CN1322019A - Microporous polymer diaphragm for secondary lithium battery and preparation method thereof - Google Patents

Microporous polymer diaphragm for secondary lithium battery and preparation method thereof Download PDF

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CN1322019A
CN1322019A CN00107243A CN00107243A CN1322019A CN 1322019 A CN1322019 A CN 1322019A CN 00107243 A CN00107243 A CN 00107243A CN 00107243 A CN00107243 A CN 00107243A CN 1322019 A CN1322019 A CN 1322019A
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solvent
weight
unsaturated polyester
thermosetting resin
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CN1142602C (en
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顾辉
黄学杰
陈立泉
任旭梅
吴锋
单忠强
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State Center Of High Technology New Energy Storage Material Engineering Developm
Institute of Physics of CAS
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State Center Of High Technology New Energy Storage Material Engineering Developm
Institute of Physics of CAS
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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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The present invention belongs to the technical field of high-energy batteries for manufacturing room-temperature secondary lithium batteries. The invention dissolves thermosetting resin, initiator, accelerant, cross linker and thermoplastic polymer in the mixed solution of solvent and non-solvent to form homogeneous solution or suspension, and adopts dry method, wet method or thermal method phase inversion technique to obtain the microporous polymer diaphragm by controlling temperature and time. The diaphragm has the advantages of simple preparation process, low cost, high porosity, controllable pore size, large liquid absorption amount, strong surface adhesion, higher mechanical strength, and contribution to manufacturing secondary lithium batteries with good safety and long cycle life, and the secondary lithium batteries are suitable for large-current charging and discharging. The membrane may also be used as a separation membrane and a support membrane.

Description

A kind of micropore polymer diaphragm that is used for serondary lithium battery and preparation method thereof
The invention belongs to the high-energy battery field, particularly make the high-energy battery technical field of room temperature serondary lithium battery.
Along with the progress of information, material and energy technology, serondary lithium battery technology and associated materials thereof are also developed rapidly.In serondary lithium battery, micropore polymer diaphragm connects and separates positive pole and negative material, and barrier film is the insulator of electronics, but allows the ion migration to pass through, and is the important component part of battery.The quality of membrane properties is determining the interfacial structure of battery, the internal resistance of battery, and then affect the key characteristics such as capacity, cyclicity, charging and discharging currents density of battery, so the barrier film of excellent performance has important effect for the combination property that improves battery.
At present, at the microporous barrier of the industry-wide micropore polymer diaphragm of serondary lithium battery for the production of Celgard method, this method mainly is to obtain hemicrystalline thin polymer film by melt extruding, then it is stretched, produce many micropores in film, do not need solvent in the manufacture process, throughput rate is higher, used macromolecular material is extensive commercial polypropylene (PP) and polyethylene (PE), belongs to one of the most cheap membrane material.But the aperture, crack of the microporous barrier that the Celgard method is produced is the longest to be 0.4um, the wideest 0.04um, porosity is the highest by 40%, all within the aperture and porosity ranges of phase inversion method barrier film, so its liquid absorption to electrolyte is low, limit the raising of lithium ion mobility, be unfavorable for the high current charge-discharge of battery; Polypropylene ductility is relatively poor, and surface energy is low, belongs to hard bonding plastics, is unfavorable for bonding with positive and negative plate, and barrier film combines not tight with electrode interface, influence the energy density of battery; In addition, Celgard method equipment complexity, manufacturing cost is higher, and price is also expensive, finally causes the rising of battery cost (to see document 1, R.E.Kesting, Synthetic Polymeric Membranes.Second Edition, John Wiley﹠amp; Sons, 1985).
Polymer paraphase film is to be that to be transformed into a polymer be that the process of preparing of the three-dimensional macromolecular network gel of continuous phase forms for the polymer solution of continuous phase at dicyandiamide solution, paraphase technology comprises: dry process, wet processing, hot method technology, polymer helps method technology with fixed attention.By telomerized polymer and solvent, non-solvent or and cosolvent between proportioning, the control temperature, solvent evaporates speed, factors such as time in non-solvent is bathed can be prepared has different-thickness, aperture size, the microporous polymer paraphase film of porosity, the aperture size maximum can reach more than the 600um, porosity is the highest to surpass 80%, the specific surface of barrier film is bigger, have enough liquid absorptions, and barrier film preparation technology is simple, do not need extruding and stretcher in the Celgard method, can directly utilize existing coating device, cost is lower, be a kind of microporous barrier preparation technology of less expensive, the research of at present relevant paraphase film is more, main as diffusion barrier (mainly be to produce liquid or the gas that purifies, as micro-filtration, ultrafiltration, high filter), is used for the electrochemical membrane also developed (seeing document [2]-[7]) of battery and electrolytic cell simultaneously with support membrane (being the non-application that separates).[2]A.D.Pasquier,I.Plits,G.G.Amatucci,T.zheng,A.S.Gozdz?andJ.M.Tarascon.Plastic?PVDF-HPF?Electrolyte?Laminates?Prepared?by?aPhase-Inversion?Process.12 th?International?Conference?on?Solid?StateIonics,Halkidiki,A-14-P(1999)[3]S.P.Nunes,M.L.Sforca?and?K.V.Peinemann.Dense?HydrophilicComposite?Membranes?for?Ultrafiltration.Journal?of?MembraneScience.No.106,49(1995)[4]K.Jian,P.N.Pintauro?and?R.?Ponangi.?Separation?of?Organic/WaterMixtures?With?Asymmetric?Poly(vinylidene?fluoride)Membranes.Journal?ofMembrane?Science.No.117,117(1996)[5]M.Tomaszewska.Preparation?and?Properties?Of?Plat-Sheet?MembranesFrom?Poly(vynylidene?fluoride)?for?MembranesDistillation.Desalination.Vol.104,1(1996)[6]?P.N.Pintauro?and?K.Z.Jian.?Integral?Asymmetric?FluoropolymerPervaporation?Membranes?and?Method?of?Making?the?Same.United?StatesPatent.1995,5387378[7]J.P.Puglia?and?D.F.Mckinley.Self?Supporting?Hollow?Fiber?Membraneand?Method?of?Construction.Patent?Cooperation?Treaty.1997,WO97/28891
The micropore paraphase film that is used for serondary lithium battery is relatively poor relatively because of mechanical strength, and does not possess the self-closing mechanism under the high temperature, so can not be directly used in the manufacturing of serondary lithium battery.
The object of the present invention is to provide a kind of be used for serondary lithium battery have many components micropore polymer diaphragm of high-temperature self-closing mechanism and preparation method thereof, with thermosetting resin and initator thereof, promoter, crosslinking agents etc. and thermoplastic polymer are dissolved in the mixed liquor of solvent and non-solvent altogether (if thermoplastic polymer is powder or short fiber, also can be insoluble to solvent) form homogeneous phase solution or suspension-turbid liquid as casting solution, adopt dry method, wet method or hot method paraphase technology, control by to temperature, time etc. obtains micropore polymer diaphragm.Preparation technology is simple for this barrier film, cost is low, the porosity height, liquid absorption is big, surface adhesive is strong, has higher mechanical strength, and fusion can take place at high temperature low-melting thermoplastic polymer component, thereby block the barrier film micropore resistance is improved, help making the better serondary lithium battery of fail safe.Serondary lithium battery with micropore polymer diaphragm preparation of the present invention has better chemical property.Because the membrane surface adhesiveness is good, can form good bondingly with positive and negative plate, improve the interface and adhered to compactness, reduced the interface impedance and the internal resistance of cell of electrolyte and electrode; Simultaneously because barrier film porosity height, specific surface is big, and is big to the adsorbance of electrolyte, the migration that is very beneficial for lithium ion with transport, its ionic conductivity is improved, so battery first all efficient height, irreversible capacity loss is little, have extended cycle life, fail safe is good, can stand high current charge-discharge.
The object of the present invention is achieved like this:
The micropore polymer diaphragm that is used for serondary lithium battery and has a high-temperature self-closing mechanism of the present invention is a kind of microporous barrier of being made up of crosslinked thermosetting resin, low melting point thermoplastic polymer and nanophase oxide powder (account for the 10%-80% of polymer weight, also can not add).Form crosslinked three-dimensional framework structure behind thermosetting resin (accounting for the 20%-80% of barrier film weight) and initator, crosslinking agent and the booster response, play a supportive role, the low melting point thermoplastic polymer is scattered in the skeleton structure, after temperature raises, the hole in the network is stopped up in low melting point thermoplastic polymer (accounting for the 20%-80% of barrier film weight) fusion, thereby makes diaphragm seals.Conductance measurement under different temperatures and scanning electron microscopic observation prove that barrier film has the self-enclosed effect of good high-temperature.
Being used to prepare the each component material that is used for the micropore polymer diaphragm of serondary lithium battery of the present invention comprises:
(1) thermosetting resin: the water and the organic solvent that are insoluble to behind the curing cross-linked in the electrolyte (comprise ethylene carbonate, propene carbonate, diethyl carbonate, dimethyl carbonate, gamma-butyrolacton, dimethyl-tetrahydrofuran) and have good chemical and electrochemical stability and thermal stability.Thermosetting resin accounts for the 20%-80% of barrier film weight.
(1) epoxy resin: as the glycidol ether type, glycidyl ester type, glycidic amine type, cycloaliphatic epoxy resin, alicyclic glycidol ether type, alicyclic glycidyl ester type, aliphatic epoxy resin, spiral shell structural epoxy resins, novolac epoxy resin.
(2) unsaturated polyester (UP): as the cis-butenedioic anhydride type, acrylic type, propylene ester type.
(3) phenolic resins: as ammonia catalysis phenolic aldehyde, barium phenolic aldehyde, boron phenolic aldehyde, modified phenolic.
(4) polyimide resin: as alkynes end group polyimides, PMR type polyimides, bismaleimides type polyimides.
(2) initator: use during for unsaturated polyester (UP) at thermosetting resin.Alkyl peroxide, as t-butyl hydrogen peroxide, cumene hydroperoxide hydrogen; The dialkyl peroxide is as di-tert-butyl peroxide; Peroxy acid is as Peracetic acid; Diacyl peroxide, as dibenzoyl peroxide, acetyl peroxide; Peroxy esters is as the special butyl ester of peroxidating formic acid; Peroxidating derivative mixture after the ketone oxidation, as methyl ethyl ketone peroxide, cyclohexanone peroxide.Consumption accounts for the 0.1%-5.0% of unsaturated polyester (UP) weight.
(3) crosslinking agent:
(1) epoxy resin cross-linking agent: Armeen, as polyethylene polyamine, diethylin is for propylamine; Modified amine, as amine-resin, amine-glycerin ether addition product, amine-ethylene oxide adduct, cyanoethylation product, mixed amine; Alicyclic amine; Tertiary amine is as trimethylamine and derivative thereof; Tertiary ammonium salt; Aromatic amine, as modified aromatic amine, unmodified aromatic amine; Acid amides is as low molecular polyamides; Latent curing agent is as boron trifluoride amine complex compound, borate; Anhydrides, as phthalic anhydride, maleic anhydride, hexahydrophthalic anhydride, pyromellitic acid anhydride etc.; Imidazoles is as diethyl tetramethyl imidazoles.Consumption accounts for the 1.0%-100.0% of weight epoxy.
(2) unsaturated polyester cross-linking agent: as styrene, methyl methacrylate, diallyl phthalate, vinyltoluene, cyanuric acid tripropylene.Consumption accounts for the 0.1%-5.0% of unsaturated polyester (UP) weight.
(4) promoter:
(1) epoxy resin promoter: as bisphenol-A, phenol, resorcinol, nonyl phenol, 2,4,6-three (dimethylamino methyl) phenol, TGA, triphenyl phosphite ester, the boron trifluoride mono aminoethane, fatty amine, benzyl dimethylamine, dimethylaniline, pyridine, 2-ethyl-4-methylimidazole, triethanolamine borate.Consumption accounts for the 0.01%-1.0% of weight epoxy.
(2) unsaturated polyester (UP) promoter: metallic compound, as cobalt naphthenate, cobalt octoate, manganese promoter, copper promoter, vanadium promoter; Tertiary amines, as dimethylaniline, diethylaniline, dimethyl-p-toluidine; 2, the 4-pentanedione.Consumption accounts for the 0.05%-1.0% of unsaturated polyester (UP) weight.
(5) thermoplastic polymer: the water and the organic solvent that are insoluble in the electrolyte (comprise ethylene carbonate, propene carbonate, diethyl carbonate, dimethyl carbonate, gamma-butyrolacton, dimethyl-tetrahydrofuran) and the fusing point with good chemical and electrochemical stability 60-140 ℃ polymeric film material, as Kynoar (PVDF) and copolymer (Copolymer) thereof, gather (6-caprolactone) (PCL), poly 1 butene, poly--1 amylene, random polystyrene, copolymerized methanal, ethylene-vinyl acetate copolymer (EVA), polybutyl methacrylate (PBMA), styrene-butadiene block copolymer (SBS), the polyacrylic acid allyl ester, cellulose acetate (CA) gathers 1,4-butadiene (PB), poly-ethanedioic acid propylene diester, polyethylene succinate, polydecamethylene adipamide (NYLON610), poly-decanedioyl o-phenylenediamine, the poly dimethyl propylene, poly-valeral.Thermoplastic polymer accounts for the 20%-80% of barrier film weight.
(6) solvent: the thermosetting resin of energy dissolve uncrosslinked, initator, crosslinking agent, promoter and thermoplastic polymer (, also can be insoluble to solvent) if thermoplastic polymer is powder or short fiber, as acetone, N, dinethylformamide, N, N-dimethylacetylamide, triethyl phosphate, oxolane, N-methyl pyrrolidone, dimethyl sulfoxide (DMSO), benzene, toluene, dimethylbenzene, chlorobenzene, carrene, chloroform, carbon tetrachloride, methyl alcohol, ethanol, propyl alcohol, isobutanol, 1-butanols, n-hexane, cyclohexane, pentane, trichloroethylene, o-dichlorohenzene, methyl formate, ethyl acetate, hexafluoroisopropanol, dioxane, dioxolanes, sulfolane, cyclohexanone, N-dihydroxy ethyl ox ester amine, formic acid, dioctyl phthalate, tetrachloroethanes, methylethylketone, o-chlorphenol, trifluoroethanol, N-methyl caprolactam, HMPA, tetramethylurea, 1-amylalcohol, sec-n-octyl alcohol, cyclohexanol, phenmethylol, ether, ethylene glycol monoethyl ether, furfural, diethylenetriamine, pyridine, dichloroethanes.
(7) non-solvent: energy and solvent are miscible mutually, as methyl alcohol, and ethanol, propyl alcohol, isobutanol, 1-butanols, glycerol, ethylene glycol, cyclobutanol, cyclohexanol, formamide, water, trifluoroethanol, methyl-sulfoxide, hexafluoroisopropanol, N-dihydroxy ethyl ox ester amine, dichloro-benzenes, trans stilbenes.Solvent boiling point needs lower more than 30 ℃ than non-solvent.
(8) cosolvent: thermosetting resin, initator, crosslinking agent, promoter and the thermoplastic polymer of energy dissolve uncrosslinked are (if thermoplastic polymer is powder or short fiber, also can be insoluble to solvent), its low temperature is non-solvent, high temperature is solvent, as saturated long-chain alcohol, 1,4-butanediol, laurate.Only adopt cosolvent when hot method technology system film, do not have other solvent and non-solvent in the solution system this moment, and cosolvent accounts for the 5%-90% of casting solution weight.
(9) nanophase oxide powder: strengthen or plasticising usefulness, as nano silicon, nano aluminium oxide, addition accounts for the 10%-80% of polymer weight.
The basic structure of micropore polymer diaphragm of the present invention is: crosslinked thermosetting resin constitutes support frame with continuous three-dimensional network, thermoplastic polymer (being dissolved in solvent) is scattered in the support frame with molecular level, form microporous barrier, nanophase oxide powder (can not add) is dispersed in thermosetting resin and the thermoplastic polymer.
The structure of barrier film can also be: crosslinked thermosetting resin constitutes support frame with continuous three-dimensional network, thermoplastic polymer (being insoluble to solvent) is with graininess (grain size 1 μ m-100 μ m) or fibrous (length is 0.1mm-1mm) is dispersed in the support frame or between the skeleton, nanophase oxide powder (can not add) is dispersed in the thermosetting resin; Or two-layer thermosetting resin microporous barrier folder one deck thermoplastic polymer microporous barrier or one deck thermoplastic polymer microporous barrier and the film formed structure of composite membrane of one deck thermosetting resin micropore.
The micropore polymer diaphragm that is used for serondary lithium battery of the present invention prepares according to the following steps:
(1) with thermosetting resin, can be dissolved in the low melting point thermoplastic polymer (also can be that the particle diameter that is insoluble to solvent is that powder or the length of 1-100um is the fiber of 0.1-1mm) of solvent, (thermosetting resin adds during for unsaturated polyester (UP) initator, consumption accounts for the 0.1%-5.0% of unsaturated polyester (UP) weight, can not add) yet, (thermosetting resin adds when being unsaturated polyester (UP) or epoxy resin crosslinking agent, unsaturated polyester cross-linking agent consumption accounts for the 0.1%-5.0% of unsaturated polyester (UP) weight, epoxy resin cross-linking agent accounts for the 1.0%-100.0% of weight epoxy, can not add) yet, (the epoxy resin accelerator dosage accounts for the 0.01%-1.0% of weight epoxy to promoter, the 0.05%-1.0% that unsaturated polyester (UP) promoter accounts for unsaturated polyester (UP) can not add yet), the nanophase oxide powder (can not add yet, account for the 10%-80% of polymer weight), solvent and non-solvent mix the uniform solution (being suspension-turbid liquid when thermoplastic polymer is insoluble to solvent) of (can heat) formation as casting solution, thermosetting resin weight accounts for 5%-50% in the casting solution, thermoplastic polymer accounts for 5%-50%, solvent accounts for 50%-80%, and non-solvent accounts for 5%-25%.
(2) at normal temperatures and pressures casting solution is coated on clean glass, plastics or the metallic substrates by roller coat or blade coating (scraper gap 0.10mm-1.00mm).
(3) adopt dry process to prepare barrier film, by regulating heating-up temperature and time control solvent evaporates speed, temperature range is the boiling point that room temperature arrives non-solvent, loses viscosity up to casting solution.Then barrier film is placed on 12h-24h in the vacuum drying oven that is lower than the thermoplastic polymer softening point temperature, can obtain pore size is that 5um-50um, porosity are 30%-80%, the barrier film of thickness 10um-50um.
Above-mentioned steps (3) can also be adopted hot method technology, adopt cosolvent to replace solvent and non-solvent, cosolvent accounts for the 5%-90% of casting solution weight.
Can also adopt wet processing to prepare barrier film above-mentioned steps (3), be coated in suprabasil casting solution and in the temperature range of the boiling point from the room temperature to the non-solvent, vapor away partial solvent, keep viscosity greater than 10 handkerchief seconds, be immersed in the non-solvent bath that contains a small amount of solvent (solvent accounts for the 0%-50% of non-solvent weight), non-solvent bath temperature scope is 0 ℃ of boiling point to solvent.
Can also according to said method prepare the composite microporous polymer barrier film:
(1) thermoplastic polymer and nanophase oxide powder (also can not adding) are dissolved in according to the above ratio the casting solution that forms homogeneous in the mixed liquor of its solvent and non-solvent or the cosolvent (in hot method technology), making thickness 5um-20um, pore size by above-mentioned dry method, wet method or hot method technology is that 5um-50um, porosity are 30% one 80% support membrane;
(2) with thermosetting resin, nanophase oxide powder (also can not adding), initator (thermosetting resin for unsaturated polyester (UP) time add), (thermosetting resin adds when being unsaturated polyester (UP) and epoxy resin crosslinking agent, can not add yet) and promoter (also can not adding) be dissolved in the casting solution that forms homogeneous in the mixed liquor of its solvent and non-solvent according to the above ratio, be coated in the single face or the two sides of support membrane, by dry process make thickness 10um-50um, pore size is that 5-50um, porosity are 30%-80% composite microporous polymer film.
Manufacturing process of the present invention is simple, and cost is low, the porosity height, and the aperture size may command, plasticity is good, has high-temperature self-closing mechanism.Micropore polymer diaphragm with high-temperature self-closing mechanism of the present invention can be used for preparing the lithium ion battery or the lithium battery of plurality of specifications, as button (individual layer), and column type (multilaminate coiled), slim (multilayer folding) battery etc.The battery of preparation is applicable to multiple occasion, as mobile phone, and beep-pager, notebook computer, palmtop PC, field camera and machine, electronic toy, electric tools etc. are specially adapted to the hybrid-electric car and the power assist vehicle field of high current charge-discharge.Micropore polymer diaphragm with high-temperature self-closing mechanism of the present invention in addition also can be used as diffusion barrier (waste water treatment/concentrate, gas separations/enrichment, dialysis etc.) and support membrane (control discharges).
Below in conjunction with chart and embodiment the present invention is done further narration:
Fig. 1 is the stereoscan photograph of the embodiment of the invention 1 microporous barrier,
Fig. 2 is be heated a barrier film stereoscan photograph after closing of the embodiment of the invention 1 micropore.
The cyclicity parameter is that the difference of the tenth all discharge capacities and first all discharge capacities is divided by the discharge capacity first time in the table 1.The reversible capacity value is based on anode material, and promptly the tenth all discharge capacities are divided by the active material of positive electrode quality.First all efficient is meant that first all discharge capacities are divided by first all charging capacitys.Second all efficient is meant that second all discharge capacities are divided by second all charging capacitys.[embodiment 1]
With Kynoar (Kynar2851 type PVDF), 618 epoxy resin, N, the N-dimethyl benzylamine, acetone, glycerol (glycerine) was by weight 10: 8: 1.2: 160: 7 mixed, heating for dissolving forms the solution of transparent and homogeneous as casting solution, be coated on the clean substrate of glass, room temperature was placed 5 minutes, at room temperature immersed volume ratio then and be in the mixed liquor of 1: 3 acetone and water 5 minutes, immersed again after the taking-up in the mixed liquor that 0 ℃ acetone and water volume ratio be 1: 3 25 minutes, in 40 ℃ vacuum drying oven, place baking in 36 hours and remove residual solvent and non-solvent.The stereoscan photograph of barrier film is seen Fig. 1, and the electromicroscopic photograph that micropore is closed after 160 ℃ of heating is seen Fig. 2.
Barrier film after the oven dry is cut into 1.8cm 2Disk is made negative electrode with metallic lithium foil, makes anode with MCMB, dresses up the chemical property that the button Experimental cell is studied barrier film with barrier film.Cathode preparation method is as follows: the compound slurry that MCMB (granularity 15um) is become homogeneous with dimethyl formamide (DMF) solution mixing system of bonding agent such as certain density Kynoar (PVDF), evenly be coated in then on the Copper Foil (thickness 10-15um), gained film thickness 40-90um, 100-160 ℃ of oven dry down, densification continues to dry by the fire 12 hours down at 100-160 ℃ then.In the pole piece after the oven dry, MCMB accounts for the 94wt% that always is coated with application, and Kynoar (PVDF) accounts for 6wt%, and the gained pole piece is cut into 1.0cm 2Disk as anode.Electrolyte adopts 1MLiPF 6(EC/DEC volume ratio 1: 1).The be assembled in water, oxygen content of battery are lower than in the argon gas glove box of 1ppm and carry out.
Utilize micro-processor controlled auto charge and discharge instrument that Experimental cell is carried out the charge and discharge cycles test.Current density is 0.2mA/cm 2, charging cut-ff voltage 2.0V, discharge cut-off voltage 0.001V discharges and recharges data and lists in the table 1.[embodiment 2]
With Kynoar (Kynar2851 type PVDF), 618 epoxy resin, dicyandiamide, acetone, glycerol (glycerine) was by weight 10: 8: 0.5: 160: 7 mixed, heating for dissolving forms the solution of transparent and homogeneous as casting solution, be coated on the clean substrate of glass, room temperature was placed 5 minutes, at room temperature immersed volume ratio then and be in the mixed liquor of 1: 3 acetone and water 5 minutes, immersed again after the taking-up in the mixed liquor that 0 ℃ acetone and water volume ratio be 1: 3 25 minutes, and in 40 ℃ baking oven, placed baking in 36 hours and remove residual solvent and non-solvent.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 3]
With Kynoar (Kynar2851 type PVDF), 618 epoxy resin, polyethylene polyamine, acetone, glycerol (glycerine) was by weight 10: 8: 1.5: 160: 7 mixed, heating for dissolving forms the solution of homogeneous as casting solution, taking-up is coated on the clean substrate of glass, room temperature was placed 5 minutes, at room temperature immersed volume ratio then and be in the mixed liquor of 1: 3 acetone and water 5 minutes, immersed again after the taking-up in the mixed liquor that 0 ℃ acetone and water volume ratio be 1: 3 25 minutes, and in 40 ℃ baking oven, placed baking in 10 hours and remove residual solvent and non-solvent.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 4]
With Kynoar (Kynar2851 type PVDF), 618 epoxy resin, adjacent hydroxybenzyl dimethylamine, acetone, glycerol (glycerine) was by weight 10: 8: 0.8: 160: 7 mixed, heating for dissolving forms the solution of transparent and homogeneous as casting solution, be coated on the clean substrate of glass, room temperature was placed 5 minutes, at room temperature immersed volume ratio then and be in the mixed liquor of 1: 3 acetone and water 5 minutes, immersed again after the taking-up in the mixed liquor that 0 ℃ acetone and water volume ratio be 1: 3 25 minutes, and in 40 ℃ baking oven, placed baking in 10 hours and remove residual solvent and non-solvent.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 5]
With Kynoar (Kynar2851 type PVDF), 618 epoxy resin, m-xylene diamine, acetone, glycerol (glycerine) was by weight 10: 8: 1.5: 160: 7 mixed, heating for dissolving forms the solution of homogeneous as casting solution, taking-up is coated on the clean substrate of glass, room temperature was placed 5 minutes, at room temperature immersed volume ratio then and be in the mixed liquor of 1: 3 acetone and water 5 minutes, immersed again after the taking-up in the mixed liquor that 0 ℃ acetone and water volume ratio be 1: 3 25 minutes, and in 40 ℃ baking oven, placed baking in 10 hours and remove residual solvent and non-solvent.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 6]
With Kynoar (Kynar2851 type PVDF), 618 epoxy resin, N, the N-dimethyl benzylamine, acetone, glycerol (glycerine) was by weight 10: 8: 1.2: 160: 7 mixed, heating for dissolving forms the solution of transparent and homogeneous, add the nanophase silicon dioxide that accounts for PVDF weight 30% again, the back that stirs is coated on the clean substrate of glass as casting solution, room temperature was placed 5 minutes, at room temperature immersed volume ratio then and be in the mixed liquor of 1: 3 acetone and water 5 minutes, immersed again after the taking-up in the mixed liquor that 0 ℃ acetone and water volume ratio be 1: 3 25 minutes, in 40 ℃ vacuum drying oven, place baking in 36 hours and remove residual solvent and non-solvent.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 7]
With Kynoar (Kynar2851 type PVDF), 618 epoxy resin, dicyandiamide, acetone, glycerol (glycerine) was by weight 10: 8: 0.5: 160: 7 mixed, heating for dissolving forms the solution of transparent and homogeneous, add the nanophase silicon dioxide that accounts for PVDF weight 30% again, stir the back as casting solution, be coated on the clean substrate of glass, room temperature was placed 5 minutes, at room temperature immersed volume ratio then and be in the mixed liquor of 1: 3 acetone and water 5 minutes, immersed again after the taking-up in the mixed liquor that 0 ℃ acetone and water volume ratio be 1: 3 25 minutes, and in 40 ℃ vacuum drying oven, placed baking in 36 hours and remove residual solvent and non-solvent.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 8]
With Kynoar (Kynar2851 type PVDF), 618 epoxy resin, polyethylene polyamine, acetone, glycerol (glycerine) was by weight 10: 8: 1.5: 160: 7 mixed, heating for dissolving forms the solution of transparent and homogeneous, add the nanophase silicon dioxide that accounts for PVDF weight 30% again, stir the back as casting solution, be coated on the clean substrate of glass, room temperature was placed 5 minutes, at room temperature immersed volume ratio then and be in the mixed liquor of 1: 3 acetone and water 5 minutes, immersed again after the taking-up in the mixed liquor that 0 ℃ acetone and water volume ratio be 1: 3 25 minutes, and in 40 ℃ vacuum drying oven, placed baking in 36 hours and remove residual solvent and non-solvent.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 9]
With Kynoar (Kynar2851 type PVDF), 618 epoxy resin, adjacent hydroxybenzyl dimethylamine, acetone, glycerol (glycerine) was by weight 10: 8: 0.8: 160: 7 mixed, heating for dissolving forms the solution of transparent and homogeneous, add the nanophase silicon dioxide that accounts for PVDF weight 30% again, stir the back as casting solution, be coated on the clean substrate of glass, room temperature was placed 5 minutes, at room temperature immersed volume ratio then and be in the mixed liquor of 1: 3 acetone and water 5 minutes, immersed again after the taking-up in the mixed liquor that 0 ℃ acetone and water volume ratio be 1: 3 25 minutes, and in 40 ℃ vacuum drying oven, placed baking in 36 hours and remove residual solvent and non-solvent.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 10]
With Kynoar (Kynar2851 type PVDF), 618 epoxy resin, m-xylene diamine, acetone, glycerol (glycerine) was by weight 10: 8: 1.0: 160: 7 mixed, heating for dissolving forms the solution of transparent and homogeneous, add the nanophase silicon dioxide that accounts for PVDF weight 30% again, stir the back as casting solution, be coated on the clean substrate of glass, room temperature was placed 5 minutes, at room temperature immersed volume ratio then and be in the mixed liquor of 1: 3 acetone and water 5 minutes, immersed again after the taking-up in the mixed liquor that 0 ℃ acetone and water volume ratio be 1: 3 25 minutes, and in 40 ℃ vacuum drying oven, placed baking in 36 hours and remove residual solvent and non-solvent.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 11]
With Kynoar (Kynar2851 type PVDF), 618 epoxy resin, N, the N-dimethyl benzylamine, acetone, glycerol (glycerine) was by weight 10: 8: 1.2: 160: 7 mixed, heating for dissolving forms the solution of transparent and homogeneous as casting solution, be coated on the clean substrate of glass, room temperature was placed 30 minutes, places baking in 36 hours then and remove residual solvent and non-solvent in 40 ℃ vacuum drying oven.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 12]
With Kynoar (Kynar2851 type PVDF), 618 epoxy resin, polyethylene polyamine, acetone, glycerol (glycerine) was by weight 10: 8: 1.5: 160: 7 mixed, heating for dissolving form the solution of transparent and homogeneous as casting solution, are coated on the clean substrate of glass, room temperature was placed 30 minutes, places baking in 36 hours then and remove residual solvent and non-solvent in 40 ℃ vacuum drying oven.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 13]
With Kynoar (Kynar2851 type PVDF), 618 epoxy resin, dicyandiamide, acetone, glycerol (glycerine) was by weight 10: 8: 0.5: 160: 7 mixed, heating for dissolving form the solution of transparent and homogeneous as casting solution, are coated on the clean substrate of glass, room temperature was placed 30 minutes, places baking in 36 hours then and remove residual solvent and non-solvent in 40 ℃ vacuum drying oven.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 14]
With Kynoar (Kynar2851 type PVDF), 618 epoxy resin, adjacent hydroxybenzyl dimethylamine, acetone, glycerol (glycerine) was by weight 10: 8: 0.8: 160: 7 mixed, heating for dissolving form the solution of transparent and homogeneous as casting solution, are coated on the clean substrate of glass, room temperature was placed 30 minutes, places baking in 36 hours then and remove residual solvent and non-solvent in 40 ℃ vacuum drying oven.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 15]
With Kynoar (Kynar2851 type PVDF), 618 epoxy resin, m-xylene diamine, acetone, glycerol (glycerine) was by weight 10: 8: 1.0: 160: 7 mixed, heating for dissolving form the solution of transparent and homogeneous as casting solution, are coated on the clean substrate of glass, room temperature was placed 30 minutes, places baking in 36 hours then and remove residual solvent and non-solvent in 40 ℃ vacuum drying oven.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 16]
With Kynoar (Kynar2851 type PVDF), 618 epoxy resin, N, N-dimethyl benzylamine, acetone, glycerol (glycerine) was by weight 10: 8: 1.2: 160: 7 mixed, and heating for dissolving forms the solution of transparent and homogeneous, adds the nanophase silicon dioxide that accounts for PVDF weight 30% again, stir the back as casting solution, be coated on the clean substrate of glass, room temperature was placed 25 minutes, places baking in 36 hours then and remove residual solvent and non-solvent in 40 ℃ vacuum drying oven.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 17]
With Kynoar (Kynar2851 type PVDF), 618 epoxy resin, polyethylene polyamine, acetone, glycerol (glycerine) was by weight 10: 8: 15: 160: 7 mixed, heating for dissolving forms the solution of transparent and homogeneous, add the nanophase silicon dioxide that accounts for PVDF weight 30% again, the back that stirs is coated on the clean substrate of glass as casting solution, room temperature was placed 25 minutes, places baking in 36 hours then and remove residual solvent and non-solvent in 40 ℃ vacuum drying oven.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 18]
With Kynoar (Kynar2851 type PVDF), 618 epoxy resin, adjacent hydroxybenzyl dimethylamine, acetone, glycerol (glycerine) was by weight 10: 8: 0.8: 160: 7 mixed, heating for dissolving forms the solution of transparent and homogeneous, add the nanophase silicon dioxide that accounts for PVDF weight 30% again, the back that stirs is coated on the clean substrate of glass as casting solution, room temperature was placed 25 minutes, places baking in 36 hours then and remove residual solvent and non-solvent in 40 ℃ vacuum drying oven.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 19]
With Kynoar (Kynar2851 type PVDF), 618 epoxy resin, m-xylene diamine, acetone, glycerol (glycerine) was by weight 10: 8: 1.0: 160: 7 mixed, heating for dissolving forms the solution of transparent and homogeneous, add the nanophase silicon dioxide that accounts for PVDF weight 30% again, the back that stirs is coated on the clean substrate of glass as casting solution, room temperature was placed 25 minutes, places baking in 36 hours then and remove residual solvent and non-solvent in 40 ℃ vacuum drying oven.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 20]
With Kynoar (Kynar2851 type PVDF), 618 epoxy resin, dicyandiamide, acetone, glycerol (glycerine) was by weight 10: 8: 0.5: 160: 7 mixed, heating for dissolving forms the solution of transparent and homogeneous, add the nanophase silicon dioxide that accounts for PVDF weight 30% again, the back that stirs is coated on the clean substrate of glass as casting solution, room temperature was placed 25 minutes, places baking in 36 hours then and remove residual solvent and non-solvent in 40 ℃ vacuum drying oven.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 21]
With Kynoar " Kynar2851 type PVDF), unsaturated polyester (UP) (SMC level), dibenzoyl peroxide, diallyl phthalate, acetone, glycerol (glycerine) was by weight 5: 5: 0.1: 1: 80: 4 mixed, heating makes the Kynoar dissolving form the solution of transparent and homogeneous as casting solution, be coated in after mixing on the clean substrate of glass, room temperature was placed 5 minutes, at room temperature immersed volume ratio then and be in the mixed liquor of 1: 3 acetone and water 5 minutes, immersed again after the taking-up in the mixed liquor that 0 ℃ acetone and water volume ratio be 1: 3 25 minutes, in 40 ℃ vacuum drying oven, place baking in 24 hours and remove residual solvent and non-solvent solvent.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 22]
With Kynoar (Kynar2851 type PVDF), unsaturated polyester (UP) (SMC level), dibenzoyl peroxide, methyl methacrylate, acetone, glycerol (glycerine) was by weight 5: 5: 0.1: 1: 80: 4 mixed, heating makes the Kynoar dissolving form the solution of transparent and homogeneous as casting solution, be coated in after mixing on the clean substrate of glass, room temperature was placed 5 minutes, at room temperature immersed volume ratio then and be in the mixed liquor of 1: 3 acetone and water 5 minutes, immersed again after the taking-up in the mixed liquor that 0 ℃ acetone and water volume ratio be 1: 3 25 minutes, in 40 ℃ vacuum drying oven, place baking in 24 hours and remove residual solvent and non-solvent solvent.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 23]
With Kynoar (Kynar2851 type PVDF), unsaturated polyester (UP) (SMC level), dibenzoyl peroxide, diallyl phthalate, acetone, glycerol (glycerine) was by weight 5: 5: 0.1: 1: 80: 4 mixed, heating makes the Kynoar dissolving form the solution of transparent and homogeneous as casting solution, account for the nanophase silicon dioxide of PVDF weight 30% in adding, be coated in after mixing on the clean substrate of glass, room temperature was placed 5 minutes, at room temperature immersed volume ratio then and be in the mixed liquor of 1: 3 acetone and water 5 minutes, immersed again after the taking-up in the mixed liquor that 0 ℃ acetone and water volume ratio be 1: 3 25 minutes, and in 40 ℃ vacuum drying oven, placed baking in 24 hours and remove residual solvent and non-solvent solvent.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 24]
With Kynoar (Kynar2851 type PVDF), unsaturated polyester (UP) (SMC level), dibenzoyl peroxide, methyl methacrylate, acetone, glycerol (glycerine) was by weight 5: 5: 0.1: 1: 80: 4 mixed, heating makes the Kynoar dissolving form the solution of transparent and homogeneous as casting solution, account for the nanophase silicon dioxide of PVDF weight 30% in adding, be coated in after mixing on the clean substrate of glass, room temperature was placed 5 minutes, at room temperature immersed volume ratio then and be in the mixed liquor of 1: 3 acetone and water 5 minutes, immersed again after the taking-up in the mixed liquor that 0 ℃ acetone and water volume ratio be 1: 3 25 minutes, and in 40 ℃ vacuum drying oven, placed baking in 24 hours and remove residual solvent and non-solvent solvent.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 25]
With Kynoar (Kynar2851 type PVDF), unsaturated polyester (UP) (SMC level), dibenzoyl peroxide, methyl methacrylate, acetone, glycerol (glycerine) was by weight 5: 5: 0.1: 1: 80: 4 mixed, heating makes the Kynoar dissolving form the solution of transparent and homogeneous as casting solution, be coated in after mixing on the clean substrate of glass, room temperature was placed 25 minutes, places baking in 24 hours then and remove residual solvent and non-solvent solvent in 40 ℃ vacuum drying oven.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment 1.[embodiment 26]
With Kynoar (Kynar2851 type PVDF), unsaturated polyester (UP) (SMC level), dibenzoyl peroxide, diallyl phthalate, acetone, glycerol (glycerine) was by weight 5: 5: 0.1: 1: 80: 4 mixed, heating makes the Kynoar dissolving form the solution of transparent and homogeneous as casting solution, be coated in after mixing on the clean substrate of glass, room temperature was placed 25 minutes, places baking in 24 hours then and remove residual solvent and non-solvent solvent in 40 ℃ vacuum drying oven.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 27]
With Kynoar (Kynar2851 type PVDF), unsaturated polyester (UP) (SMC level), dibenzoyl peroxide, diallyl phthalate, acetone, glycerol (glycerine) was by weight 5: 5: 0.1: 1: 80: 4 mixed, heating makes the Kynoar dissolving form the solution of transparent and homogeneous as casting solution, account for the nanophase silicon dioxide of PVDF weight 30% in adding, be coated in after mixing on the clean substrate of glass, room temperature was placed 25 minutes, places baking in 24 hours then and remove residual solvent and non-solvent solvent in 40 ℃ vacuum drying oven.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 28]
With Kynoar (Kynar2851 type PVDF), unsaturated polyester (UP) (SMC level), dibenzoyl peroxide, methyl methacrylate, acetone, glycerol (glycerine) was by weight 5: 5: 0.1: 1: 80: 4 mixed, heating makes the Kynoar dissolving form the solution of transparent and homogeneous as casting solution, account for the nanophase silicon dioxide of PVDF weight 30% in adding, be coated in after mixing on the clean substrate of glass, room temperature was placed 5 minutes, at room temperature immersed volume ratio then and be in the mixed liquor of 1: 3 acetone and water 5 minutes, immersed again after the taking-up in the mixed liquor that 0 ℃ acetone and water volume ratio be 1: 3 25 minutes, and in 40 ℃ vacuum drying oven, placed baking in 24 hours then and remove residual solvent and non-solvent solvent.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 29]
With Kynoar (Kynar2851 type PVDF), unsaturated polyester (UP) (SMC level), dibenzoyl peroxide, diallyl phthalate, acetone, glycerol (glycerine) was by weight 2.5: 5: 0.1: 1: 80: 4 mixed, heating makes the Kynoar dissolving form the solution of transparent and homogeneous as casting solution, account for the nanophase silicon dioxide of PVDF weight 30% in adding, be coated in after mixing on the clean substrate of glass, room temperature was placed 25 minutes, places baking in 24 hours then and remove residual solvent and non-solvent solvent in 40 ℃ vacuum drying oven.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment one.[embodiment 30]
With Kynoar (Kynar2851 type PVDF), unsaturated polyester (UP) (SMC level), dibenzoyl peroxide, methyl methacrylate, acetone, glycerol (glycerine) was by weight 2.5: 5: 0.1: 1: 80: 4 mixed, heating makes the Kynoar dissolving form the solution of transparent and homogeneous as casting solution, account for the nanophase silicon dioxide of PVDF weight 30% in adding, be coated in after mixing on the clean substrate of glass, room temperature was placed 25 minutes, places baking in 24 hours then and remove residual solvent and non-solvent solvent in 40 ℃ vacuum drying oven.
The Integration Assembly And Checkout method of the preparation of anode and battery discharges and recharges data and lists in table 1 with embodiment 1.
Table .1
The embodiment numbering Reversible capacity (mAh/g) The cyclicity parameter First all efficient (%) Second all efficient (%)
????1 ????2 ????3 ????4 ????5 ????6 ????7 ????8 ????9 ????10 ????11 ????12 ????13 ????14 ????15 ????16 ????17 ????18 ????19 ????20 ????21 ????22 ????23 ????24 ????25 ????26 ????27 ????28 ????29 ????30 ????310 ????310 ????304 ????316 ????308 ????305 ????315 ????315 ????318 ????301 ????300 ????296 ????308 ????307 ????298 ????310 ????311 ????300 ????315 ????309 ????316 ????312 ????307 ????305 ????302 ????297 ????296 ????306 ????305 ????301 ????-0.10 ????-0.21 ????-0.19 ????-0.09 ????-0.11 ????-0.12 ????-0.21 ????-0.26 ????-0.16 ????-0.19 ????-0.21 ????-0.11 ????-0.18 ????-0.15 ????-0.15 ????-0.21 ????-0.14 ????-0.18 ????-0.14 ????-0.30 ????-0.27 ????-0.19 ????-0.12 ????-0.24 ????-0.15 ????-0.23 ????-0.28 ????-0.16 ????-0.31 ????-0.26 ????87.0 ????84.5 ????85.0 ????86.1 ????85.2 ????86.3 ????86.4 ????84.6 ????83.4 ????86.9 ????82.0 ????82.1 ????86.2 ????78.3 ????85.5 ????82.6 ????80.9 ????87.9 ????84.7 ????83.3 ????83.2 ????82.5 ????93.5 ????81.1 ????81.6 ????83.0 ????81.1 ????76.3 ????78.9 ????79.0 ????96 ????94 ????94 ????92 ????95 ????96 ????95 ????94 ????91 ????93 ????93 ????94 ????95 ????95 ????95 ????91 ????92 ????92 ????93 ????91 ????90 ????90 ????90 ????91 ????92 ????90 ????90 ????91 ????92 ????93

Claims (16)

1, a kind of micropore polymer diaphragm that is used for serondary lithium battery, it is characterized in that: the each component material that is used for preparing micropore polymer diaphragm comprises: (one) thermosetting resin: water insoluble and organic solvent electrolyte (comprises ethylene carbonate behind the curing cross-linked, propene carbonate, diethyl carbonate, dimethyl carbonate, gamma-butyrolacton, dimethyl-tetrahydrofuran) and have good chemical and electrochemical stability and a thermal stability, consumption accounts for the 20%-80% of barrier film weight, (2) initator: thermosetting resin uses during for unsaturated polyester (UP), consumption accounts for the 0.1%-5.0% of unsaturated polyester (UP) weight, (3) crosslinking agent: epoxy resin cross-linking agent (consumption accounts for the 1.0%-100.0% of weight epoxy) or unsaturated polyester cross-linking agent (consumption accounts for the 0.1%-5.0% of unsaturated polyester (UP) weight), (4) promoter: epoxy resin promoter (consumption accounts for the 0.01%-1.0% of weight epoxy) or unsaturated polyester (UP) promoter (consumption accounts for the 0.05%-1.0% of unsaturated polyester (UP) weight), (5) thermoplastic polymer: the organic solvent in the water insoluble and electrolyte (comprises ethylene carbonate, propene carbonate, diethyl carbonate, dimethyl carbonate, gamma-butyrolacton, dimethyl-tetrahydrofuran) and the fusing point with good chemical and electrochemical stability 60-140 ℃ polymeric film material, consumption accounts for the 20%-80% of barrier film weight, (6) solvent: the thermosetting resin of energy dissolve uncrosslinked, initator, crosslinking agent, promoter and thermoplastic polymer are (if thermoplastic polymer is powder or short fiber, also can be insoluble to solvent), (7) non-solvent: energy and solvent are miscible mutually, solvent boiling point needs lower more than 30 ℃ than non-solvent, (8) cosolvent: the thermosetting resin of energy dissolve uncrosslinked, initator, crosslinking agent, promoter and thermoplastic polymer are (if thermoplastic polymer is powder or short fiber, also can be insoluble to cosolvent), its low temperature is non-solvent, high temperature is solvent, only when hot method technology system film, adopt cosolvent, do not have other solvent and non-solvent in the solution system this moment, and (nine) nanophase oxide powder: addition accounts for the 10%-80% of polymer weight;
The basic structure of micropore polymer diaphragm is: crosslinked thermosetting resin constitutes support frame with continuous three-dimensional network, thermoplastic polymer (being dissolved in solvent) is scattered in the support frame with molecular level, form microporous barrier, nanophase oxide powder (can not add) is dispersed in thermosetting resin and the thermoplastic polymer.
2, by the described micropore polymer diaphragm that is used for serondary lithium battery of claim 1, it is characterized in that: the structure of barrier film can also be: crosslinked thermosetting resin constitutes support frame with continuous three-dimensional network, thermoplastic polymer (being insoluble to solvent) is with graininess (grain size 1 μ m-100 μ m) or fibrous (length is 0.1mm-1mm) is dispersed in the support frame or between the skeleton, nanophase oxide powder (can not add) is dispersed in the thermosetting resin.
3, by the described micropore polymer diaphragm that is used for serondary lithium battery of claim 1, it is characterized in that: the structure of barrier film can also be: two-layer thermosetting resin microporous barrier folder one deck thermoplastic polymer microporous barrier or one deck thermoplastic polymer microporous barrier and the film formed structure of composite membrane of one deck thermosetting resin micropore.
4, by the described micropore polymer diaphragm that is used for serondary lithium battery of claim 1, it is characterized in that: described thermosetting resin can be:
(1) epoxy resin: glycidol ether type, glycidyl ester type, glycidic amine type, cycloaliphatic epoxy resin, alicyclic glycidol ether type, alicyclic glycidyl ester type, aliphatic epoxy resin, spiral shell structural epoxy resins or novolac epoxy resin;
(2) unsaturated polyester (UP): cis-butenedioic anhydride type, acrylic type or propylene ester type;
(3) phenolic resins: ammonia catalysis phenolic aldehyde, barium phenolic aldehyde, boron phenolic aldehyde or modified phenolic;
(4) polyimide resin: alkynes end group polyimides, PMR type polyimides or bismaleimides type polyimides.
5; by the described micropore polymer diaphragm that is used for serondary lithium battery of claim 1; it is characterized in that: described initator can be: alkyl peroxide (comprising t-butyl hydrogen peroxide, cumene hydroperoxide hydrogen); dialkyl peroxide (comprising di-tert-butyl peroxide); peroxy acid (comprising Peracetic acid); diacyl peroxide (comprising dibenzoyl peroxide, acetyl peroxide); peroxy esters (comprising the special butyl ester of peroxidating formic acid), the peroxidating derivative mixture (comprising methyl ethyl ketone peroxide, cyclohexanone peroxide) after the ketone oxidation.
6, by the described micropore polymer diaphragm that is used for serondary lithium battery of claim 1, it is characterized in that: described crosslinking agent can be:
(1) epoxy resin cross-linking agent: Armeen (comprises polyethylene polyamine, diethylin is for propylamine), modified amine (comprises amine-resin, amine-glycerin ether addition product, amine-ethylene oxide adduct, the cyanoethylation product, mixed amine), alicyclic amine, tertiary amine (comprising trimethylamine and derivative thereof), tertiary ammonium salt, aromatic amine (comprises modified aromatic amine, unmodified aromatic amine), acid amides (comprising low molecular polyamides), latent curing agent (comprises boron trifluoride amine complex compound, borate), anhydrides (comprises phthalic anhydride, maleic anhydride, hexahydrophthalic anhydride, pyromellitic acid anhydride), imidazoles (comprising diethyl tetramethyl imidazoles);
(2) unsaturated polyester cross-linking agent: comprise styrene, methyl methacrylate, diallyl phthalate, vinyltoluene, cyanuric acid tripropylene.
7, by the described micropore polymer diaphragm that is used for serondary lithium battery of claim 1, it is characterized in that: described promoter can be:
(1) epoxy resin promoter: comprise bisphenol-A, phenol, resorcinol, nonyl phenol, 2,4,6-three (dimethylamino methyl) phenol, TGA, triphenyl phosphite ester, the boron trifluoride mono aminoethane, fatty amine, benzyl dimethylamine, dimethylaniline, pyridine, 2-ethyl-4-methylimidazole, triethanolamine borate;
(2) unsaturated polyester (UP) promoter: metallic compound (comprising cobalt naphthenate, cobalt octoate, manganese promoter, copper promoter, vanadium promoter), tertiary amines (comprising dimethylaniline, diethylaniline, dimethyl-p-toluidine), 2,4-pentanedione.
8, by the described micropore polymer diaphragm that is used for serondary lithium battery of claim 1, it is characterized in that: described thermoplastic polymer can be: Kynoar (PVDF) and copolymer (Copolymer) thereof, gather (6-caprolactone) (PCL), poly 1 butene, poly--1 amylene, random polystyrene, copolymerized methanal, ethylene-vinyl acetate copolymer (EVA), polybutyl methacrylate (PBMA), styrene-butadiene block copolymer (SBS), the polyacrylic acid allyl ester, cellulose acetate (CA) gathers 1,4-butadiene (PB), poly-ethanedioic acid propylene diester, polyethylene succinate, polydecamethylene adipamide (NYLON610), poly-decanedioyl o-phenylenediamine, the poly dimethyl propylene, poly-valeral.
9, by the described micropore polymer diaphragm that is used for serondary lithium battery of claim 1, it is characterized in that: described solvent can be: acetone, N, dinethylformamide, N, N-dimethylacetylamide, triethyl phosphate, oxolane, N-methyl pyrrolidone, dimethyl sulfoxide (DMSO), benzene, toluene, dimethylbenzene, chlorobenzene, carrene, chloroform, carbon tetrachloride, methyl alcohol, ethanol, propyl alcohol, isobutanol, 1-butanols, n-hexane, cyclohexane, pentane, trichloroethylene, o-dichlorohenzene, methyl formate, ethyl acetate, hexafluoroisopropanol, dioxane, dioxolanes, sulfolane, cyclohexanone, N-dihydroxy ethyl ox ester amine, formic acid, dioctyl phthalate, tetrachloroethanes, methylethylketone, o-chlorphenol, trifluoroethanol, N-methyl caprolactam, HMPA, tetramethylurea, 1-amylalcohol, sec-n-octyl alcohol, cyclohexanol, phenmethylol, ether, ethylene glycol monoethyl ether, furfural, diethylenetriamine, pyridine, dichloroethanes.
10, by the described micropore polymer diaphragm that is used for serondary lithium battery of claim 1, it is characterized in that: described non-solvent can be: methyl alcohol, ethanol, propyl alcohol, isobutanol, 1-butanols, glycerol, ethylene glycol, cyclobutanol, cyclohexanol, formamide, water, trifluoroethanol, methyl-sulfoxide, hexafluoroisopropanol, N-dihydroxy ethyl ox ester amine, dichloro-benzenes, trans stilbenes.
11, by the described micropore polymer diaphragm that is used for serondary lithium battery of claim 1, it is characterized in that: described cosolvent can be saturated long-chain alcohol, 1, and 4-butanediol, laurate.
12, by the described micropore polymer diaphragm that is used for serondary lithium battery of claim 1, it is characterized in that: described nanophase oxide powder can be: nano silicon, nano aluminium oxide.
13, a kind of described micropore polymer diaphragm that is used for serondary lithium battery of claim 1 for preparing is characterized in that: may further comprise the steps:
(1) with thermosetting resin, can be dissolved in the low melting point thermoplastic polymer (also can be that the particle diameter that is insoluble to solvent is that powder or the length of 1-100um is the fiber of 0.1-1mm) of solvent, (thermosetting resin adds during for unsaturated polyester (UP) initator, consumption accounts for the 0.1%-5.0% of unsaturated polyester (UP) weight, can not add) yet, (thermosetting resin adds when being unsaturated polyester (UP) or epoxy resin crosslinking agent, unsaturated polyester cross-linking agent consumption accounts for the 0.1%-5.0% of unsaturated polyester (UP) weight, epoxy resin cross-linking agent accounts for the 1.0%-100.0% of weight epoxy, can not add) yet, (the epoxy resin accelerator dosage accounts for the 0.01%-1.0% of weight epoxy to promoter, the 0.05%-1.0% that unsaturated polyester (UP) promoter accounts for unsaturated polyester (UP) can not add yet), the nanophase oxide powder (can not add yet, account for the 10%-80% of polymer weight), solvent and non-solvent mix the casting solution that (can heat) forms homogeneous, thermosetting resin weight accounts for 5%-50% in the casting solution, thermoplastic polymer accounts for 5%-50%, solvent accounts for 50%-80%, and non-solvent accounts for 5%-25%;
(2) at normal temperatures and pressures casting solution is coated on clean glass, plastics or the metallic substrates by roller coat or blade coating (scraper gap 0.10mm-1.00mm);
(3) adopt dry process to prepare barrier film, regulate heating-up temperature and time control solvent evaporates speed, temperature range is the boiling point that room temperature arrives non-solvent, lose viscosity up to casting solution, then barrier film is placed on 12h-24h in the vacuum drying oven that is lower than the thermoplastic polymer softening point temperature, can obtain pore size is that 5um-50um, porosity are 30%-80%, the barrier film of thickness 10um-50um.
14, by the described method that is used for the micropore polymer diaphragm of serondary lithium battery of the described preparation of claim 13 claim 1, it is characterized in that: step (3) can also be adopted hot method technology, use cosolvent replace solvents and non-solvent, cosolvent accounts for the 5%-90% of casting solution weight.
15, by the described method that is used for the micropore polymer diaphragm of serondary lithium battery of the described preparation of claim 13 claim 1, it is characterized in that: can also adopt wet processing to prepare barrier film step (3), be coated in suprabasil casting solution and in the temperature range of the boiling point from the room temperature to the non-solvent, vapor away partial solvent, keep casting solution viscosity greater than 10 handkerchief seconds, be immersed in the non-solvent bath that contains a small amount of solvent (solvent accounts for the 0%-50% of non-solvent weight), non-solvent bath temperature scope is 0 ℃ of boiling point to solvent.
16, by the described method that is used for the micropore polymer diaphragm of serondary lithium battery of the described preparation of claim 13 claim 1, it is characterized in that: can also according to said method prepare the composite microporous polymer barrier film: (1) is dissolved in the casting solution that forms homogeneous in the mixed liquor of its solvent and non-solvent or the cosolvent (in hot method technology) according to the above ratio with thermoplastic polymer and nanophase oxide powder (also can not adding), by above-mentioned dry method, wet method or hot method technology make thickness 5um-20um, pore size is that 5um-50um, porosity are the support membrane of 30%-80%; (2) with thermosetting resin, nanophase oxide powder (also can not adding), initator (thermosetting resin for unsaturated polyester (UP) time add), (thermosetting resin adds when being unsaturated polyester (UP) and epoxy resin crosslinking agent, can not add yet) and promoter (also can not adding) be dissolved in the casting solution that forms homogeneous in the mixed liquor of its solvent and non-solvent according to the above ratio, be coated in the single face or the two sides of support membrane, by dry process make thickness 10um-50um, pore size is that 5-50um, porosity are 30%-80% composite microporous polymer film.
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