CN101280065A - Polymer film having micropore structure, preparation and application thereof - Google Patents
Polymer film having micropore structure, preparation and application thereof Download PDFInfo
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- CN101280065A CN101280065A CNA2008100382195A CN200810038219A CN101280065A CN 101280065 A CN101280065 A CN 101280065A CN A2008100382195 A CNA2008100382195 A CN A2008100382195A CN 200810038219 A CN200810038219 A CN 200810038219A CN 101280065 A CN101280065 A CN 101280065A
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Abstract
The invention belongs to the electrochemical technical field, which is particularly a polymer electrolyte with porous structure, and the preparation method and application of the polymer electrolyte. First of all, the vesicant which has carbonate and organic acid as the main components is prepared and dispersed into polymer solution; the solvent is volatilized to get polymer film, and then the film is foamed under microwave conditions so as to obtain organic and inorganic polymer composites with porous structures. The polymer composite can be used as polymer electrolyte materials for lithium-ion secondary batteries and has very good ion conductivity and mechanical properties. Moreover, the invention has strong operability and stable quality of products.
Description
Technical field
The invention belongs to technical field of electrochemistry, be specifically related to a kind of microporous polymer electrolyte and preparation method and application.
Background technology
Lithium-ion secondary cell has that energy density height, specific power are big, good cycle, memory-less effect, characteristics such as pollution-free, has good economic benefits, social benefit and strategic importance, becomes the Green Chemistry power supply that attracts most attention at present.But there are unsafe factors such as electrolytic solution leakage.At present, the method for solution is to adopt polymer dielectric to replace liquid electrolyte (referring to Wu Yuping, Dai Xiaobing, horse army flag, the pre-river of journey, " lithium ion battery---use and put into practice ", Beijing: Chemical Industry Press,, the 301st page in 2004).The ionic conductivity of general pure solid polymer electrolyte does not often reach the requirement of application.Therefore, many investigators microporous polymer electrolyte that begins one's study.There is the liquid phase that is separated in this ionogen when keeping the polymer backbone mechanical stability, have very high ionic conductivity, therefore, have a extensive future, and be to study more polymer electrolyte system recently.At present, the preparation method of microporous polymer electrolyte mainly contains solution casting method and phase reversion method.But the solution casting method need adopt a large amount of volatile solvents, and cost is higher and have potential safety hazard, and phase reversion method complex process, parameter is numerous, need carry out strict control, cost height to preparation condition.
Summary of the invention
An object of the present invention is to provide a kind of preparation method with polymkeric substance of microvoid structure.
Another object of the present invention provides a kind of polymkeric substance that is had microvoid structure by this inventive method preparation.
Also purpose of the present invention provides the application of a kind of polymeric film with microvoid structure by the inventive method preparation as lithium ion battery electrolyte materials.
Preparation method with polymkeric substance of microvoid structure provided by the invention is called the microwave foaming, and at first preparing with carbonate and organic acid is the composite foamable agent of main component; Then composite foamable agent is distributed in the polymers soln, solvent flashing obtains polymeric film; Under microwave condition, foam at last.In composite foamable agent, also can add some nucleators in addition.This method makes and produces a large amount of microvoid structures in the polymeric film, thereby improved the ionic conductivity of polymer dielectric well.These method concrete steps are as follows:
(1) first preparation composite foamable agent: with carbonate and organic acid by 20: 1-1: 20 mass ratio mixes, and grinding is even, obtains composite foamable agent.
(2) preparation solid polymer membrane: polymer dissolution in solvent, is obtained polymers soln, then composite foamable agent is joined in the polymers soln, the mass ratio of whipping agent and polymkeric substance is 1: 2-1: 200; Solvent flashing obtains solid polymer membrane;
(3) foaming: this solid polymer membrane is placed microwave reactor, be heated to 40 ℃-140 ℃, reacted 20 seconds-30 minutes, obtain having the polymeric film of microvoid structure.
Carbonate described in the above-mentioned steps (1) is the carbonate or the supercarbonate of basic metal, alkaline-earth metal, for example sodium bicarbonate, yellow soda ash, salt of wormwood, saleratus, lime carbonate or sodium glycine carbonate etc.; The described organic acid of step (1) is for easily being decomposed into the organic acid of gas, for example citric acid, tartrate, glucuronic acid, mannuronic acid, formic acid, acetate, oxalic acid or glycine; Carbonate described in the step (1) and organic acid mass ratio are 20: 1-1: 20, be preferably 2: 1-1: 2.
Polymkeric substance described in the above-mentioned steps (2) can be blend, the copolymerization system as polyoxyethylene, polyacrylonitrile, polymethylmethacrylate, polyvinylidene difluoride (PVDF), polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer and the above-mentioned polymkeric substance of matrix in the polymer dielectric; The described solvent of step (2) is abundant dissolve polymer, and whipping agent is reached preferably disperse, for example 1-Methyl-2-Pyrrolidone, dimethyl formamide, acetone etc.; The mass ratio of whipping agent described in the step (2) and polymkeric substance is 1: 200-1: 2, preferred 1: 100-1: 50.
In the above-mentioned steps (3), described temperature of reaction is 40-140 ℃, is preferably 80-130 ℃; Reaction times described in the step (3) is 20 seconds-30 minutes, is preferably 1-10 minute.
Can also add certain nucleator in above-mentioned steps (1), described nucleator is Trisodium Citrate or nano zine oxide powder etc.Wherein the mass ratio of nucleator and carbonate is from 5: 1-1: 5, be preferably 2: 1-1: 2.
The present invention also provides a kind of and has a microvoid structure polymeric film by method for preparing.
The present invention also provides the application by the polymeric film with microvoid structure of method for preparing, promptly as the lithium-ion secondary cell microporous polymer electrolyte, in this composite polymer electrolyte, because foaming has produced many micropores, for the migration of lithium ion provides passage, improved the ionic conductivity of multipolymer, but so in the using polymer lithium-ion secondary cell.
The present invention is by microwave reactor, and as temperature reference and foaming media, whipping agent decomposes generation gas under microwave action with water, thereby realizes foaming.Therefore, claim that the inventive method is the microwave foaming.
The polymeric film with microvoid structure by the present invention's preparation can be used as the polymer dielectric of lithium-ion secondary cell, and good ionic conductivity and mechanical property is arranged.And strong operability of the present invention, cost is low than other method, favorable reproducibility, the constant product quality of gained.
Description of drawings
Fig. 1 is the stereoscan photograph of the polymeric film with microvoid structure that obtains of the embodiment of the invention 1.
Fig. 2 is the stereoscan photograph of the polymeric film with microvoid structure that obtains of Comparative Examples of the present invention.
Embodiment
To be described in more detail by embodiment below, but protection scope of the present invention is not limited to these embodiment.
Embodiment 1:
Get 1 gram sodium bicarbonate and 1.25 gram Trisodium Citrates (nucleator) and use the mortar ground and mixed even earlier, add 0.54 gram citric acid then, even with the mortar ground and mixed, obtain composite foamable agent.Getting 0.05 gram composite foamable agent, to join 4.5 gram concentration be in the 1-Methyl-2-Pyrrolidone solution of polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer of 10%, stirs after 4 hours, polymers soln is applied on the sheet glass solvent flashing.The gained solid polymer membrane is put in the microwave reactor 120 ℃ of foaming 3 minutes, obtain having the polymeric film of microvoid structure.
The stereoscan photograph of the polymeric film of above-mentioned microvoid structure is shown in accompanying drawing 1, can see tangible microvoid structure from this figure.
Embodiment 2
Get 1 gram sodium bicarbonate and 0.54 gram oxalic acid, even with the mortar ground and mixed, obtain composite foamable agent.Getting 0.10 gram composite foamable agent, to join 4 gram concentration be the N of 10% polyvinylidene difluoride (PVDF), in N '-dimethyl formamide solution, stirs after 1 hour, polymers soln is applied on the sheet glass solvent flashing.The gained solid polymer membrane is put in the microwave reactor 150 ℃ of foaming 1 minute, obtain having the polymeric film of microvoid structure.
Embodiment 3
Get 1 gram sodium bicarbonate and 1.25 gram formic acid, even with the mortar ground and mixed, obtain composite foamable agent.Getting 0.10 gram composite foamable agent, to join 8 gram concentration be the N of 10% polyacrylonitrile, in N '-dimethyl formamide solution, stirs after 2 hours, polymers soln is applied on the sheet glass solvent flashing.The gained solid polymer membrane is put in the microwave reactor 100 ℃ of foaming 20 minutes, obtain having the polymeric film of microvoid structure.
Embodiment 4
Get 1 gram lime carbonate, 1.25 gram tartrate and 0.1 gram nano-ZnO particle (median size is 20nm), even with the mortar ground and mixed, obtain composite foamable agent.Getting 0.05 gram composite foamable agent, to join 4.5 gram concentration be in the acetone soln of polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer of 10%, stirs after 4 hours, polymers soln is applied on the sheet glass solvent flashing.The gained solid polymer membrane is put in the microwave reactor 120 ℃ of foaming 3 minutes, obtain having the polymeric film of microvoid structure.
Comparative Examples
Get 0.05 gram sodium bicarbonate and join in the 1-Methyl-2-Pyrrolidone solution of 4.5 grams, polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer of 10%, stir after 4 hours, polymers soln is applied on the sheet glass solvent flashing.The gained solid polymer membrane is put in the microwave reactor 120 ℃ of foaming 3 minutes, had the polymeric film of certain microvoid structure a little.
The stereoscan photograph of the polymeric film of Comparative Examples gained is shown in Fig. 2.This figure shows, only exist under the condition of carbonate also can obtain vesicular structure, but the homogeneity of abscess and porosity is all poor than carbonate and the composite foamed system of organic acid in the resulting polymers film.
Embodiment 5
The polymer solids film of embodiment 1 is immersed electrolytic solution (1mol/l LiPF
6EC/DMC/DEC) after 10 minutes, obtain polymer dielectric.This polymer dielectric is fixed on the centre of stainless steel electrode, it is carried out the test of alternating-current impedance, according to following equation:
σ＝l/RS (1)
Can calculate the ionic conductivity of this polymeric film, wherein l is the thickness of film, and R is the resistance of this polymeric film of being obtained by ac impedance spectroscopy, and S is the area of polymeric film.The ionic conductivity of above-mentioned polymer dielectric is 1.7mS/cm.
Embodiment 6
The polymer dielectric that the foregoing description 5 is obtained is assembled into lithium ion battery, and the active material of negative pole is the natural graphite of modification, and the anodal active material is LiCoO
2After changing into, carry out loop test, voltage range is 3V-4.2V.Test result shows that 500 times circulation back capability retention is 95%.
Claims (6)
1. preparation method with polymeric film of microvoid structure, this method comprises the steps:
(1) first preparation composite foamable agent: with carbonate and organic acid with 20: 1-1: 20 mass ratio mixes, and grinding is even, obtains composite foamable agent;
(2) preparation solid polymer membrane: polymer dissolution in solvent, is obtained polymers soln, then composite foamable agent is joined in the polymers soln, the mass ratio of composite foamable agent and polymkeric substance is 1: 2-1: 200, and solvent flashing obtains solid polymer membrane;
(3) foaming: this solid polymer membrane is placed microwave reactor, be heated to 40 ℃-140 ℃, reacted 20 seconds-30 minutes, obtain having the polymeric film of microvoid structure;
Wherein, described carbonate is the carbonate or the supercarbonate of basic metal, alkaline-earth metal, and described organic acid is citric acid, tartrate, glucuronic acid, mannuronic acid, formic acid, acetate, oxalic acid or glycine;
Described polymkeric substance is polyoxyethylene, polyacrylonitrile, polymethylmethacrylate, polyvinylidene difluoride (PVDF) or polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer, perhaps is the blend or the copolymerization system of these polymkeric substance.
2. preparation method according to claim 1 is characterized in that described temperature of reaction is 80-130 ℃; The described reaction times is 1-10 minute.
3, preparation method according to claim 1 is characterized in that in composite foamable agent also adding that nucleator, the mass ratio of nucleator and carbonate are arranged is 5: 1-1: 5.
4, preparation method according to claim 3 is characterized in that described nucleator is Trisodium Citrate or nano zine oxide powder.
5. microporous polymer membranes that obtains by the described preparation method of claim 1.
6. one kind as the application of microporous polymer membranes as described in the claim 5 as polymer dielectric in the lithium-ion secondary cell.
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| CN101914215A (en) * | 2010-06-04 | 2010-12-15 | 同济大学 | Method for preparing high-active piezoelectric functional membranes by microwave irradiation |
| CN101577349B (en) * | 2009-06-19 | 2011-08-31 | 哈尔滨工业大学 | All-solid-state composite polymer electrolyte and preparation method thereof |
| CN102977458A (en) * | 2012-12-11 | 2013-03-20 | 苏州工业园区润佳工程塑料有限公司 | Micropore foaming agent for polypropylene, microcellular foamed polypropylene composite material and methods for preparing micropore foaming agent for polypropylene and microcellular foamed polypropylene composite material |
| CN103030852A (en) * | 2011-09-29 | 2013-04-10 | 陈光炎 | Polymer microporous membrane and its preparation method |
| CN104558672A (en) * | 2014-01-06 | 2015-04-29 | 嘉兴市世纪今典景观工程有限公司 | Expandable polyphenyl plastic microwave foaming technique |
| CN105482146A (en) * | 2014-09-19 | 2016-04-13 | 丁飞鹏 | Environmentally-friendly micro foaming agent |
| CN105504330A (en) * | 2015-12-23 | 2016-04-20 | 广州市奥菲特有限公司 | Preparation method of foam particles, foam particles prepared with same and application of foam particles |
| CN105622979A (en) * | 2014-11-01 | 2016-06-01 | 丁飞鹏 | Environment-friendly foamer for rubber and plastic |
| CN108963162A (en) * | 2018-07-27 | 2018-12-07 | 宁德卓高新材料科技有限公司 | The method for preparing micropore ceramics diaphragm |
| CN108987651A (en) * | 2018-07-27 | 2018-12-11 | 江苏卓高新材料科技有限公司 | A method of preparing micropore ceramics composite diaphragm |
| CN112448027A (en) * | 2019-09-03 | 2021-03-05 | 华南师范大学 | Blended gel polymer electrolyte and preparation method and application thereof |
Family Cites Families (5)
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| US5540741A (en) * | 1993-03-05 | 1996-07-30 | Bell Communications Research, Inc. | Lithium secondary battery extraction method |
| CN1260278C (en) * | 2004-12-30 | 2006-06-21 | 北京科技大学 | Process for preparing blended micrometer TiO2 polymer electrolyte |
| CN101154749A (en) * | 2006-09-28 | 2008-04-02 | 万向电动汽车有限公司 | Gel polymer electrolyte film used for high-capacity polymer lithium ion power cell |
| CN100513467C (en) * | 2007-05-15 | 2009-07-15 | 浙江大学 | Porous gel polyelectrolyte thin film and preparation method thereof |
| CN100494240C (en) * | 2007-05-24 | 2009-06-03 | 复旦大学 | Organic inorganic composite polymer with microporous structure, its preparing method and use |
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| CN101577349B (en) * | 2009-06-19 | 2011-08-31 | 哈尔滨工业大学 | All-solid-state composite polymer electrolyte and preparation method thereof |
| CN101914215A (en) * | 2010-06-04 | 2010-12-15 | 同济大学 | Method for preparing high-active piezoelectric functional membranes by microwave irradiation |
| CN103030852A (en) * | 2011-09-29 | 2013-04-10 | 陈光炎 | Polymer microporous membrane and its preparation method |
| CN103030852B (en) * | 2011-09-29 | 2015-02-25 | 陈光炎 | Polymer microporous membrane and its preparation method |
| CN102977458A (en) * | 2012-12-11 | 2013-03-20 | 苏州工业园区润佳工程塑料有限公司 | Micropore foaming agent for polypropylene, microcellular foamed polypropylene composite material and methods for preparing micropore foaming agent for polypropylene and microcellular foamed polypropylene composite material |
| CN104558672A (en) * | 2014-01-06 | 2015-04-29 | 嘉兴市世纪今典景观工程有限公司 | Expandable polyphenyl plastic microwave foaming technique |
| CN105482146A (en) * | 2014-09-19 | 2016-04-13 | 丁飞鹏 | Environmentally-friendly micro foaming agent |
| CN105622979A (en) * | 2014-11-01 | 2016-06-01 | 丁飞鹏 | Environment-friendly foamer for rubber and plastic |
| CN105504330A (en) * | 2015-12-23 | 2016-04-20 | 广州市奥菲特有限公司 | Preparation method of foam particles, foam particles prepared with same and application of foam particles |
| CN105504330B (en) * | 2015-12-23 | 2019-04-23 | 广州市奥菲特有限公司 | A kind of preparation method of expanded particle and its expanded particle being prepared and application |
| CN108963162A (en) * | 2018-07-27 | 2018-12-07 | 宁德卓高新材料科技有限公司 | The method for preparing micropore ceramics diaphragm |
| CN108987651A (en) * | 2018-07-27 | 2018-12-11 | 江苏卓高新材料科技有限公司 | A method of preparing micropore ceramics composite diaphragm |
| CN112448027A (en) * | 2019-09-03 | 2021-03-05 | 华南师范大学 | Blended gel polymer electrolyte and preparation method and application thereof |
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