CN102311559B - Composite isolation membrane and formation method thereof - Google Patents
Composite isolation membrane and formation method thereof Download PDFInfo
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Abstract
The invention provides a composite isolation membrane and a formation method thereof, and the method comprises the following steps: transforming a SO2F group or a H-type sulfonic group in perfluorosulfonate resin into a SO3Li group to obtain a perfluorosulfonate ion exchange resin with a SO3Li functional group; dissolving the obtained perfluorosulfonate ion exchange resin in a solvent to obtain a resin solution; performing surface treatment of a polyolefin micropore diaphragm to obtain a treated micropore diaphragm; soaking the polyolefin micropore diaphragm after surface treatment in the resin solution, taking the diaphragm out and drying to obtain a composite isolation membrane. According to the invention, by combining the perfluorosulfonate ion exchange resin which has a Li ion exchange function after ion transformation with the polyolefin micropore diaphragm after surface treatment, the polyolefin micropore diaphragm is modified; because of the high thermal stability, hydrophilicity, and ion exchange capability of the perfluorosulfonate ion exchange resin, the liquid absorption capacity, heat resistance and ion penetration capability of the isolation membrane are increased.
Description
Technical field
The invention belongs to polyolefin film manufacturing technology field, be specifically related to the formation method of a kind of composite isolated film and composite isolated film.
Background technology
At present, the polyolefin film material obtains increasing application and development, and current the application the most widely is the barrier material as lithium ion battery, becomes one of crucial interior layer assembly of lithium ion battery.Barrier material has fundamental influence to the performance of actual battery, and barrier film itself is the poor conductor of electronics, but also allows electrolyte ion to pass through.In addition, barrier material also must possess good chemistry, electrochemical stability and mechanism performance and in the repeated charge process, electrolytic solution kept the height wellability.Interface compatibility between barrier material and the electrode, barrier film all have considerable influence to the charge-discharge performance of lithium ion battery, cycle performance etc. to electrolytical retentivity.Polyolefin micropore barrier diaphragm has the stability in good mechanical performance and the electrolytic solution, but because polyolefinic nonpolar, wellability is not good enough between barrier film and the electrolytic solution, and there are defectives such as internal resistance is high, capacity is low in the battery that causes assembling.
Perfluorinated sulfonic resin is succeeded in developing the seventies by E.I.Du Pont Company the earliest, and is processed into the perfluorinated sulfonic acid PEM, is mainly used in modern chlorine industry and fuel cell field.The linear structure that perfluorinated sulfonic acid ion exchange resin main chain is formed for fluorine carbon, side chain is the perfluor ether structure that has sulfonic acid or sulfonic acid fluoride group.Wherein, main chain has given resin high thermostability, chemicalstability and higher physical strength.Side chain is then given the ability of resin IX.General adopt two yuan of ternarys even quarternary copolymerized forming such as the monomer that contains the sulfonic acid fluoride group and tetrafluoroethylene, R 1216, and contain the monomer structure of sulfonic acid fluoride.
For this reason, if thermostability, wetting ability and ion-exchange capacity and polyalkene diaphragm favorable mechanical performance that can perfluorinated sulfonic acid ion exchange resin is high combine, open up the raising that a kind of new composite isolated film will help the lithium cell overall performance.
Summary of the invention
In view of this, a kind of composite isolated film with higher electrolytic solution imbibition ability and lithium ion penetrativity and forming method thereof is provided.
A kind of formation method of composite isolated film, it comprises the steps:
With the SO in the perfluorinated sulfonic resin
2F group or H type sulfonic acid group change into SO
3The Li group, obtaining functional group is SO
3The perfluorinated sulfonic acid ion exchange resin of Li;
The perfluorinated sulfonic acid ion exchange resin that obtains is dissolved in the solvent, obtains resin solution;
With the polyolefin micropore barrier diaphragm surface treatment, the micro-pore septum that obtains handling;
Surface treated polyolefin micropore barrier diaphragm is immersed in the said resin solution, takes out drying, obtain composite isolated film.
And, a kind of composite isolated film, it comprises that polyolefin micropore barrier diaphragm and functional group are SO
3The perfluorinated sulfonic acid ion exchange resin of Li, the said perfluorinated sulfonic acid ion exchange resin formation method through above-mentioned composite isolated film is coated on said polyolefin micropore barrier diaphragm and constitutes said composite isolated film.
In above-mentioned composite isolated film and forming method thereof; Employing has the perfluorinated sulfonic acid ion exchange resin of Li ion exchanging function after ion transforms compound with the polyolefin micropore barrier diaphragm after surface treatment; Polyolefin micropore barrier diaphragm is carried out modification; Because high thermostability, wetting ability and the ion-exchange capacity of perfluorinated sulfonic acid ion exchange resin, thereby imbibition ability, thermotolerance and the ion penetration ability of raising barrier film.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is described further, in the accompanying drawing:
Fig. 1 is the formation method flow diagram of the composite isolated film of the embodiment of the invention;
Fig. 2 is the sem photograph of original polyolefin micropore barrier diaphragm;
Fig. 3 be among the embodiment 1 through surperficial uv irradiation with apply after the sem photograph of polyolefin micropore barrier diaphragm;
Fig. 4 be among the embodiment 2 through chemical conversion treatment with apply after the sem photograph of polyolefin micropore barrier diaphragm;
Fig. 5 is the sem photograph that directly applies the back polyolefin micropore barrier diaphragm among the embodiment 4;
Fig. 6 is the conductivity test result of the polyolefin micropore barrier diaphragm before applying;
Fig. 7 is the conductivity test result of the polyolefin micropore barrier diaphragm after applying in the embodiment of the invention.
Embodiment
In order to make the object of the invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with accompanying drawing and embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
See also Fig. 1, be the schema of the composite isolated film formation method of the embodiment of the invention, this method comprises the steps:
S01: with the SO in the perfluorinated sulfonic resin
2F group or H type sulfonic acid group change into SO
3The Li group, obtaining functional group is SO
3The perfluorinated sulfonic acid ion exchange resin of Li;
S02: the perfluorinated sulfonic acid ion exchange resin that obtains is dissolved in the solvent, obtains resin solution;
S03: with the polyolefin micropore barrier diaphragm surface treatment, the micro-pore septum that obtains handling;
S04: surface treated polyolefin micropore barrier diaphragm is immersed in the said resin solution, takes out drying, obtain composite isolated film.
In step S01, perfluorinated sulfonic resin can be wherein a kind of or their mixture such as the Nafion of E.I.Du Pont Company, the Dafion of Eastern Mountain, Shandong divine boat, the Flemion of rising sun pin, the Aciplex of Asahi Chemical Industry.Perfluorinated sulfonic resin can be that all hydrogen are all replaced by fluorine, and SO is promptly arranged
2The F group; Perhaps sulfonic acid group keeps, and SO is promptly arranged
3H is H type sulfonic acid group, can also both all have, and SO is arranged
2F group and H type sulfonic acid group, these groups all are converted to SO
3The Li group is SO to obtain functional group
3The perfluorinated sulfonic acid ion exchange resin of Li.
Concrete conversion process is: perfluorinated sulfonic resin is added in the LiOH aqueous solution, and at 80 ℃～120 ℃ refluxed 24h～72h, obtaining functional group is SO
3The perfluorinated sulfonic acid ion exchange resin of Li.Particularly, the concentration of the LiOH aqueous solution is 10%-30%.
In step S02, solvent can be water or organic solvent, perfluorinated sulfonic acid ion exchange resin being dissolved.Organic solvent can be ethanol, Virahol, terepthaloyl moietie, N, the mixing of one or more in dinethylformamide, DMSO 99.8MIN., the N-Methyl pyrrolidone.In these solvents, water, ethanol, Virahol belong to low boiling point solvent, terepthaloyl moietie, N, and dinethylformamide, DMSO 99.8MIN., N-Methyl pyrrolidone etc. belong to high boiling solvent.When dissolving perfluorinated sulfonic acid ion exchange resin forms resin, can also select lower boiling and high boiling mixed solvent for use earlier with replacing low boiling point solvent with high boiling solvent again behind the lower boiling dissolution with solvents wiring solution-forming.Dissolution conditions can carry out under normal pressure, also can under HTHP, carry out.After the dissolving, the mass concentration that forms perfluorinated sulfonic acid ion exchange resin is the resin solution of 3～5wt%.
Among the step S03, polyolefin micropore barrier diaphragm can be single-layer polypropylene (Polypropylene is abbreviated as PP) or high density polyethylene(HDPE) (Polyethylene is abbreviated as PP) micro-pore septum, also can be two-layer PP/PE or three layers of PP/PE/PP compound micro-pore septum.The commercially available prod can made or directly adopt to polyolefin micropore barrier diaphragm in advance, and both can be based on the thermal induction phase disengagement method is that wet method is made, and also can be based on melt stretching principle is that dry method is made.Polyolefin micropore barrier diaphragm thickness is preferably 12～60 microns.
Surface treatment can adopt chemical oxidation treatment or uv irradiation to handle, through perfluorinated sulfonic acid ion exchange resin polyolefin micropore barrier diaphragm is carried out surface modification treatment.Uv irradiation is handled and is specifically comprised the steps: above-mentioned micro-pore septum is immersed in the photoinitiator solution, soaks 10min～30min, carries out uv irradiation after the taking-up and handles 5min～60min.Photoinitiator solution is preferably the acetone soln that contains the light trigger UVNUL MS-40; Pass through light trigger; It forms radical on the polyolefin micropore barrier diaphragm surface under uv irradiation; And further under the oxygen effect, form polar group, thereby make perfluorinated sulfonic acid ion exchange resin to carry out chemically composited with polyolefin micropore barrier diaphragm easily.Chemical oxidation treatment is to adopt strong oxidizer to carry out chemical treatment, specifically comprises the steps: polyolefin micropore barrier diaphragm is immersed in by CrO
3, dense H
2SO
4And H
2O is in the treatment solution of forming in 1: 3: 4～1: 5: 10 by mass ratio, and treatment time 3min～10min cleans vacuum-drying, dense H then
2SO
4Be the sulphuric acid soln of mass concentration more than 70%, be preferably the sulfuric acid of normally used mass concentration 98.3%.Wherein, clean and in dense HCl, deionized water and acetone, carry out successively, dense HCl is meant the hydrochloric acid soln of mass concentration more than 37%.Vacuum-drying is down with vacuum drying oven drying two hours at 80 ℃.Chemical oxidation treatment makes the polyolefin micropore barrier diaphragm surface oxidation form polar group and increase surfaceness mainly through strong oxidation, makes perfluorinated sulfonic acid ion exchange resin carry out chemically composited with polyolefin micropore barrier diaphragm easily equally.
Among the step S04, polyolefin micropore barrier diaphragm is immersed in the above-mentioned resin solution through after the surface treatment, and soak time 5～60min takes out drying under 50-80 ℃ then, obtains composite isolated film.
After above-mentioned steps, the composite isolated film of acquisition comprises that polyolefin micropore barrier diaphragm and functional group are SO
3The perfluorinated sulfonic acid ion exchange resin of Li, this perfluorinated sulfonic acid ion exchange resin formation method through above-mentioned composite isolated film is coated on said polyolefin micropore barrier diaphragm and constitutes said composite isolated film.
In composite isolated film of above-mentioned formation and forming method thereof; Employing has the perfluorinated sulfonic acid ion exchange resin of Li ion exchanging function after ion transforms compound with the polyolefin micropore barrier diaphragm after surface treatment; Polyolefin micropore barrier diaphragm is carried out modification; Because high thermostability, wetting ability and the ion-exchange capacity of perfluorinated sulfonic acid ion exchange resin, thereby imbibition ability, thermotolerance and the Li ion penetration ability of raising barrier film.
Above-mentioned composite isolated film can be applicable in the lithium ion battery, promotes the over-all properties of lithium ion battery.Diaphragm application for example is installed in barrier film on the electrode materials when lithium ion battery, carries out the operations such as installation, location and encapsulation of other parts again, forms lithium ion battery.Through adopting the said polyolefins micro-pore septum, utilize its excellent imbibition ability, thermotolerance and ion penetration ability, promote the chemical property of lithium ion battery.
Below illustrate above-mentioned composite package isolation preparation method through a plurality of embodiment, with and aspect such as performance.Simultaneously, with its with do not carry out the surface-treated micro-pore septum and compare.
Embodiment 1
Get 1g perfluorinated sulfonic resin (Nafion of Du Pont) and put into container, the adding mass concentration is 27% the LiOH aqueous solution, and resin is immersed in the solution fully, and 100 ℃ were refluxed 48 hours, with the SO in the resin
2The F groups converted becomes SO
3The Li group, it is neutral fully washing to pH value, obtaining functional group is SO
3The perfluorinated sulfonic acid ion exchange resin of Li with ion exchanging function.Take by weighing the resin after the above-mentioned conversion, place three mouthfuls of containers (like there-necked flask), add the solvent DMSO 99.8MIN., logical nitrogen is removed air wherein.Be heated to more than 170 ℃, insulated and stirred dissolving in 2.5 hours obtains mass concentration and is approximately 5% even limpid resin solution.In beaker, dissolve in the 0.02g UVNUL MS-40 in the 20ml acetone, be fully immersed in the acetone that is dissolved with the light trigger UVNUL MS-40 soak time 10min to double-deck Vestolen PP 7052 micro-pore septum (40 microns).Taking-up is placed on irradiation 20min under the UV-light.Being fully immersed in 10min in the perfluor sulfoacid resin solution through the double-deck Vestolen PP 7052 micro-pore septum of UV-light surface-treated.Take out, vacuum-drying obtains composite isolated film.
Get 1g perfluorinated sulfonic resin (Nafion of Du Pont) and put into container, the adding mass concentration is 27% the LiOH aqueous solution, and resin is immersed in the solution fully, and 100 ℃ were refluxed 48 hours, with the SO in the resin
2The F groups converted becomes SO
3The Li group, it is neutral fully washing to pH value, obtaining functional group is SO
3The perfluorinated sulfonic acid ion exchange resin of Li with ion exchanging function.Take by weighing the resin after the above-mentioned conversion, place three mouthfuls of containers (like there-necked flask), add the solvent DMSO 99.8MIN., logical nitrogen is removed air wherein.Be heated to more than 170 ℃, insulated and stirred dissolving in 2.5 hours obtains mass concentration and is approximately 5% even limpid resin solution.In beaker, prepare CrO
3, dense H
2SO
4And H
2The O mass ratio is 1: 3: 4 a treatment solution; Be fully immersed in double-deck Vestolen PP 7052 micro-pore septum (40 microns) in this treatment solution; Treatment time 10min is positioned over successively in dense HCl, deionized water and the acetone afterwards and cleans, and is down subsequent use with vacuum drying oven drying two hours at 80 ℃.Be fully immersed in 10min in the perfluor sulfoacid resin solution through chemically treated double-deck Vestolen PP 7052 micro-pore septum.Take out, vacuum-drying obtains composite isolated film.
Embodiment 3
Get 1g perfluorinated sulfonic resin (Nafion of Du Pont) and put into container, the adding mass concentration is 27% the LiOH aqueous solution, and resin is immersed in the solution fully, and 100 ℃ were refluxed 48 hours, with the SO in the resin
2The F groups converted becomes SO
3The Li group, it is neutral fully washing to pH value, obtaining functional group is SO
3The perfluorinated sulfonic acid ion exchange resin of Li with ion exchanging function.Take by weighing the resin after the above-mentioned conversion, place three mouthfuls of containers (like there-necked flask), add the solvent DMSO 99.8MIN., logical nitrogen is removed air wherein.Be heated to more than 170 ℃, insulated and stirred dissolving in 2.5 hours obtains mass concentration and is approximately 5% even limpid resin solution.In beaker, prepare CrO
3, dense H
2SO
4And H
2The O mass ratio is 1: 5: 10 a treatment solution; Be fully immersed in double-deck Vestolen PP 7052 micro-pore septum (40 microns) in this treatment solution; Treatment time 10min; Being positioned over mass concentration afterwards successively is to clean in 37% hydrochloric acid soln, deionized water and the acetone, down subsequent use with vacuum drying oven drying two hours at 80 ℃.Be fully immersed in 10min in the perfluor sulfoacid resin solution through chemically treated double-deck Vestolen PP 7052 micro-pore septum.Take out, vacuum-drying obtains composite isolated film.
Get 1g perfluorinated sulfonic resin (Nafion of Du Pont) and put into container, the adding mass concentration is 27% the LiOH aqueous solution, and resin is immersed in the solution fully, and 100 ℃ were refluxed 48 hours, with the SO in the resin
2The F groups converted becomes SO
3The Li group, it is neutral fully washing to pH value, obtaining functional group is SO
3The perfluorinated sulfonic acid ion exchange resin of Li with ion exchanging function.Take by weighing the resin of above-mentioned processing, place three mouthfuls of containers, add the solvent DMSO 99.8MIN., logical nitrogen is removed air wherein.Be heated to more than 170 ℃, insulated and stirred dissolving in 2.5 hours obtains mass concentration and is approximately 5% even limpid resin solution.Be fully immersed in 10min in the perfluor sulfoacid resin solution to double-deck Vestolen PP 7052 micro-pore septum (40 microns).Take out, vacuum-drying obtains composite isolated film.
Comparative example 1
Original double-deck Vestolen PP 7052 barrier film, 40 microns of thickness.
Test and result:
As relatively, the composite isolated film that the method in the foregoing description and the comparative example makes is tested as follows suction electrolytic solution ability and specific conductivity performance test when mainly investigating its barrier film that is applied to do in the lithium ion battery electrode.
Inhale the electrolytic solution aptitude tests: adopt 1mol/L LiPF
6/ EC:DEC=1: 1 electrolytic solution, with reference to the SJ/T10171.1 standard, barrier film is immersed in this electrolytic solution 4 hours, after barrier film is taken out, unsettled 30 seconds, the weight before and after the test barrier film soaks on electronic balance was calculated pick up.
Room-temperature conductivity test: adopt AC impedence method, barrier film is immersed 1mol/LLiPF
6/ EC:DEC=1: in 1 the electrolytic solution 2 hours, pick up with tweezers, filter paper blots the electrolysis drop.With scissors clip one fritter barrier film, and the one of which end is clipped on the stainless steel electrode, the other end is soaked in the electrolytic solution of above-mentioned same concentrations; Adopt AC impedence method; With CHI electrochemical analyser testing conductivity, it is 5 millivolts that test process exchanges the perturbation amplitude, and range of frequency is 1-10
5Hz.
Above-mentioned each embodiment and comparative example comparative result are seen Fig. 2,3,4,5,6.Fig. 2 is the sem photograph of primary polyolefine isolating film in the comparative example 1; Fig. 3 is the compound separated membranous sem photograph of surperficial uv irradiation and coating back among the embodiment 1; Fig. 4 is the sem photograph that chemical conversion treatment also applies the composite isolated film of back formation among the embodiment 2, and Fig. 5 is the sem photograph of direct coating back polyalkene diaphragm among the embodiment 4.Particularly, compare with Fig. 2 at Fig. 3,4, the barrier film surface among Fig. 3 and 4 can see having uniform wetting ability sulfonic acid tectum, improves the electrolytic solution ability of inhaling thus.Fig. 5 can know that directly coating procedure is owing to a little less than the affinity of polyolefine and perfluorinated sulfonic resin, cause coat to be not easy to apply and come off easily.And after uv irradiation and chemical treatment, improved the binding property of coat and base layer.Fig. 6 and Fig. 7 are respectively the conductivity test results of barrier film before and after applying, and can be known by figure, apply back this body resistance of barrier film and and electrode between interface resistance all obviously reduce.
Ionic conductivity through calculating is seen table 1.Visible by table 1, after surface-coated was handled, the pick up of barrier film obviously improved, and specific conductivity obtains certain raising.
Table 1 coated insulation film pick up and ionic conduction ability
The above is merely preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. the formation method of a composite isolated film, it comprises the steps:
With the SO in the perfluorinated sulfonic resin
2F group or H type sulfonic acid group change into SO
3The Li group, obtaining functional group is SO
3The perfluorinated sulfonic acid ion exchange resin of Li;
The perfluorinated sulfonic acid ion exchange resin that obtains is dissolved in the solvent, obtains resin solution;
With the polyolefin micropore barrier diaphragm surface treatment, the micro-pore septum that obtains handling;
Surface treated polyolefin micropore barrier diaphragm is immersed in the said resin solution, takes out drying, obtain composite isolated film;
Said with the SO in the perfluorinated sulfonic resin
2F group or H type sulfonic acid group change into SO
3The step of Li group comprises: perfluorinated sulfonic resin is added in the LiOH aqueous solution, and at 80 ℃～120 ℃ refluxed 24h～72h, obtaining functional group is SO
3The perfluorinated sulfonic acid ion exchange resin of Li;
Said surface treatment comprises the steps: polyolefin micropore barrier diaphragm is soaked in the photoinitiator solution, soaks 10min～30min, carries out uv irradiation after the taking-up and handles 5min～60min; Perhaps polyolefin micropore barrier diaphragm is immersed in by CrO
3, the H of mass concentration more than 70%
2SO
4Solution and H
2O is in the treatment solution of forming in 1: 3: 4～1: 5: 10 by mass ratio, and treatment time 3min～10min cleans vacuum-drying then.
2. the formation method of composite isolated film as claimed in claim 1 is characterized in that, said photoinitiator solution is the acetone soln that contains UVNUL MS-40.
3. the formation method of composite isolated film as claimed in claim 1 is characterized in that, said cleaning is in mass concentration 37% above hydrochloric acid soln, deionized water and acetone, to carry out successively.
4. the formation method of composite isolated film as claimed in claim 1 is characterized in that, said solvent is water, ethanol, Virahol, terepthaloyl moietie, N, the mixing of one or more in dinethylformamide, DMSO 99.8MIN., the N-Methyl pyrrolidone.
5. the formation method of composite isolated film as claimed in claim 1 is characterized in that, the mass concentration of perfluorinated sulfonic acid ion exchange resin is 3%-5% in the said resin solution.
6. the formation method of composite isolated film as claimed in claim 1; It is characterized in that; The thickness of said polyolefin micropore barrier diaphragm is 12 microns～60 microns, and said polyolefin micropore barrier diaphragm is single-layer polypropylene, high density polyethylene(HDPE) or two layers of polypropylene/Vilaterm or three-layer polypropylene/polyethylene/polypropylene compound micro-pore septum.
7. a composite isolated film is characterized in that, comprises that polyolefin micropore barrier diaphragm and functional group are SO
3The perfluorinated sulfonic acid ion exchange resin of Li, said perfluorinated sulfonic acid ion exchange resin are coated on said polyolefin micropore barrier diaphragm through the formation method like the arbitrary described composite isolated film of claim 1-9 and constitute said composite isolated film.
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| CN106159301B (en) * | 2016-08-19 | 2019-07-02 | 电子科技大学 | A kind of preparation method of perfluorosulfonic acid proton exchange film |
| CN106601968A (en) * | 2016-11-09 | 2017-04-26 | 安徽兰兮工程技术开发有限公司 | Method for producing battery diaphragm |
| CN108075088B (en) * | 2016-11-10 | 2021-01-22 | 苏州高通新材料科技有限公司 | Lithium battery diaphragm containing sulfonated graphene lithium salt, preparation method and application thereof |
| CN109546052A (en) * | 2018-09-29 | 2019-03-29 | 大连中比动力电池有限公司 | A kind of preparation method of perfluorinated sulfonic acid lithium coating diaphragm |
| CN109585750B (en) * | 2018-10-26 | 2021-10-15 | 大连中比动力电池有限公司 | Composite diaphragm and preparation method thereof |
| CN115693028A (en) | 2019-03-27 | 2023-02-03 | 宁德新能源科技有限公司 | Separator, and electrochemical device and electronic device comprising same |
| CN110416477A (en) * | 2019-07-19 | 2019-11-05 | 田韬 | A kind of lithium-sulphur cell positive electrode ion infiltration type cladding membrane material |
| CN111180637A (en) * | 2020-01-07 | 2020-05-19 | 四川东为氢源科技有限公司 | Sodium ion battery diaphragm and preparation method and application thereof |
| CN111916638A (en) * | 2020-08-04 | 2020-11-10 | 珠海冠宇电池股份有限公司 | Battery diaphragm, preparation method and battery |
| CN112886140A (en) * | 2021-01-29 | 2021-06-01 | 苏州科技大学 | Modified diaphragm of lithium-sulfur battery and preparation method and application thereof |
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