CN101267027A - A method for making filth-resisting polythene-vinyl alcohol battery separation film - Google Patents
A method for making filth-resisting polythene-vinyl alcohol battery separation film Download PDFInfo
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- CN101267027A CN101267027A CNA2008100358872A CN200810035887A CN101267027A CN 101267027 A CN101267027 A CN 101267027A CN A2008100358872 A CNA2008100358872 A CN A2008100358872A CN 200810035887 A CN200810035887 A CN 200810035887A CN 101267027 A CN101267027 A CN 101267027A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a preparation method of anti-pollution polyethylene-vinyl alcohol battery isolation membrane which comprises the flowing steps: first of all, weighing respectively the polyethylene-vinyl alcohol, isopropyl alcohol and distilled water added into a container, heating in water bath and refluxing, and stirring to dissolve; then add sulfonation agent and initiator into the container, heating and stirring; secondly, implementing electro spinning respectively to sulfonation solution, obtaining a certain thickness non-woven cloth membrane on collected wheel; finally, causing the non-woven cloth immersed into cross-linked liquid dipped by glutaraldehyde, distilled water and HCl, keeping constant temperature for proper time, then taking out the non-woven cloth, washing and drying. The isolation membrane has good selectivity, ion conduction and anti-pollution ability after being sulfonated by sulfonation agent. As the number of cross-linking point between fibers increases, the dimensional stability of the isolation membrane enhances, the dimension of the isolation membrane is more stable after being cross-linked by the glutaraldehyde.
Description
Technical field
The present invention relates to the modification method for preparing technical field of a kind of battery with polythene-ethenol.
Background technology
Battery diaphragm is called battery " the 3rd utmost point ", is one of important component part of cadmium-nickel, nickel-hydrogen battery, plays to isolate anode and cathode battery is short-circuited, and conductive ion can be passed through smoothly for Electolyte-absorptive, and allows effect such as gas permeation barrier film.The quality of its quality directly has influence on the charge-discharge performance, high temperature performance of battery, charged storage and useful life or the like, therefore requires battery diaphragm material must have excellent acid alkalescence and low resistive.Usually battery diaphragm more options synthetic fibers are as Fypro, poly-ethanol fiber, polypropylene fibre, polyester fiber, polyolefine fiber etc., wherein polyolefine fiber is with its good resistance to wear, elasticity, excellent acid and alkali-resistance, oxidative resistance, heat-resisting quantity and in light weight be preferred material.But the hydrophily extreme difference of polyolefine fiber must carry out modification to it and handle, and just can satisfy the requirement of battery diaphragm.
The maximum difficult point of current existence is, the used barrier film of lithium-ions battery has been failed substantial breakthrough.China produces each producer of lithium ion battery, all depends on external import, and its price is even accounted for more than 20% of production cost! In fact, what precious materials the used barrier film of lithium ion battery is not, just China so far the technology aspect large-scale production do not reach a standard yet! If these technological difficulties are solved, the production cost of China's lithium-ions battery can also descend significantly.
But premium properties such as alkaline secondary cell discharges and recharges often owing to having, long fast charging and discharging, high-multiplying power discharge and overcharging resisting of life-span are more and more paid attention to by people.But there are very big gap all the time in homemade alkaline secondary cell of China and import battery such as Panasonic, Toshiba etc., and wherein the quality problems of battery diaphragm are one of major reasons.Improving membrane properties is to improve the most direct means of battery cycle life.
Battery diaphragm is as an indispensable part in the battery, and it mainly plays and prevents inside battery because the dendritic growth of electrode, overlaps mutually and the battery short circuit that produces and allow the freely through effect of relevant ions.At present, the most frequently used alkaline battery separator is the polypropylene nonwoven film, because its surface is nonpolarity, hydrophily is bad, and then causes lower electrolyte adsorption capacity.The non-weaving cloth fibre diameter that adopts traditional melt-blown process to make is thicker, the aperture is bigger, and skewness, influences in the electrolytic solution non-weaving cloth to the lenticular obstruct of electrode, strengthened the probability of the short circuit phenomenon of inside battery, thereby reduced the useful life of battery.
The non-weaving cloth of high-voltage electrostatic spinning technology preparation is a kind of porous material with nanometer micropore, and it has high specific area and surface energy, thereby is showing specificity aspect physics, the chemical property, has multiple potential use.
Summary of the invention
The purpose of this utility model is to provide a kind of preparation method's technology of filth-resisting polythene-vinyl alcohol battery separation film, and a kind of new battery diaphragm is provided.
Usually ethylene-vinyl alcohol copolymer is made by ethene and vinyl acetate copolymerized, alcoholysis, and the gas barrier properties, hydrophily that are a kind of processability of gathering ethene and polyvinyl alcohol are in the half hitch crystal formation block copolymer of one.This paper is solvent by introducing sulfonating agent with isopropyl alcohol and water, adopts the high-voltage electrostatic spinning technology to prepare not weaving fabric of superfine fiber, and after method such as crosslinked it is carried out modification, and the performance of non-weaving cloth barrier film is studied.
For reaching above-mentioned purpose, the concrete technical scheme that the present invention takes is as follows:
The preparation method of filth-resisting polythene-vinyl alcohol battery separation film the steps include:
Take by weighing polythene-ethenol, isopropyl alcohol and distilled water at first respectively and add in the container, the water-bath reflux is stirred to dissolving;
In container, add sulfonating agent and initator then, add thermal agitation;
Secondly the solution after the sulfonation is carried out electrospinning respectively, on the collection wheel, obtain certain thickness non-weaving cloth film;
Non-weaving cloth is immersed in the crosslinked fluid that is made into by glutaraldehyde, distilled water and HCl at last, in baking oven, takes out behind the constant temperature appropriate time, clean and dry.
The preparation method of above-mentioned filth-resisting polythene-vinyl alcohol battery separation film, used polythene-ethenol preferably contains the polymer of 68%～71% vinyl alcohol repetitive.
The preparation method of above-mentioned filth-resisting polythene-vinyl alcohol battery separation film, the temperature of first step water-bath reflux is 80～100 ℃.
The preparation method of above-mentioned filth-resisting polythene-vinyl alcohol battery separation film, used sulfonating agent comprises conventional sulfonating agent, as sulfuric acid, chlorosulfonic acid, sulfur trioxide etc., can also adopt gentle sulfonating agents such as sulphonic acid ester, preferred sulfonation condition is that condition solution pH value is less than 2.
The preparation method of above-mentioned filth-resisting polythene-vinyl alcohol battery separation film, the temperature at the baking oven inner drying is set in 50～80 ℃ at last, and fitst water is 60～70 ℃.
Beneficial effect of the present invention:
The present invention carries out sulfonation with polythene-ethenol and makes the non-weaving cloth battery diaphragm, and barrier film demonstrates good selectivity, ionic conductivity and contamination resistance after the sulfonating agent sulfonation.Simultaneously, when the molecular energy of its fiber surface and solution were had an effect, film showed very strong suction alkalescence, and alkali absorbing rate can reach 95%; The dimensional stability of barrier film strengthens along with increasing of crosslinking points between fiber, and the size of the barrier film behind glutaraldehyde cross-linking is more stable.
Embodiment
Embodiment 1
One, experimental raw and reagent
Polythene-ethenol contains 68%～71% vinyl alcohol repetitive: Japanese synthetic chemical industry company;
Isopropyl alcohol: analyze purely, Dihua worker Co., Ltd is won in Tianjin;
Glutaraldehyde: analyze pure, Tianjin Da Mao chemical reagent factory;
Hydrochloric acid: analyze pure, the magnificent chemical plant of shining, Tianjin;
Chlorosulfonic acid: general commercially available getting final product;
Potassium hydroxide: analyze purely, reagent Co., Ltd is learned in triumphant Tonghua, Tianjin.
Two, experimental provision
Electronic thermostatic water-bath: Tianjin Si Taite Instr Ltd.;
8522 type constant temperature blender with magnetic force: Jintan City the earth self-reacting device factory;
High-voltage electrostatic spinning machine: Jintan City the earth self-reacting device factory
Three, the preparation of polythene-ethenol nonwovens
Take by weighing 3 parts of 10g polythene-ethenols, 70mL isopropyl alcohol and 30mL distilled water respectively and add in the three-necked bottle, reflux in 80 ℃ of waters bath with thermostatic control is stirred to dissolving.Take off wherein two three-necked bottles, wherein solution is designated as S1, S2 respectively; Add 11g chlorosulfonic acid and hydrochloric acid one by one in another three-necked bottle, stir rapidly and heat, wherein mixed solution is designated as S3.An amount of spinning solution is added in the syringe, and the distance that adopts the 16# syringe needle to regulate between spinning head and the fiber collecting wheel is that 10cm, voltage are 20kV.Above-mentioned S1, S2, S3 solution are carried out electrospinning respectively, on the collection wheel, obtain certain thickness non-weaving cloth film behind the 4h, be designated as S1, S2, S3 respectively.Non-weaving cloth SE2 is immersed in the crosslinked fluid that is made into by 20mL glutaraldehyde, 1000mL distilled water and 20mLHCl, in 70 ℃ baking oven, takes out behind the constant temperature 2h, clean and dry, be designated as S2.
Four, structural characterization and performance test
FEI Sirion type scanning electron microscopy: Dutch PHILIPS Co.;
JJ C21 type soaks into angle tester: Changchun optical instrument head factory;
The performance test of polythene-ethenol nonwovens battery diaphragm is to test according to electronics industry standard SJ/T10171291.
Five experimental results
1, the non-weaving cloth microscopic appearance is analyzed
Concentration for the 10%v/v spinning solution utilize high-voltage electrostatic spinning make its fibre diameter of non-weaving cloth for 3m about, the bonding phenomenon appears in the aperture between 18m part fiber, this may be because during electrospinning, solvent can not in time vapor away, make when fiber still is a semisolid, just on the reception wheel, be collected, cause occurring between fiber bonding;
Non-weaving cloth is through the crosslinked SEM figure of glutaraldehyde solution, and the diameter of fiber is that the mesh rate is less about 2 μ m, and the aperture is about 7m, and interfibrous crosslinking points is more.This is that the aldehyde cross-linking reaction is further carried out, and bonds together between the fiber and make because under effect of electric field;
Non-weaving cloth SEM figure after sulfonation, fiber is flat band shape, and diameter is that the mesh rate is bigger about 4 μ m, and the aperture is about 8m.Dimensional stability is analyzed battery diaphragm material must have certain dimensional stability.Size stability mainly is subjected to what influence of crosslinking points between the orientation of fiber in the film and fiber.Table 1 has been listed the breathing rate data of non-weaving cloth.
The breathing rate statistics of table 1 non-weaving cloth
Data from table 1 as can be seen, the variation of non-weaving cloth thickness is big relatively, horizontal and vertical change in size is less.Thickness change with non-weaving cloth in interfibrous crosslinked relevant, when interfibrous crosslinking points more for a long time, interfibrous active force is bigger, fiber is difficult for deforming, so dimensional stability is better.The horizontal and vertical change in size of non-weaving cloth mainly is because the fiber in the non-weaving cloth has taken place in KOH solution by readjusting of orientation, makes energy reach minimum, and therefore horizontal and vertical size is more stable.
2, wettability analysis
Contact angle has embodied the wetting property of non-weaving cloth, and contact angle is more little, and wettability is good more.The static contact angle method of testing is adopted in this test, and 15 microlitre drops are dripped to membrane surface, reads the contact angle that contact angle numerical value is this barrier film during 15s.
Table 2 has provided film two surperficial inner surfaces: tabular surface contacts with the collection wheel; Outer surface: matsurface respectively with the contact angle numerical value of water and alkali lye.
The contact angle of the non-manufacturing cloth of table 2
Tabular surface in the table 2 is close to the one side of collecting wheel during for electrostatic spinning, and matsurface is the another side of film.Experimental water is a deionized water, and electrolyte is 40% KOH solution.
Data from table 2 as can be seen, bigger than the contact angle of KOH solution with the contact angle of water through the tabular surface of the non-weaving cloth of sulfonating agent sulfonation and glutaraldehyde cross-linking, tabular surface is littler than the contact angle of matsurface and alkali with the contact angle of alkali.The surface energy of contact is low more, stable more.When liquid soaked at film surface, the functional group of film surface molecule can have an effect with liquid, and wettability is better.The contact angle of water is bigger than the contact angle of KOH solution, and this is because the surface energy of KOH solution is low, and the OH in the solution is more, can cause with the molecule of the membrane surface institute that has an effect.Because the significant difference of polymer and organic molecule material performance demonstrates good selectivity, ionic conductivity and contamination resistance.And aldehyde is crosslinked mainly is in the molecule-the dehydration etherification reaction takes place, generates C-O-C in OH.The polarity of ehter bond is littler than the polarity of hydroxyl, and its imbibition ability is also little.Data from table as can be seen, the contact angle of the non-weaving cloth film of crosslinked mistake increases.
3, resistance and alkali absorbing rate analysis
The resistance of barrier film is to weigh one of good index of membrane properties.The resistance of barrier film is relevant with the thickness of barrier film, aperture and tightness etc.Table 3 has been listed the relation of the performance of resistance and barrier film.
The relation of table 3 resistance and membrane properties
| Project | Thickness | Quantitatively | Tightness | Face resistance | Opposite face resistance | Alkaline-resisting loss | Alkali absorbing rate |
| S1 | 0.301 | 150 | 5.21 | 1.59 | 4.93 | -5.98 | 791 |
| S2 | 0.267 | 51 | 2.37 | 0.08 | 1.02 | -1.37 | 154 |
| S3 | 0.280 | 42 | 1.93 | 1.08 | 5.01 | 1.41 | 988 |
As can be seen from Table 3, the mesh rate of film, aperture, thickness directly influence the resistance of film.Film is thick more, and resistance is big more.The mesh rate is big more, and resistance is more little.Film quantitatively relevant with the thickness of film, film is thick more, and is then quantitatively big more.Tightness has characterized the tightness degree of fiber accumulations in the film.
Data from table 3 as can be seen, the tightness of film is big more, the resistance of film is big more; The thickness of film is thick more, and then the resistance of film is big more.Because in alkaline battery, conductive materials is mainly ion, and the factor that influences ion motion can produce very big influence to resistance.The mesh rate of film is big more, and the aperture is big more, and film is thin more, and ion is easy of more film, and resistance is more little then.The alkali absorbing rate of barrier film and alkaline-resisting loss have embodied the good of the suction alkalescence of film and chemical stability.The suction alkali of non-weaving cloth mainly is divided into two parts, and in the space of a part in non-weaving cloth, another part then is adsorbed on the surface of fiber.The alkali absorbing rate of film is along with the space in the film is increased and increased.Big more and can have an effect with solution the time, the suction alkalescence of film is bigger when the surface area of fiber in the film.The crosslinked content of the C-O-C in the molecule that makes raises, and reduces the adsorption capacity of fiber surface.The alkaline-resisting loss of barrier film is all less as can be seen from Table 3, and the chemical stability of hence one can see that EVOH non-weaving cloth is stronger.
This shows
The resistance of non-weaving cloth barrier film and its thickness, mesh rate, tightness, aperture are relevant, and reduce along with the increase in aperture, increase along with the increase of thickness; The alkali absorbing rate of non-weaving cloth barrier film is relevant with the mesh rate with the specific area of barrier film, increases along with the increase of barrier film mesh rate; Barrier film is after sulfonation, and it demonstrates good selectivity, ionic conductivity and contamination resistance; The dimensional stability of barrier film strengthens along with increasing of crosslinking points between fiber, and the size of the barrier film behind glutaraldehyde cross-linking is more stable.
Claims (10)
1, a kind of preparation method of filth-resisting polythene-vinyl alcohol battery separation film the steps include:
Take by weighing polythene-ethenol, isopropyl alcohol and distilled water at first respectively and add in the container, the water-bath reflux is stirred to dissolving;
In container, add sulfonating agent and initator then, add thermal agitation;
Secondly the solution after the sulfonation is carried out electrospinning respectively, on the collection wheel, obtain certain thickness non-weaving cloth film;
Non-weaving cloth is immersed in the crosslinked fluid that is made into by glutaraldehyde, distilled water and HCl at last, in baking oven, takes out behind the constant temperature appropriate time, clean and dry.
2, the preparation method of filth-resisting polythene-vinyl alcohol battery separation film as claimed in claim 1 is characterized in that: used polythene-ethenol is the polymer that contains 68%～71% vinyl alcohol repetitive.
3, the preparation method of filth-resisting polythene-vinyl alcohol battery separation film as claimed in claim 1 is characterized in that: the temperature of first step water-bath reflux is 80～100 ℃.
4, the preparation method of filth-resisting polythene-vinyl alcohol battery separation film as claimed in claim 3 is characterized in that: the temperature of first step water-bath reflux is 95～100 ℃.
5, the preparation method of filth-resisting polythene-vinyl alcohol battery separation film as claimed in claim 1 is characterized in that: used sulfonating agent comprises sulfuric acid, chlorosulfonic acid and sulfur trioxide.
6, the preparation method of filth-resisting polythene-vinyl alcohol battery separation film as claimed in claim 5 is characterized in that: used sulfonating agent is a chlorosulfonic acid.
7, the preparation method of filth-resisting polythene-vinyl alcohol battery separation film as claimed in claim 1 is characterized in that: used sulfonating agent is a sulphonic acid ester.
8, as the preparation method of claim 5 or 6 described filth-resisting polythene-vinyl alcohol battery separation films, it is characterized in that: the solution pH value is less than 2.
9, the preparation method of filth-resisting polythene-vinyl alcohol battery separation film as claimed in claim 1 is characterized in that: the temperature at the baking oven inner drying is set in 50～80 ℃ at last.
10, the preparation method of filth-resisting polythene-vinyl alcohol battery separation film as claimed in claim 9 is characterized in that: the temperature at the baking oven inner drying is set in 60～70 ℃ at last.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618943A (en) * | 2012-03-13 | 2012-08-01 | 西安交通大学 | Method for preparing ethylene vinyl alcohol (EVOH) nano tubular fibers for treating burns |
| CN114752164A (en) * | 2022-03-18 | 2022-07-15 | 国家电投集团氢能科技发展有限公司 | Ethylene-vinyl alcohol copolymer compound and application thereof |
-
2008
- 2008-04-10 CN CNA2008100358872A patent/CN101267027A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618943A (en) * | 2012-03-13 | 2012-08-01 | 西安交通大学 | Method for preparing ethylene vinyl alcohol (EVOH) nano tubular fibers for treating burns |
| CN102618943B (en) * | 2012-03-13 | 2014-09-03 | 西安交通大学 | Method for preparing ethylene vinyl alcohol (EVOH) nano tubular fibers for treating burns |
| CN114752164A (en) * | 2022-03-18 | 2022-07-15 | 国家电投集团氢能科技发展有限公司 | Ethylene-vinyl alcohol copolymer compound and application thereof |
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Open date: 20080917 |