * | 2013-06-27 | 2013-11-06 | 江苏华东锂电技术研究院有限公司 | Preparation method of polyimide micro-pore diaphragm |
| CN103383996B (en) * | 2013-06-27 | 2015-07-22 | 江苏华东锂电技术研究院有限公司 | Preparation method of polyimide micro-pore diaphragm |
| WO2015003725A1 (en) | 2013-07-09 | 2015-01-15 | Friedrich-Schiller-Universität Jena | Electroactive polymers, manufacturing process thereof, electrode and use thereof |
| US10103384B2 (en) | 2013-07-09 | 2018-10-16 | Evonik Degussa Gmbh | Electroactive polymers, manufacturing process thereof, electrode and use thereof |
| CN104213333A (en) * | 2014-09-05 | 2014-12-17 | 北京化工大学常州先进材料研究院 | Polyimide/polyolefin complex fiber membrane with cross-linked structure and preparation method |
| CN113809469A (en) * | 2018-07-19 | 2021-12-17 | 河南义腾新能源科技有限公司 | Battery diaphragm casting sheet and manufacturing method thereof, and battery diaphragm and manufacturing method thereof |
| CN111755649A (en) * | 2019-03-28 | 2020-10-09 | 河北金力新能源科技股份有限公司 | PEI coating slurry, diaphragm and preparation method and application thereof |
| CN111816840A (en) * | 2019-04-11 | 2020-10-23 | 宁德时代新能源科技股份有限公司 | Lithium supplement layer, negative pole piece thereof and lithium ion battery |
| US11777085B2 (en) | 2019-04-11 | 2023-10-03 | Contemporary Amperex Technology Co., Limited | Lithium-supplement layer and its negative electrode sheet, lithium ion battery and device |
| CN110286075A (en) * | 2019-06-12 | 2019-09-27 | 河北金力新能源科技股份有限公司 | A kind of test method of lithium ion battery separator closed pore temperature |
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