CN100487042C - Quasi-solid polymer water solution system electrolyte film and its preparing method - Google Patents
Quasi-solid polymer water solution system electrolyte film and its preparing method Download PDFInfo
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- CN100487042C CN100487042C CNB2005100004022A CN200510000402A CN100487042C CN 100487042 C CN100487042 C CN 100487042C CN B2005100004022 A CNB2005100004022 A CN B2005100004022A CN 200510000402 A CN200510000402 A CN 200510000402A CN 100487042 C CN100487042 C CN 100487042C
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Abstract
The present invention relates to a kind of quasi-solid polymer aqua system electrolyte film unlike that in lithium ion cell and its preparation process. The quasi-solid polymer aqua system electrolyte film is specially for water solution electrolyte energy conversion system. Two or more kinds of polymer material and additive are prepared into solid polymer electrolyte film through emulsification, film coating, drying and other steps, and there are at least a kind of polymer material without swelling in alkali aqua and at least a kind of strong hydroscopic resin. The solid polymer electrolyte film has the advantages of powerful electrolyte liquid maintaining capacity, high conductivity, high stability, etc. and can raise the circulating service life of cell and capacity, lower self discharge, avoid liquid leakage and simplify technological process.
Description
Technical field
The present invention relates to a kind of dielectric film, particularly a kind of quasi-solid polymer water solution system electrolyte film and preparation method belong to new green power material field.
Background technology
Ionic conduction behavior in the inorganic salt crystal just was familiar with by people as far back as 19 end of the centurys, and after 1913 found that α-AgI crystal has very large ionic conductance, solid electrolyte just really was subject to people's attention.Wright finds that the seventies polyethylene oxide (PEO) and inorganic salt can form the complex compound with higher ionic conductivity, this class is in solid state also can dissolve supporting electrolyte as liquid, and the macromolecular material of ion migration phenomenon can take place, be called as polymer solid electrolyte (solid polymer electrolyte, be called for short SPE), polymeric Solid Ionic Conductor (polymeric solidionic conductor), macromolecale rapid ionic conductive (polymeric fast ionic conductor), with the sub-polymer of diversion (ion-conducting polymer), real polymer solid electrolyte with practical value is prepared at the end of the seventies by people such as Armand, very fast, this family macromolecule solid electrolyte just is widely used in fuel cell and lithium cell, up to the present, be applied to alkaline cell such as Ni-MH battery, the Ni-Cd battery, Ni-Zn battery etc. mainly is a polymer gel electrolyte, though also obtain remarkable progress in recent years, also be not used in the industrialization of these batteries.The one, the gel electrolyte manufacturability is poor, add difficulty during use, the 2nd, the ventilation property difference influences the diffusion of inside battery gas, the 3rd, intensity difference, also need to add in addition barrier film or electrode from far away, reduce space availability ratio, in addition because these batteries all can't break away from potassium hydroxide and water at present, so the research of the solid electrolyte on the absolute sense is very difficult.
There is scientist to be devoted to the research of the solid electrolyte of alkaline aqueous solution system from the eighties both at home and abroad always, and being not limited to macromolecular material, the solid electrolyte of having reported at present can be divided three classes: inorganic hydrate solid electrolyte, organic salt hydrate solids ionogen and polymer solid electrolyte.
With Sb
2O
5XH
2O is the inorganic hydrate solid electrolyte of representative, has opened up the beginning of the solid electrolyte research of alkaline aqueous solution system, but has up to the present also had only this report.Organic salt hydrate solids ionogen has five hydration tetramethyl-ammonium (CH
34NOH5H
2O; What report was maximum at present is polymer solid electrolyte, is actually macromolecular material+KOH+H
2The multicomponent system of O, macromolecular material commonly used have PEO, PVA, PPA, P (ECH-co_EO) etc.The work-ing life that can improve battery with this preparation of electrolyte alkaline cell.
Also be not used at present the report of all solid state electrolyte truly of alkaline cell, existing report all is all solid state electrolyte on the relative meaning, and just the content of water is a little less relatively.The G.Q.Zhang of Xinjiang University is miscible with the PVA and the KOH aqueous solution, films in the PTFE surface, and drying is removed part moisture and prepared all solid state solid polyelectrolyte membrane and be used for Zn/MnO
2Battery, experiment show, use the discharge performance and the electrolytical stability of the KOH solution battery of 2-4M that good performance is all arranged.
The present invention is a kind of quasi-solid polymer water solution system electrolyte film between gel electrolyte and all solid state electrolyte, can replace conventional membrane, both can keep certain shape, thickness and intensity have higher ionic conductivity and superpower water hold facility and water transmittability again.Preparation method of the present invention is simple and practical, highly versatile, general water-soluble material is poorly soluble in organic solvent, and the material that is dissolved in organic solvent is often water insoluble, therefore look for a kind of solvent to dissolve difficulty of two or more macromolecular materials of different nature simultaneously, the present invention utilizes emulsion and emulsive method to solve this contradiction well.The present invention can be applied to various alkaline celies (comprising alkaline fuel cell), in the device such as electrical condenser.
Summary of the invention
A kind of quasi-solid polymer water solution system electrolyte film provided by the present invention had both had certain shape, and thickness and intensity have higher ionic conductivity and superpower water hold facility and water transmittability again.By emulsifying technology, with a kind of in water or alkaline solution non-swelling polymkeric substance evenly be coated on the hydrogel particle, form water in oil structure, the moisture of aqueous phase is difficult for scattering and disappearing like this, both kept a high proportion of moisture, do not had free electrolyte again, suitable intensity can also have been arranged.
This quasi-solid polymer water solution system electrolyte film can be applied to alkaline cell, ultracapacitor or alkaline fuel cell etc., and its aqueous portion is the main contributor of high conductivity, specific conductivity can reach 10 under the room temperature
-3Scm
-1Non-swelling polymer backbone in water or alkaline solution that the present invention uses except increasing film strength, stops outside the water loss, owing to its hydrophobic nature, can also improve the ventilation property of film.Quasi-solid polymer water solution system electrolyte film of the present invention can be coated with very thinly (as 10 microns), is used for the preparation of hull cell and microbattery.
The making method of quasi-solid polymer water solution system electrolyte film is as follows:
1 water-sol in the ratio of 0.1wt%～20wt% preparation hydroscopic high-molecular resin: the hydroscopic high-molecular resin of calculated amount slowly is sieved in the deionized water that is stirring according to the above ratio, dissolves fully up to hydroscopic high-molecular resin.The strong absorptive resin comprises cross linked polyacrylate, crosslinked salt polyacrylate, polyvinylpyrrolidone (PVP), polyethylene oxide (PEO), polyoxyethylene glycol (PEG) and polyvinyl alcohol (PVA).If use two or more water-absorbing resin simultaneously, then the overall control of two or more water-absorbing resins is at 0.1wt%～20wt%.
2 take by weighing the macromolecule emulsion of the above-mentioned water-sol and water insoluble or alkali lye in solid content than for 1:1 (gram/gram)～1:15 (gram/gram) ratio; High-molecular bone frame material water insoluble and basic solution is made the emulsion of 20wt%～70wt% concentration in advance; High-molecular bone frame material water insoluble or alkali lye comprises ptfe emulsion, polystyrene CALCIUM ACRYLATE emulsion, polyacrylate dispersion, polypropylene emulsion, vinylon emulsion and polyethylene emulsion.The macromolecule emulsion of water insoluble or alkali lye is slowly joined the water-sol aqueous phase that is stirring as oil phase, fully emulsified, make oil phase and water be uniformly mixed to form white emulsifiable paste.Additive can be before emulsification or is added during emulsification again.Additive is two class materials, and a class is nano-metal-oxide (Y
2O
3, CeO
2, Al
2O
3, TiO
2Deng), a class is inorganic or organic water thing (KCl, MgCl
2, Mg (NO
3) 2, (CH
3)
4NOH5H
2O etc.).Acetone or alcohol be can add at last and the pore opening and the uniformity coefficient of dielectric film adjusted.
3 evenly paint the uniform film of thickness, drying with above-mentioned emulsifiable paste at smooth surface.The gauge control of film is 10～300 micrometer ranges after drying, because the too easy short circuit of thin battery, if dielectric film thickness surpasses 300 microns, then the ventilation property of film is poor, and internal resistance is also big.The water content of film is controlled at 5wt%～60wt% according to application target.
After the 4 film dryings, film is peeled from sheet glass, 4h～24h in the potassium hydroxide alkali lye of immersion 2N～20N concentration takes out dry 1h～5h in vacuum drier/case.Fig. 1, Fig. 2 are scanning electronic microscope (SEM) photos that polymeric film of the present invention soaks the electrolytic solution front and back,
If first potassium hydroxide alkali lye with 2N～20N concentration prepares polyalcohol hydrogel and does water emulsification, can prepare quasi-solid polymer water solution system electrolyte film of the present invention equally, just when the 1st goes on foot the hydrogel of the hydroscopic high-molecular resin of preparing 0.1wt%～20wt%, hydroscopic high-molecular resin slowly is sieved in the potassium hydroxide alkali lye of the 2N～20N concentration that is stirring, dissolves fully up to hydroscopic high-molecular resin; Need be with vacuum-drying or dry under noble gas protection in the drying in the 3rd step, reach the invention requirement up to the water content of film, to prevent the potassium hydroxide reaction in carbon dioxide in air and the ionogen.This method does not need to carry out the 4th step caustic dip again, and the kind of additive all is the same with addition means.
Be to improve film strength, emulsifiable paste after the emulsification can also be coated in the mesh grid that Buddhist nun's logical sequence, polymeric amide or polyolefine make.
The invention has the advantages that:
1 can not be dissolved in two or more macromolecular material uniform mixing in a kind of solvent simultaneously, and the macromolecular material that does not absorb water evenly is coated on outside the hydrogel, has slowed down the volatilization of water.
The existing certain intensity of 2 these invention quasi-solid polymer water solution system electrolyte films can absorb, keep potassium hydroxide or sodium hydroxide solution again in a large number, can substitute the PP of present use, PA, barrier films such as Buddhist nun's logical sequence non-woven fabrics or asbestos film.Use this kind dielectric film to need not to add again electrolytic solution, can reduce battery leakage largely, seal simplyr, can reduce coming off of electrode active material, increase battery life.
3 the present invention compare with the gel-type ionogen to have the electrolytic solution of adding and is easy to characteristics, and the gel-type ionogen can't add after assembling as existing technology, can only before assembling, smear or in assembling process, be coated with into, manufacturability is very poor; The present invention only needs in advance to soak in alkali lye or assembles and adds quantitative traditional electrolytic solution behind the battery and get final product, changes hardly to have production technique now.
4 not free ionogen of quasi-solid polymer water solution system electrolyte film outward appearance, the specific conductivity of film can reach 10
-3Scm
-1The order of magnitude.
Description of drawings
Fig. 1 polymeric film of the present invention soaks scanning electronic microscope (SEM) photo before the electrolytic solution.
Fig. 2 soaks scanning electronic microscope (SEM) photo behind the electrolytic solution for polymeric film of the present invention.
By photo as can be seen, soak the smooth surface of electrolytic solution cephacoria, two kinds of macromolecular materials mix, soak after the electrolytic solution, many spherical or blocky-shaped particles occur, and the space occurs, form gas diffusion paths, help the diffusion of inside battery gas, this be gel electrolyte can not compare.
Embodiment
Embodiment 1:
By 3% of water inventory (20g) take by weighing the polyacrylic acid crosslinked polymkeric substance of water-absorbing resin (as Carbopol 740B resin, Noveon, INC) 0.6g is sieved in the water of quick stirring lentamente, until the Carbopol complete swelling, forms the water-sol.In above-mentioned gel, slowly add 10g polystyrene propylene fat liquor then, stir, form white emulsifiable paste, after fully emulsified, add the 3ml acetone or alcohol again and eliminate bubble, rapidly emulsifiable paste is filmed drying afterwards on film applicator, obtain the homogeneous polymer film, this film can store, transport as conventional membrane.This film in use, with film and battery plus-negative plate (as nickel hydroxide positive plate, hydrogen storage alloy negative) immerses in 5 ~ 10N potassium hydroxide solution 5～20 hours together, take out and be stranded dried alkali lye, put into the dry 2h of vacuum drying oven, the positive and negative electrode of battery should add the described water-absorbing resin of 0.5wt%～15wt% and make tackiness agent in making processes.
The positive pole of battery and negative pole separate with above-mentioned quasi-solid polymer water solution system electrolyte film, are wound into the pole plate group, in the AA type of packing into the battery case, need not to annotate electrolytic solution, seal.Make AA type nickel metal hydride battery.
Embodiment 2:
Take by weighing Mierocrystalline cellulose and acrylic crosslinking polymer water-absorbing resin by 5% of 6N potassium hydroxide aqueous solution total amount (20g), be sieved into lentamente in the above-mentioned 6N potassium hydroxide aqueous solution of quick stirring,, form gel until the polymkeric substance complete swelling.The polystyrene propylene fat liquor emulsification that in above-mentioned gel, slowly adds gel weight 30% then, form white emulsifiable paste, after fully emulsified, rapidly emulsifiable paste is being coated on ganoid glass or other substrates, vacuum-drying 2h has so just prepared the alkaline cell quasi-solid polymer water solution system electrolyte film that the present invention describes.
Embodiment 3:
Under ultrasonic wave, 0.054g nanometer Y2O3 is added in the 20g 6N potassium hydroxide aqueous solution, continue Y2O3 fully to be disperseed in ultrasonic 15 minutes.Take by weighing the crosslinked salt polyacrylate water-absorbing resin and the 1.0wt% PVA water-absorbing resin of alkali lye weight 3.0%, above-mentioned lentamente two kinds of water-absorbing resins are sieved in the above-mentioned 6N potassium hydroxide aqueous solution of quick stirring, until the polymkeric substance complete swelling, form gel.The polypropylene methyl esters emulsion emulsification that in above-mentioned gel, slowly adds gel weight 30% then, form white emulsifiable paste, after fully emulsified, rapidly emulsifiable paste is being coated on ganoid glass or other substrates, vacuum-drying 2h has so just prepared the alkaline cell quasi-solid polymer water solution system electrolyte film that the present invention describes.
Table 1 is different water-absorbing resins, the comparison of the specific conductivity of the quasi-solid polymer water solution system electrolyte film that different not swelling framework materials and different additive are made
Application example 1:
Make barrier film with the polymeric film that makes among the embodiment 1, replacing the rated capacity of commercially producing is the Ni/MH battery diaphragm of 2000mAh, positive and negative electrode, concentration of electrolyte, amount and other assembly technologies are constant, the Ni/MH battery rated capacity of producing still can reach 2000mAh, but the life-span with the battery of dielectric film production of the present invention is significantly improved, and can reach 500 times, and has only 300 times the conventional batteries life-span.
Application example 2:
The mixed that active carbon powder, nano level acetylene black and ptfe emulsion are pressed 87:10:3, by size mixing, the positive and negative electrode of prepared electrochemical capacitor in double electrode layer such as smear, vacuum-drying, compressing tablet, vacuum impregnation electrolytic solution, the quasi-solid polymer water solution system electrolyte film of embodiment 2 preparations is made barrier film assembling double layer capacitor, its single electrode active substance specific storage reaches 226F/g, the 24h self-discharge only has 26.9%, and electrical condenser is at 16mA/cm
2Current cycle 1000 times, condenser capacity does not change.
Claims (7)
1. quasi-solid polymer water solution system electrolyte film, it is characterized in that: use a kind of in alkaline aqueous solution non-swelling high-molecular bone frame material make the oil phase of dielectric film, wherein the high-molecular bone frame material is tetrafluoroethylene, polystyrene CALCIUM ACRYLATE, polyacrylic ester, polypropylene, vinylon and one of poly; Make the ionogen carrier with at least a strong absorptive resin and additive water in addition, form the structure of oil phase parcel water by emulsification; Emulsifiable paste is through filming, and the dry water content that forms is from 5wt%～60wt%, but the outward appearance softness, flexible does not have free electrolyte, has the polymer dielectric film of good ionic conductance again, for improving film strength, also uses the reticulated film matrix.
2. the preparation method of a kind of quasi-solid polymer water solution system electrolyte film according to claim 1, its characteristics are: use emulsifying technology with above-mentioned oil phase and water uniform mixing, high-molecular bone frame material water insoluble and basic solution is made the emulsion of 20wt%～70wt% concentration in advance, strong water-absorbing resin is made the water-sol of 0.1wt%～20wt% concentration, then with the above-mentioned emulsion and the water-sol mixing and emulsifying of 1: 1 (gram/gram)～1:15 (gram/gram) of solid content ratio, adequately emulsified emulsifiable paste uniform coating, dry, immerse 4h～24h in 2N～20N potassium hydroxide alkali lye again, dry again; Additive adds when making the water-sol, perhaps adds when emulsification.
3. be characterised in that according to a kind of quasi-solid polymer water solution system electrolyte film described in the claim 1, used strong absorptive resin comprises cross linked polyacrylate, crosslinked salt polyacrylate, polyvinylpyrrolidone, polyethylene oxide, one or more in polyoxyethylene glycol and the polyvinyl alcohol, if use two kinds or two or more water-absorbing resin simultaneously, then the overall control of two or more water-absorbing resins is 0.1%～20%.
4. according to the quasi-solid polymer water solution system electrolyte film described in the claim 1, the additive that it is characterized in that it comprises a kind of in the following two class materials, and a class is a nano-metal-oxide, and a class is inorganic or organic hydrate.
5. according to a kind of quasi-solid polymer water solution system electrolyte film described in the claim 1, the thickness that it is characterized in that film is 10～300 microns.
6. according to a kind of quasi-solid polymer water solution system electrolyte film described in the claim 1, it is characterized in that the reticulated film matrix comprises by a kind of mesh grid core of making in Buddhist nun's logical sequence, polymeric amide or the polyolefine.
7. according to the preparation method of a kind of quasi-solid polymer water solution system electrolyte film described in the claim 2; it is characterized in that preparing the water-absorbing resin hydrogel of 0.1wt%～20wt% concentration with 2N～20N potassium hydroxide alkali lye earlier; and then emulsification; the system film; adopt vacuum-drying or dry under the noble gas protection when dry, need not caustic dip again.
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| CN100565994C (en) * | 2007-12-20 | 2009-12-02 | 成都中科来方能源科技有限公司 | High temperature proton exchange film for fuel cell and preparation method thereof |
| CN101853947B (en) * | 2010-05-21 | 2012-11-07 | 东华大学 | Compound crosslinking alkaline polymer film for fuel cell, preparation method and application |
| CN103811196B (en) * | 2014-01-22 | 2016-08-17 | 东风商用车有限公司 | A kind of ultracapacitor aqueous electrolyte |
| CN106898843A (en) * | 2015-12-17 | 2017-06-27 | 中国科学院大连化学物理研究所 | A kind of metal-air batteries electrolyte and its preparation and application |
| CN113140807B (en) * | 2021-04-21 | 2022-08-05 | 浙江大学 | Water battery with incombustibility |
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| CN1560129A (en) * | 2004-03-12 | 2005-01-05 | 南亚塑胶工业股份有限公司 | High molecule electrolyte film by basic polyethenyl alcohol mixed with poly-epoxy chloro propane and application thereof |
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| CN1560129A (en) * | 2004-03-12 | 2005-01-05 | 南亚塑胶工业股份有限公司 | High molecule electrolyte film by basic polyethenyl alcohol mixed with poly-epoxy chloro propane and application thereof |
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