CN1331935C - Composite microporous polymer electrolyte and its preparing method - Google Patents
Composite microporous polymer electrolyte and its preparing method Download PDFInfo
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- CN1331935C CN1331935C CNB2005100880638A CN200510088063A CN1331935C CN 1331935 C CN1331935 C CN 1331935C CN B2005100880638 A CNB2005100880638 A CN B2005100880638A CN 200510088063 A CN200510088063 A CN 200510088063A CN 1331935 C CN1331935 C CN 1331935C
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Abstract
The present invention relates to a composite microporous polymer electrolyte and a preparing method thereof, particularly to a novel inorganic stuffing composite microporous polymer electrolyte and a manufacture method thereof. The electrolyte is suitable for polymer lithium ion batteries. The present invention provides a novel composite microporous polymer electrolyte of inorganic materials, and a manufacture method thereof. The electrolyte contains 65% to 95% of PVDF-HFP and 5% to 35% of inorganic material. The manufacture method comprises the following steps that the inorganic material is dissolved in solvent, the PVDF-HFP is added into the suspension of the inorganic material suspension to be dissolved for obtaining film casting liquid, and air bubbles are removed by static placement; the film casting liquid is coated on film forming base materials; after the film forming base materials are dried in vacuum after drying operation, a dried film is obtained; the dried film is immersed into electrolyte liquid to obtain a composite microporous film. The present invention has the advantages of no plasticizer use, no extracting section, low humiture condition requirement, simplified film producing procedure, low microporous film crystallizing degree and widened electrochemical window. The performance of an interface formed from the electrolyte and an electrode is stable.
Description
Technical field
The present invention relates to a kind of polymer dielectric, especially relate to a kind of composite microporous type polymer dielectric of novel inorganic filler and manufacture method thereof that is applicable to polymer Li-ion battery.
Background technology
Polymer Li-ion battery is the s-generation commercialization lithium ion battery after liquid lithium ionic cell.Compare with liquid lithium ionic cell, polymer Li-ion battery has following advantage: the first, and polymer Li-ion battery has overcome the leakage problem, is difficult for catching fire, exploding, and security is higher, is more suitable for as the high-power drive source; The second, polymer Li-ion battery uses plastic wrapping, need not the metal shell container, reduced battery quality, and have higher specific energy; The 3rd, the polymer Li-ion battery shaped design is more flexible, can make arbitrary shape.Therefore, polymer Li-ion battery has caused extensive concern since U.S. Bellcore company took the lead in report in 1994.At present, many companies of countries such as existing China, Japan, Korea S, the U.S. and Canada produce.
One of core technology of polymer Li-ion battery is to adopt plastic micro polymer pore network as electrolytical skeleton structure, and the liquid electrolyte molecule is fixed and wherein formed apparent dry state.Current this polymer microporous film need make through the Bellcore technology of extraction softening agent, promptly with lower boiling extraction agent high boiling softening agent is removed from polymeric matrix, stays the porous polymer layer.The shortcoming of this method is to need extraction process of experience, and film making process is comparatively complicated; In addition, because the boiling point of softening agent is higher, the debris after the extraction is difficult for removing, thereby causes cycle performance of battery to reduce.Phase inversion method is the another kind of method for preparing microporous membrane commonly used, and this method is used solvent pairs usually, utilizes two kinds of solvents that the solvability difference of polymkeric substance and volatility are not coexisted to produce in the film-casting liquid exsiccant process and is separated and makes microporous membrane.Compare with extraction process, though phase inversion method has been simplified film making process, strict temperature and humidity conditions is with the volatilization of control solvent, thereby circulation ratio is relatively poor, condition control does not with great difficulty cause the failure of microporous membrane preparation, is not applied in suitability for industrialized production at present.Therefore, the technology of preparing of existing polymer microporous film is to cause the polymer Li-ion battery complex manufacturing, one of important factor that manufacturing cost is too high, and directly influence its market outlook.It is as follows to adopt the Bellcore technology of traditional extraction softening agent to prepare the laboratory method of porous polymer electrolyte:
1. dibutyl phthalate (DBP) softening agent with 0.5ml joins 2.5ml N, in dinethylformamide (DMF) solvent, after mixing, vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) powder with 0.4g joins in the above-mentioned mixed solvent again, under 50 ℃, heat and stir into uniform viscous solution, leave standstill then and slough bubble.
With the sheet glass of smooth cleaning as becoming film base material, on slide, smear certain thickness above-mentioned film-casting liquid by the method for prolonging stream naturally.
3. film-casting liquid is dried volatilization under 70 ℃ in air and remove the DMF solvent, obtain containing the half-dried film of DBP softening agent.
4. above-mentioned half-dried film is removed Plasticizer DBP with methanol extraction, and, make microporous membrane thus, be called dry film through 70 ℃ of vacuum-drying 24h.
5. dry film is immersed electrolytic solution, promptly obtain activatory and contain electrolytic solution gel state microporous membrane, be called wet film.
At above situation, many in the world countries and high-tech company particularly are placed on consequence to the preparation research of porous polymer electrolyte in polymer Li-ion battery production commercial city at present, organize lot of manpower and material resources to concentrate and study, develop.The work of carrying out related fields in a deep going way will have important practical significance for promoting China's polymer Li-ion battery industrial expansion.
Summary of the invention
The objective of the invention is to use softening agent at existing preparation microporous membrane, its complex procedures, need extraction process, the problem to temperature and temperature condition are had relatively high expectations provides composite microporous type polymer dielectric of a kind of new inorganic material and preparation method thereof.
The composition of the said composite microporous polymer electrolyte of the present invention and be by the content of mass ratio:
Vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) is 65%～95%, and inorganic materials is 5%～35%.Said inorganic materials is selected from molecular sieve, preferred SBA-15 mesopore molecular sieve.
Its step of the preparation method of the said composite microporous polymer electrolyte of the present invention is as follows:
1), above-mentioned inorganic materials is scattered in the solvent, sonic oscillation to inorganic materials is uniformly dispersed; Again the vinylidene fluoride-hexafluoropropylene copolymer powder is added in the inorganic materials suspension liquid, make the vinylidene fluoride-hexafluoropropylene copolymer dissolving, get film-casting liquid, leave standstill then and slough bubble;
2), becoming on the film base material to smear film-casting liquid;
3), the one-tenth film base material that will smear film-casting liquid dries the final vacuum drying in air, make the inorganic materials composite micro porous film, is called dry film;
4), dry film is immersed electrolytic solution, the gel state composite micro porous film that contains electrolytic solution that has promptly obtained activating is called wet film.
In step 1), said solvent is selected from a kind of or its mixed solvent in acetone, DMF, the N-N-methyl-2-2-pyrrolidone N-(NMP) etc., is 1 by quality than the content of vinylidene fluoride-hexafluoropropylene copolymer and solvent: (3.7～12.5); The sonic oscillation time is preferably 5～35min.
In step 2) in, become film base material preferably to be selected from sheet glass.
In step 3), the temperature of drying in air is preferably 30～100 ℃.Vacuum drying temperature is preferably 30～100 ℃.
Compare with the Bellcore technology of traditional extraction softening agent, not only need not to use softening agent among the preparation technology of the present invention, avoided the extraction link, low to the temperature and humidity conditional request, can greatly simplify film making process, and the decline of prepared microporous membrane degree of crystallinity, electrochemical window is slightly widened, and is more stable with the interfacial property that electrode is formed.This development to battery industry has much realistic meaning.Relevant experimental result can be able to further instruction from following embodiment.
Description of drawings
Fig. 1 is the surface (a) and section (b) the SEM image of the prepared porous polymer electrolyte of Bellcore technology of extraction softening agent.In Fig. 1, scale (a) is 20 μ m, and scale (b) is 10 μ m.
Fig. 2 is the surface (a) and section (b) the SEM image of the composite microporous type polymer dielectric of the prepared inorganic materials of the present invention.In Fig. 2, the scale of (a) and (b) is 10 μ m.
Fig. 3 is that the XRD of the composite microporous type polymer dielectric of inorganic materials characterizes.(a) PVDF-HFP powder, (b) PVDF-HFP blank film, (c) the composite microporous type PVDF-HFP film of inorganic materials.X-coordinate be 2 θ/(°).
Fig. 4 is the electrochemical stability window test of the composite microporous type polymer dielectric of inorganic materials.Sweep velocity 1mV/s, (a) the prepared porous polymer electrolyte of Bellcore technology of extraction softening agent, (b) the composite microporous type polymer dielectric of inorganic materials.X-coordinate is E/V (vs.Li
+/ Li), ordinate zou is I/ μ A.
Fig. 5 is the composite microporous type polymer dielectric of inorganic materials/lithium electrode interface stability Journal of Sex Research (Li/ polymer dielectric/Li battery is placed the electrochemical impedance spectroscopy behind the different time).(a) the prepared porous polymer electrolyte of Bellcore technology of extraction softening agent, (b) the composite microporous type polymer dielectric of inorganic materials.X-coordinate is Z '/Ω, and ordinate zou is-Z "/Ω.
Fig. 6 is the composite microporous type polymer dielectric of Li/ inorganic materials/MCF battery 1st, 2nd, 10th, 20th cycle charge-discharge curve, the cycle charge-discharge electric current is 0.1C first, continue after the cycle charge-discharge electric current be 0.5C.The composite microporous type polymer dielectric of Li/ inorganic materials/MCF battery charging and discharging curve cycle charge-discharge electric current first is 0.1C, continue after the cycle charge-discharge electric current be 0.5C, X-coordinate is Q/mAh, ordinate zou is U/V.
Fig. 7 is the composite microporous type polymer dielectric of Li/ inorganic materials/the 2nd～20 circulation volume curve of MCF battery, and charging and discharging currents is 0.5C.X-coordinate is Cycle numbers, and ordinate zou is Q/mAh.
Embodiment
Following examples will the present invention is further illustrated in conjunction with the accompanying drawings.
Embodiment 1:
The prepared porous polymer electrolyte SEM of the Bellcore technology pattern of employing extraction softening agent is the spongy microvoid structure that runs through mutually as seen from Figure 1, and porosity is higher, and hole is evenly distributed, and the aperture is less than 5 μ m.Conductivity at room temperature can reach 10
-3Scm
-1More than.
Embodiment 2:
Inorganic materials SBA-15 mesopore molecular sieve is scattered in the solvent acetone, and the mass content that inorganic materials accounts in the composite microporous type polymer dielectric is 5%, and the consumption of acetone is 2.5ml, and sonic oscillation 10min is uniformly dispersed to inorganic materials; PVDF-HFP powder with 0.4g adds in the above-mentioned inorganic materials suspension liquid again, makes the PVDF-HFP dissolving, gets film-casting liquid, leaves standstill then and sloughs bubble; On film forming substrate glass sheet, smear film-casting liquid; The sheet glass of smearing film-casting liquid is dried in air, and bake out temperature is 50 ℃, oven dry back vacuum-drying in vacuum drying oven, and vacuum drying temperature is 60 ℃, makes the inorganic materials composite micro porous film, is called dry film; Dry film is immersed electrolytic solution, and the gel state composite micro porous film that contains electrolytic solution that has promptly obtained activating is called wet film.
Adopt the prepared composite microporous type polymer dielectric of the inorganic materials SEM pattern of the present invention as seen from Figure 2, be abundant netted pore space structure, hole is evenly distributed, and the aperture is less than 10 μ m.Compare with embodiment 1, the pore-forming mechanism that the difference of both patterns is different with them is relevant.The prepared composite microporous type polymer dielectric of the inorganic materials conductivity at room temperature of the present invention can reach 0.5 * 10
-3Scm
-1More than, can satisfy the needs of actual battery system.Embodiment 3: the XRD diffraction spectra of the composite microporous type polymer dielectric of inorganic materials that employing the present invention is prepared as shown in Figure 3.The PVDF-HFP powder is crystalline state and amorphous mixed state, wherein again based on crystalline state, can be observed by Fig. 3 (a), its respectively in 2 θ=17.8 ° and 19.5 ° two spikes are arranged, and 2 θ=26.2 ° and 38.0 ° two broad peaks are arranged, belong to the characteristic diffraction peak of (100) (020) among the PVDF, (110), (021) and (002) crystal face respectively.When the PVDF-HFP powder is made polymer electrolyte film (Fig. 3 (b)), the intensity of its diffraction peak reduces, and the diffraction peak that is positioned at 2 θ=38.0 ° disappears, and shows that PVDF-HFP crystalline state content descends; Further in polymeric film, add (Fig. 3 (c)) behind the used inorganic pore-creating filler of the present invention, the diffraction peak that is positioned at 2 θ=26.2 ° also disappears, 2 θ=17.8 a ° diffraction peak of locating then reduces to become acromion, illustrates that PVDF-HFP crystalline state content further reduces in the composite microporous type polymer dielectric of prepared mineral filler.The reduction of polymer dielectric crystalline state content will help it to the absorption of electrolytic solution and the plasticizing of self, thereby improve the ionic conductivity of polymer dielectric.
Because the lithium ion battery operating voltage is higher, so the ionogen of its use also must have the electrochemical stability window of broad.Investigate a kind of NEW TYPE OF COMPOSITE polymer dielectric, except dopant material itself will have good electrochemical stability, must consider that also it is to the particularly influence of organic electrolyte electrochemical stability of composite polymer electrolyte system.The test of polymer electrolyte electrochemical stability window adopts linear sweep voltammetry to measure, assembling Li/ polymer dielectric/stainless steel is measured system, the research electrode is a stainless steel, counter electrode and reference electrode are same lithium electrode, sweep forward polarization research electrode under the speed, the resistance of oxidation of observing polymer dielectric at certain current potential.Used inorganic materials itself be sure of to have highly stable electrochemical properties.Fig. 4 provides the prepared porous polymer electrolyte of Bellcore technology of extraction softening agent and the linear volt-ampere scanning correlation curve of the composite microporous type polymer dielectric of the prepared inorganic materials of the present invention wet film (behind the Electolyte-absorptive), by Fig. 4 (a) as can be seen, the electrochemical stability window of used electrolytic solution is greater than 4.5V, in low potential district fainter impurity current peak arranged; After the doping inorganic materials, shown in Fig. 4 (b), electrochemical stability window slightly improves, and the impurity current peak in low potential district disappears, this may be because the adding of inorganic materials has absorbed the impurity in the electrolytic solution, oxygen and moisture etc., thereby has improved the electrochemical stability window of polymer dielectric.
Interfacial property for test polymer ionogen and lithium electrode, assembling Li/ polymer dielectric/Li battery, the electrochemical impedance spectroscopy that this battery changes with storage period under open circuit voltage as seen from Figure 5, provide a series of compression semicircles that do not pass through initial point among the figure, corresponding to lithium electrode/polymer dielectric interface process, its diameter increases with the prolongation of battery storage period, show passive film in time prolongation and progressive additive.But from as can be seen through the size of 12 days rear semicircle diameters, the interface that composite microporous type polymer dielectric of inorganic materials that the present invention is prepared and lithium electrode constitute, the rising tendency of its interface impedance is comparatively slow, through 12 days, its interface impedance value has only increased about 91.06 Ω, and tend towards stability gradually, show that the rising tendency of interface impedance has obtained obvious suppression (Fig. 5 (a)); And adopt the prepared porous polymer electrolyte of Bellcore technology (not adding any filler) that extracts softening agent, the interface that itself and lithium electrode constituted is Initial R not only
IntBe worth greatlyyer, and interface impedance rate of growth in time is very fast, and through 12 days, its interface impedance value increased by 495.8 Ω (Fig. 5 (b)) approximately.This shows with the prepared porous polymer electrolyte of Bellcore technology compares, can form the more good passive film of performance between composite microporous type polymer dielectric of inorganic materials that the present invention is prepared and the lithium electrode, this layer passive film not only has lower initial interface resistance value, and comparatively stable, can stop the consumption of lithium electrode effectively.The reaction of impurity such as softening agent and a spot of moisture and lithium electrode is the ever-increasing major cause of passive film.The adding of inorganic materials can improve the interface stability between polymer dielectric and the lithium electrode, owing to its impurity such as moisture in can the absorbing polymeric ionogen.This point is verified in the test of embodiment 4 electrochemical stability windows.
The lithium sheet is a negative pole; Positive active material is graphitized carbon fibre (MCF), and itself and carbon black and binding agent PVDF-HFP are coated on the clean Copper Foil of roughened with NMP furnishing slurry, through roll-in, cut out and divide and oven dry is handled, makes positive plate.Ionogen adopts the composite microporous type polymer dielectric of the prepared inorganic materials of the present invention.Take out MCF electrode slice and polymer dielectric film soaked 20min in electrolytic solution after, its surface electrolyte is blotted gently, be assembled into button cell then with filter paper.Fig. 6 is by being assembled Li/ inorganic materials composite microporous polymer electrolyte/MCF battery circulate first (1st) and 2nd, 10th, 20th round-robin charging and discharging curve, the metacyclic multiplying power that charges and discharge that circulates first and continue is respectively 0.1C and 0.5C, and the charging/discharging voltage scope is 0.002～1.5V.Can find out from charging and discharging curve, this battery has charge and discharge platform comparatively stably, and owing to the formation of SEI film, coulombic efficiency is about 85.0% in circulating first, 20th circulation back coulombic efficiency reaches 98% (in lithium/carbon half-cell, coulombic efficiency is defined as the ratio of charging capacity and loading capacity).It may be noted that to descend greatlyyer that this is that latter's charging and discharging currents is bigger, thereby must add the internal polarization of macrocell because front and back twice round-robin charging and discharging currents difference causes, and then causes cell container to reduce from being recycled to 2nd cycle charging capacity first.
Fig. 7 provides battery the 2-20 time round-robin capacity curve after changing into first, can see charge and discharge 19 times with 0.5 C constant current after, the battery charge capability retention is about 94.0%.The stable performance in charge and discharge process of the composite microporous type polymer dielectric of the prepared inorganic materials of the present invention is described, battery its performance after optimizing also is expected to further raising.
The above results shows that adopting the said method of the present invention to prepare microporous membrane need not to use softening agent, has avoided the extraction link, and is low to the temperature and humidity conditions requirement, can greatly simplify film making process; Prepared composite micro porous film degree of crystallinity descends, and electrochemical window is slightly widened, and is more stable with the interfacial property of electrode.This development to battery industry has much realistic meaning, and shows important value of the present invention.
Embodiment 3:
Similar to Example 1, its difference is inorganic materials SBA-15 mesopore molecular sieve is scattered in the solvent DMF, the mass content that inorganic materials accounts in the composite microporous type polymer dielectric is 10%, and the consumption of DMF is 3.5ml, and sonic oscillation 20min is uniformly dispersed to inorganic materials; PVDF-HFP powder with 0.4g adds in the above-mentioned inorganic materials suspension liquid again, makes the PVDF-HFP dissolving, gets film-casting liquid, leaves standstill then and sloughs bubble; On film forming substrate glass sheet, smear film-casting liquid; The sheet glass of smearing film-casting liquid is dried in air, and bake out temperature is 60 ℃, oven dry back vacuum-drying in vacuum drying oven, and vacuum drying temperature is 70 ℃, makes the inorganic materials composite micro porous film, is called dry film; Dry film is immersed electrolytic solution, and the gel state composite micro porous film that contains electrolytic solution that has promptly obtained activating is called wet film.
Embodiment 4:
Similar to Example 1, its difference is inorganic materials SBA-15 mesopore molecular sieve is scattered in the solvent N-N-methyl-2-2-pyrrolidone N-(NMP), the mass content that inorganic materials accounts in the composite microporous type polymer dielectric is 15%, the consumption of N-N-methyl-2-2-pyrrolidone N-(NMP) is 1.5ml, and sonic oscillation 5min is uniformly dispersed to inorganic materials; PVDF-HFP powder with 0.4g adds in the above-mentioned inorganic materials suspension liquid again, makes the PVDF-HFP dissolving, gets film-casting liquid, leaves standstill then and sloughs bubble; On film forming substrate glass sheet, smear film-casting liquid; The sheet glass of smearing film-casting liquid is dried in air, and bake out temperature is 30 ℃, oven dry back vacuum-drying in vacuum drying oven, and vacuum drying temperature is 45 ℃, makes the inorganic materials composite micro porous film, is called dry film; Dry film is immersed electrolytic solution, and the gel state composite micro porous film that contains electrolytic solution that has promptly obtained activating is called wet film.
Embodiment 5:
Similar to Example 1, its difference is inorganic materials SBA-15 mesopore molecular sieve is scattered in the solvent N-N-methyl-2-2-pyrrolidone N-(NMP), the mass content that inorganic materials accounts in the composite microporous type polymer dielectric is 20%, the consumption of N-N-methyl-2-2-pyrrolidone N-(NMP) is 4ml, and sonic oscillation 15min is uniformly dispersed to inorganic materials; PVDF-HFP powder with 0.4g adds in the above-mentioned inorganic materials suspension liquid again, makes the PVDF-HFP dissolving, gets film-casting liquid, leaves standstill then and sloughs bubble; On film forming substrate glass sheet, smear film-casting liquid; The sheet glass of smearing film-casting liquid is dried in air, and bake out temperature is 80 ℃, oven dry back vacuum-drying in vacuum drying oven, and vacuum drying temperature is 30 ℃, makes the inorganic materials composite micro porous film, is called dry film; Dry film is immersed electrolytic solution, and the gel state composite micro porous film that contains electrolytic solution that has promptly obtained activating is called wet film.
Embodiment 6:
Similar to Example 1, its difference is inorganic materials SBA-15 mesopore molecular sieve is scattered in solvent N-N-methyl-2-2-pyrrolidone N-(NMP) and the acetone, the mass content that inorganic materials accounts in the composite microporous type polymer dielectric is 25%, the consumption of N-N-methyl-2-2-pyrrolidone N-(NMP) is 1.5ml, the consumption of acetone is 2.5ml, and sonic oscillation 30min is uniformly dispersed to inorganic materials; PVDF-HFP powder with 0.4g adds in the above-mentioned inorganic materials suspension liquid again, makes the PVDF-HFP dissolving, gets film-casting liquid, leaves standstill then and sloughs bubble; On film forming substrate glass sheet, smear film-casting liquid; The sheet glass of smearing film-casting liquid is dried in air, and bake out temperature is 70 ℃, oven dry back vacuum-drying in vacuum drying oven, and vacuum drying temperature is 90 ℃, makes the inorganic materials composite micro porous film, is called dry film; Dry film is immersed electrolytic solution, and the gel state composite micro porous film that contains electrolytic solution that has promptly obtained activating is called wet film.
Embodiment 7:
Similar to Example 1, its difference is inorganic materials SBA-15 mesopore molecular sieve is scattered in solvent DMF and the acetone, the mass content that inorganic materials accounts in the composite microporous type polymer dielectric is 30%, the consumption of DMF is 2.5ml, the consumption of acetone is 1.5ml, and sonic oscillation 25min is uniformly dispersed to inorganic materials; PVDF-HFP powder with 0.4g adds in the above-mentioned inorganic materials suspension liquid again, makes the PVDF-HFP dissolving, gets film-casting liquid, leaves standstill then and sloughs bubble; On film forming substrate glass sheet, smear film-casting liquid; The sheet glass of smearing film-casting liquid is dried in air, and bake out temperature is 100 ℃, oven dry back vacuum-drying in vacuum drying oven, and vacuum drying temperature is 75 ℃, makes the inorganic materials composite micro porous film, is called dry film; Dry film is immersed electrolytic solution, and the gel state composite micro porous film that contains electrolytic solution that has promptly obtained activating is called wet film.
Embodiment 8:
Similar to Example 1, its difference is inorganic materials SBA-15 mesopore molecular sieve is scattered in the solvent DMF, the mass content that inorganic materials accounts in the composite microporous type polymer dielectric is 35%, and the consumption of DMF is 5ml, and sonic oscillation 35min is uniformly dispersed to inorganic materials; PVDF-HFP powder with 0.4g adds in the above-mentioned inorganic materials suspension liquid again, makes the PVDF-HFP dissolving, gets film-casting liquid, leaves standstill then and sloughs bubble; On film forming substrate glass sheet, smear film-casting liquid; The sheet glass of smearing film-casting liquid is dried in air, and bake out temperature is 90 ℃, oven dry back vacuum-drying in vacuum drying oven, and vacuum drying temperature is 100 ℃, makes the inorganic materials composite micro porous film, is called dry film; Dry film is immersed electrolytic solution, and the gel state composite micro porous film that contains electrolytic solution that has promptly obtained activating is called wet film.
Claims (6)
1, composite microporous polymer electrolyte, contain electrolytic solution, it is characterized in that its composition and by the content of mass ratio be: vinylidene fluoride-hexafluoropropylene copolymer is 65%～95%, and inorganic materials is 5%～35%, and described inorganic materials is the SBA-15 mesopore molecular sieve.
2, the preparation method of composite microporous polymer electrolyte as claimed in claim 1 is characterized in that the steps include:
1), inorganic materials is scattered in the solvent, sonic oscillation to inorganic materials is uniformly dispersed; Again the vinylidene fluoride-hexafluoropropylene copolymer powder is added in the inorganic materials suspension liquid, make the vinylidene fluoride-hexafluoropropylene copolymer dissolving, get film-casting liquid, leave standstill then and slough bubble, described solvent is selected from a kind of or its mixed solvent in acetone, DMF, the N-N-methyl-2-2-pyrrolidone N-, is 1: 3.7～12.5 by quality than the content of vinylidene fluoride-hexafluoropropylene copolymer and solvent;
2), becoming on the film base material to smear film-casting liquid;
3), the one-tenth film base material that will smear film-casting liquid dries the final vacuum drying in air, make the inorganic materials composite micro porous film, is called dry film:
4), dry film is immersed electrolytic solution, the gel state composite micro porous film that contains electrolytic solution that has promptly obtained activating is called wet film.
3, the preparation method of composite microporous polymer electrolyte as claimed in claim 2 is characterized in that in step 1), and the sonic oscillation time is 5～35min.
4, system 2 methods of composite microporous polymer electrolyte as claimed in claim 2 is characterized in that in step 2) in, become film base material to be selected from sheet glass.
5, the preparation method of composite microporous polymer electrolyte as claimed in claim 2 is characterized in that in step 3), and the temperature of drying in air is 30～100 ℃.
6, the preparation method of composite microporous polymer electrolyte as claimed in claim 2 is characterized in that in step 3), and vacuum drying temperature is 30～100 ℃.
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| CN100465225C (en) * | 2006-10-24 | 2009-03-04 | 北京科技大学 | Process for preparing hybridized porous lithium ion cell electrolyte film |
| CN101721922B (en) * | 2008-07-22 | 2011-12-28 | 山东华夏神舟新材料有限公司 | Microporous film enhanced multilayer fluorine-containing crosslinked ion-doped film and preparation method thereof |
| CN101710614B (en) * | 2009-12-16 | 2012-06-20 | 南京大学 | Diaphragm of modified lithium battery with medium hole nano particles |
| CN102286158B (en) * | 2011-06-23 | 2012-12-12 | 中南大学 | Method for preparing porous composite polymer electrolyte film through gas volatilization |
| CN107474270B (en) | 2016-06-07 | 2021-01-12 | 上海恩捷新材料科技有限公司 | Preparation method of polymer electrolyte membrane |
| CN106450512A (en) * | 2016-09-29 | 2017-02-22 | 清华大学 | Metal battery with molecular sieve solid electrolyte layer |
| CN110165219B (en) | 2019-06-03 | 2020-10-30 | 宁德新能源科技有限公司 | Electrochemical device |
| CN115863753B (en) * | 2022-12-30 | 2023-06-13 | 沧州中孚新能源材料有限公司 | Gel electrolyte diaphragm and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1403492A (en) * | 2002-10-15 | 2003-03-19 | 清华大学 | In-situ compounding process of preparing porous polymer electrolyte |
| US20050129604A1 (en) * | 2003-11-21 | 2005-06-16 | Pak Chan-Ho | Mesoporous carbon molecular sieve and supported catalyst employing the same |
| CN1640934A (en) * | 2004-12-16 | 2005-07-20 | 上海交通大学 | Full-solid composite polymer electrolyte containing molecular sieve and preparation method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1403492A (en) * | 2002-10-15 | 2003-03-19 | 清华大学 | In-situ compounding process of preparing porous polymer electrolyte |
| US20050129604A1 (en) * | 2003-11-21 | 2005-06-16 | Pak Chan-Ho | Mesoporous carbon molecular sieve and supported catalyst employing the same |
| CN1640934A (en) * | 2004-12-16 | 2005-07-20 | 上海交通大学 | Full-solid composite polymer electrolyte containing molecular sieve and preparation method therefor |
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