CN1142602C - Microporous polymer diaphragm for secondary lithium cell and its preparation method - Google Patents
Microporous polymer diaphragm for secondary lithium cell and its preparation method Download PDFInfo
- Publication number
- CN1142602C CN1142602C CNB001072439A CN00107243A CN1142602C CN 1142602 C CN1142602 C CN 1142602C CN B001072439 A CNB001072439 A CN B001072439A CN 00107243 A CN00107243 A CN 00107243A CN 1142602 C CN1142602 C CN 1142602C
- Authority
- CN
- China
- Prior art keywords
- solvent
- thermosetting resin
- thermoplastic polymer
- crosslinking agent
- nanophase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
Abstract
The present invention belongs to the technical field for manufacturing a high energy battery of a secondary lithium battery at a room temperature. In the present invention, a thermosetting resin, an evocating agent, an accelerating agent, a cross linking agent, etc., and a thermoplastic polymer are jointly dissolved in the mixed liquor of a solvent and a nonsolvent so as to form a homogeneous solution or a suspension, a dry method, a wet method or a thermal method paraphase process is utilized, a microporous polymer membrane is obtained by controlling temperatures, time, etc. The membrane of the present invention has the advantages of simple preparation process, low cost, high factor of porosity, controllable aperture size, high liquid absorption amount, strong surface adhesion and higher mechanical strength, the present invention is favorable for manufacturing the secondary lithium battery with high safety and long cyclic life, and the battery is suitable for charging and discharging with heavy current. The membrane can be also used as a separation membrane and a supporting membrane.
Description
Technical field
The invention belongs to the high-energy battery field, particularly make the high-energy battery technical field of room temperature serondary lithium battery.
Technical background
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, 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.Pass through telomerized polymer, solvent, non-solvent, proportioning between the cosolvent, 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.Journalof?Membrane?Science.No.117，117(1996)[5]M.Tomaszewska.Preparation?and?Properties?Of?Plat-SheetMembranes?From?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.UnitedStates?Patent.1995，5387378[7]J.P.Puglia?and?D.F.Mckinley.Self?Supporting?Hollow?FiberMembrane?and?Method?of?Construction.Patent?CooperationTreaty.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 should not be directly used in the manufacturing of serondary lithium battery.
Summary of the invention
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, 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 to reach surface adhesive by force good for barrier film plasticity, can form good bondingly with anodal, cathode pole piece, 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 helps 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 invention provides a kind of micropore polymer diaphragm that is used for serondary lithium battery, it is characterized in that, this barrier film comprises thermosetting resin and thermoplastic polymer;
Described thermosetting resin is epoxy resin or unsaturated polyester (UP);
Described thermoplastic polymer is a Kynoar;
The weight ratio of thermosetting resin and thermoplastic polymer is 8-10: 10;
The structure of this micropore polymer diaphragm is: crosslinked thermosetting resin constitutes support frame with continuous three-dimensional network, and thermoplastic polymer is scattered in the support frame with molecular level by dissolving in solvent, forms microporous barrier.
The invention provides a kind of aforesaid micropore polymer diaphragm that is used for serondary lithium battery, it is characterized in that this barrier film also comprises the nanophase oxide powder;
Described nanophase oxide powder is a nanophase silicon dioxide;
The weight ratio of thermosetting resin, thermoplastic polymer and nanophase oxide powder is 8-10: 10: 1.5-3;
The structure of this micropore polymer diaphragm is: crosslinked thermosetting resin constitutes support frame with continuous three-dimensional network, thermoplastic polymer is by dissolving in solvent, be scattered in the support frame with molecular level, form microporous barrier, the nanophase oxide powder is dispersed in thermosetting resin and the thermoplastic polymer.
The invention provides a kind of described preparation method who is used for the micropore polymer diaphragm of serondary lithium battery, comprise following step:
(1) thermosetting resin, thermoplastic polymer, crosslinking agent or crosslinking agent and initator and solvent and non-solvent are mixed uniform solution that the back forms as casting solution;
(2) at normal temperatures and pressures casting solution is coated on clean glass, plastics or the metallic substrates;
(3) by conventional dry method, wet method or hot method technology, solvent and non-solvent are removed, made barrier film;
Described thermosetting resin is epoxy resin or unsaturated polyester (UP);
Described thermoplastic polymer is a Kynoar;
Described solvent is an acetone;
Described non-solvent is a glycerol;
When described thermosetting resin was epoxy resin, crosslinking agent was an epoxy resin cross-linking agent, and it comprises N, N-dimethyl benzylamine, dicyandiamide, polyethylene polyamine, adjacent hydroxybenzyl dimethylamine, m-xylene diamine; The weight part ratio of each component is a thermosetting resin: thermoplastic polymer: crosslinking agent: solvent: non-solvent=8: 10: 0.5-1.2: 160: 7;
When described thermosetting resin was unsaturated polyester (UP), crosslinking agent was the unsaturated polyester cross-linking agent, and it comprises methyl methacrylate, diallyl phthalate; Initator is a dibenzoyl peroxide; The weight part ratio of each component is a thermosetting resin: thermoplastic polymer: initator: crosslinking agent: solvent: non-solvent=5: 5: 0.1: 1: 80: 4.
The invention provides the another kind of described preparation method who is used for the micropore polymer diaphragm of serondary lithium battery, comprise following step:
(1) thermosetting resin, thermoplastic polymer, nanophase oxide powder, crosslinking agent or crosslinking agent and initator and solvent and non-solvent are mixed uniform solution that the back forms as casting solution;
(2) at normal temperatures and pressures casting solution is coated on clean glass, plastics or the metallic substrates;
(3) by conventional dry method, wet method or hot method technology, solvent and non-solvent are removed, made barrier film;
Described thermosetting resin is epoxy resin or unsaturated polyester (UP);
Described thermoplastic polymer is a Kynoar;
Described nanophase oxide powder is a nanophase silicon dioxide;
Described solvent is an acetone;
Described non-solvent is a glycerol;
When described thermosetting resin was epoxy resin, crosslinking agent was an epoxy resin cross-linking agent, and it comprises N, N-dimethyl benzylamine, dicyandiamide, polyethylene polyamine, adjacent hydroxybenzyl dimethylamine, m-xylene diamine; The weight part ratio of each component is a thermosetting resin: thermoplastic polymer: crosslinking agent: solvent: non-solvent: nanophase oxide powder=8: 10: 0.5-1.2: 160: 7: 3;
When described thermosetting resin was unsaturated polyester (UP), crosslinking agent was the unsaturated polyester cross-linking agent, and it comprises methyl methacrylate, diallyl phthalate; Initator is a dibenzoyl peroxide; The weight part ratio of each component is a thermosetting resin: thermoplastic polymer: initator: crosslinking agent: solvent: non-solvent: nanophase oxide powder=2.5-5: 5: 0.1: 1: 80: 4: 0.75-1.5.
The invention has the advantages that: manufacturing process 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.
Description of drawings
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
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: 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, 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 embodiment numbers reversible capacity cyclicity parameter first all efficient second all efficient
(mAh/g) (％) (％)1 310 -0.10 87.0 962 310 -0.21 84.5 943 304 -0.19 85.0 944 316 -0.09 86.1 925 308 -0.11 85.2 956 305 -0.12 86.3 967 315 -0.21 86.4 958 315 -0.26 84.6 949 318 -0.16 83.4 9110 301 -0.19 86.9 9311 300 -0.21 82.0 9312 296 -0.11 82.1 9413 308 -0.18 86.2 9514 307 -0.15 78.3 9515 298 -0.15 85.5 9516 310 -0.21 82.6 9117 311 -0.14 80.9 9218 300 -0.18 87.9 9219 315 -0.14 84.7 9320 309 -0.30 83.3 9121 316 -0.27 83.2 9022 312 -0.19 82.5 9023 307 -0.12 93.5 9024 305 -0.24 81.1 9125 302 -0.15 81.6 9226 297 -0.23 83.0 9027 296 -0.28 81.1 9028 306 -0.16 76.3 9129 305 -0.31 78.9 9230 301 -0.26 79.0 93
Claims (4)
1, a kind of micropore polymer diaphragm that is used for serondary lithium battery is characterized in that, this barrier film comprises thermosetting resin and thermoplastic polymer;
Described thermosetting resin is epoxy resin or unsaturated polyester (UP);
Described thermoplastic polymer is a Kynoar;
The weight ratio of thermosetting resin and thermoplastic polymer is 8-10: 10;
The structure of this micropore polymer diaphragm is: crosslinked thermosetting resin constitutes support frame with continuous three-dimensional network, and thermoplastic polymer is scattered in the support frame with molecular level by dissolving in solvent, forms microporous barrier.
2, the micropore polymer diaphragm that is used for serondary lithium battery as claimed in claim 1 is characterized in that, this barrier film also comprises the nanophase oxide powder;
Described nanophase oxide powder is a nanophase silicon dioxide;
The weight ratio of thermosetting resin, thermoplastic polymer and nanophase oxide powder is 8-10: 10: 1.5-3;
The structure of this micropore polymer diaphragm is: crosslinked thermosetting resin constitutes support frame with continuous three-dimensional network, thermoplastic polymer is by dissolving in solvent, be scattered in the support frame with molecular level, form microporous barrier, the nanophase oxide powder is dispersed in thermosetting resin and the thermoplastic polymer.
3, a kind of preparation method who is used for the micropore polymer diaphragm of serondary lithium battery as claimed in claim 1 comprises following step:
(1) thermosetting resin, thermoplastic polymer, crosslinking agent or crosslinking agent and initator and solvent and non-solvent are mixed uniform solution that the back forms as casting solution;
(2) at normal temperatures and pressures casting solution is coated on clean glass, plastics or the metallic substrates;
(3) by conventional dry method, wet method or hot method technology, solvent and non-solvent are removed, made barrier film;
Described thermosetting resin is epoxy resin or unsaturated polyester (UP);
Described thermoplastic polymer is a Kynoar;
Described solvent is an acetone;
Described non-solvent is a glycerol;
When described thermosetting resin was epoxy resin, crosslinking agent was an epoxy resin cross-linking agent, and it comprises N, N-dimethyl benzylamine, dicyandiamide, polyethylene polyamine, adjacent hydroxybenzyl dimethylamine, m-xylene diamine; The weight part ratio of each component is a thermosetting resin: thermoplastic polymer: crosslinking agent: solvent: non-solvent=8: 10: 0.5-1.2: 160: 7;
When described thermosetting resin was unsaturated polyester (UP), crosslinking agent was the unsaturated polyester cross-linking agent, and it comprises methyl methacrylate, diallyl phthalate; Initator is a dibenzoyl peroxide; The weight part ratio of each component is a thermosetting resin: thermoplastic polymer: initator: crosslinking agent: solvent: non-solvent=5: 5: 0.1: 1: 80: 4.
4, a kind of preparation method who is used for the micropore polymer diaphragm of serondary lithium battery as claimed in claim 2 comprises following step:
(1) thermosetting resin, thermoplastic polymer, nanophase oxide powder, crosslinking agent or crosslinking agent and initator and solvent and non-solvent are mixed uniform solution that the back forms as casting solution;
(2) at normal temperatures and pressures casting solution is coated on clean glass, plastics or the metallic substrates;
(3) by conventional dry method, wet method or hot method technology, solvent and non-solvent are removed, made barrier film;
Described thermosetting resin is epoxy resin or unsaturated polyester (UP);
Described thermoplastic polymer is a Kynoar;
Described nanophase oxide powder is a nanophase silicon dioxide;
Described solvent is an acetone;
Described non-solvent is a glycerol;
When described thermosetting resin was epoxy resin, crosslinking agent was an epoxy resin cross-linking agent, and it comprises N, N-dimethyl benzylamine, dicyandiamide, polyethylene polyamine, adjacent hydroxybenzyl dimethylamine, m-xylene diamine; The weight part ratio of each component is a thermosetting resin: thermoplastic polymer: crosslinking agent: solvent: non-solvent: nanophase oxide powder=8: 10: 0.5-1.2: 160: 7: 3;
When described thermosetting resin was unsaturated polyester (UP), crosslinking agent was the unsaturated polyester cross-linking agent, and it comprises methyl methacrylate, diallyl phthalate; Initator is a dibenzoyl peroxide; The weight part ratio of each component is a thermosetting resin: thermoplastic polymer: initator: crosslinking agent: solvent: non-solvent: nanophase oxide powder=2.5-5: 5: 0.1: 1: 80: 4: 0.75-1.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001072439A CN1142602C (en) | 2000-04-29 | 2000-04-29 | Microporous polymer diaphragm for secondary lithium cell and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001072439A CN1142602C (en) | 2000-04-29 | 2000-04-29 | Microporous polymer diaphragm for secondary lithium cell and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1322019A CN1322019A (en) | 2001-11-14 |
| CN1142602C true CN1142602C (en) | 2004-03-17 |
Family
ID=4578568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001072439A Expired - Fee Related CN1142602C (en) | 2000-04-29 | 2000-04-29 | Microporous polymer diaphragm for secondary lithium cell and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1142602C (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4549621B2 (en) * | 2002-12-02 | 2010-09-22 | 日東電工株式会社 | Crosslinkable polymer-supported porous film for battery separator and battery manufacturing method using the same |
| CN100388532C (en) * | 2005-09-28 | 2008-05-14 | 浙江工业大学 | Diaphragn additive for lithium secondary cell and lithium secondary cell diaphragm |
| CN101150182B (en) * | 2006-09-18 | 2011-12-07 | 深圳市比克电池有限公司 | Lithium ion battery electrode slice, electric core and its making method |
| JP5320464B2 (en) * | 2008-11-17 | 2013-10-23 | 東レバッテリーセパレータフィルム株式会社 | Microporous membranes and methods for making and using such membranes |
| JP5624117B2 (en) * | 2009-03-30 | 2014-11-12 | 東レバッテリーセパレータフィルム株式会社 | Microporous polymer membrane, battery separator, and production method thereof |
| JP5934580B2 (en) * | 2011-06-13 | 2016-06-15 | 日東電工株式会社 | Epoxy resin porous membrane, separator for nonaqueous electrolyte electricity storage device, nonaqueous electrolyte electricity storage device, composite semipermeable membrane, and production method thereof |
| JP4940367B1 (en) * | 2011-06-13 | 2012-05-30 | 日東電工株式会社 | Separator for nonaqueous electrolyte electricity storage device, nonaqueous electrolyte electricity storage device, and production method thereof |
| JP2013020947A (en) * | 2011-06-13 | 2013-01-31 | Nitto Denko Corp | Separator for nonaqueous electrolyte power storage device, nonaqueous electrolyte power storage device, and manufacturing methods thereof |
| CN103030852B (en) * | 2011-09-29 | 2015-02-25 | 陈光炎 | Polymer microporous membrane and its preparation method |
| EP2741356B1 (en) | 2012-08-28 | 2018-10-03 | LG Chem, Ltd. | Lithium ion secondary battery preventing internal short |
| CN103682462B (en) * | 2013-12-31 | 2015-11-18 | 深圳市格瑞普电池有限公司 | Pour into integrated Li-ion batteries piles and preparation method |
| CN104393217B (en) * | 2014-10-20 | 2017-07-07 | 郑少华 | A kind of overlapped coating composite lithium ion battery separator and preparation method thereof |
| CN105017546B (en) * | 2015-06-09 | 2017-08-08 | 界首市天鸿新材料股份有限公司 | A kind of dry method is double to draw lithium battery diaphragm production technology |
| CN105140451A (en) * | 2015-07-06 | 2015-12-09 | 佛山荷韵特种材料有限公司 | Lithium-ion battery diaphragm and preparation method thereof |
| CN105968696B (en) * | 2016-05-26 | 2018-05-11 | 江苏深苏电子科技有限公司 | A kind of preparation method of electrolytic membrane of lithium-ion battery |
| CN107516724A (en) * | 2016-06-16 | 2017-12-26 | 宁德新能源科技有限公司 | Battery core and energy storage device |
| CN108299772B (en) * | 2018-03-22 | 2020-12-08 | 南京君弘塑业有限公司 | Polyvinylidene fluoride film and preparation method thereof |
| CN110041660A (en) * | 2019-04-11 | 2019-07-23 | 桑顿新能源科技有限公司 | A kind of high-temperature self-crosslinking thermosetting property diaphragm and preparation method thereof |
| CN110028640B (en) * | 2019-04-23 | 2021-08-06 | 湘潭大学 | Porous polymer based on triphenyl imidazole-phloroglucinol, preparation method and application thereof |
| CN110028209B (en) * | 2019-05-30 | 2021-09-21 | 安徽欣创节能环保科技股份有限公司 | Application of MBR (membrane bioreactor) process in domestic sewage treatment |
| CN110229333B (en) * | 2019-06-25 | 2022-02-15 | 湘潭大学 | Synthetic method of polyimide |
| CN111403667B (en) * | 2020-04-13 | 2022-12-30 | 上海极紫科技有限公司 | Composition of high-temperature-resistant lithium battery diaphragm and preparation method thereof |
| CN113782911A (en) * | 2021-09-03 | 2021-12-10 | 北京阳光鸿志电气工程技术有限公司 | Modified diaphragm and solid vanadium battery assembled by same |
-
2000
- 2000-04-29 CN CNB001072439A patent/CN1142602C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1322019A (en) | 2001-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1142602C (en) | Microporous polymer diaphragm for secondary lithium cell and its preparation method | |
| CN1258234C (en) | Multi-component composite film method for preparing the same | |
| CN1918727A (en) | Organic/inorganic composite porous layer-coated electrode and electrochemical device comprising the same | |
| CN1185739C (en) | Solid polymer alloy electrolyte in homogeneous state and manufacturing method therefor, and composite electrode, lithium polymer battery and lithium ion polymer battery | |
| CN1167164C (en) | Microporous solid electrolytes and methods for preparing them | |
| CN1208867C (en) | Nonaqueous electrolyte cell | |
| CN104124427B (en) | Electrode, electrochemical device comprising electrode, and manufacture method of electrode | |
| CN1238915C (en) | Lithium ion secondary battery | |
| CN1139622C (en) | Porous composite product particularly with high specific surface area, method for preparing and electrode for electrochemical assembly formed with porous composite film | |
| CN1217432C (en) | Diaphragm for anhydrous dielectric secondary cell and the anhydrous dielectric secondary cell | |
| CN1274036C (en) | Electrochemical battery using multicomponent composite membrane | |
| CN1151577C (en) | Secondary lithium battery | |
| CN1142603C (en) | Microporous polymer diaphragm with high-temperature self-closing mechanism and its preparation method | |
| CN1767948A (en) | Polyolefin microporous membrane | |
| CN1670989A (en) | Electronic component separator and method for producing the same | |
| CN1969407A (en) | New organic/inorganic composite porous film and electrochemical device prepared thereby | |
| CN1870326A (en) | Non-aqueous solution electrochemical device polar plate and its manufacturing method | |
| CN101031421A (en) | Polyolefin microporous membrane | |
| CN1661829A (en) | Separator for electronic component and method for producing the same | |
| CN1608331A (en) | Gas diffusion backing for fuel cells | |
| CN1867622A (en) | Microporous PVDF films and method of manufacturing | |
| CN1882436A (en) | Composite microporous film, and production method and use thereof | |
| CN1639887A (en) | Electric separator, method for the production and use thereof | |
| CN1285084A (en) | Separators for electrochemical cells | |
| CN1479392A (en) | Composite polymer diaphram used for secondary lithium battery and its preparation technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |