CN1349263A - Porous polymer isolation element used for lithium ion laminated accumulator - Google Patents
Porous polymer isolation element used for lithium ion laminated accumulator Download PDFInfo
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- CN1349263A CN1349263A CN01124914A CN01124914A CN1349263A CN 1349263 A CN1349263 A CN 1349263A CN 01124914 A CN01124914 A CN 01124914A CN 01124914 A CN01124914 A CN 01124914A CN 1349263 A CN1349263 A CN 1349263A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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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
- 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
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
A mesoporous polymeric membrane for use as an ionically-conductive inter-electrode separator in a rechargeable battery cell is prepared from a coatable composition comprising a polymeric material, a volatile fluid solvers for the polymeric material, and a second fluid miscible with and of lesser volatility than the solvent, the-second fluid being a nonsolvent exhibiting no significant solvency for the polymeric material. A layer is cast from the composition to form a layer which is gelled and solidified to a self-supporting membrane by volatilizing the solvent and nonsolvent coating vehicle fluids under conditions in which the solvent volatilizes at a rate substantially faster than that of the nonsolvent. As a result the polymeric material initially gells in the more nonsolvent-predominant regions of the layer and isolates the nonsolvent as droplets substantially uniformly distributed throughout a matrix of polymeric material. The nonsolvent is subsequently volatilized from the droplets to yield a like distribution of mesopore voids throughout said membrane matrix. The porous membrane is capable of absorbing significant amounts of electrolyte solution to provide suitable ionic conductivity for use in rechargeable battery cells.
Description
The background of invention
The present invention relates to rechargeable electrolyte battery, it comprises the electrode member and the isolated component of polymer thin membrane component, and the current-collector of metal forming or silk screen, and these parts are overlapped into whole accumulator structure usually under heat and pressure effect.Specifically, the invention provides a kind of simple and economic method and prepare this isolated component film (being barrier film), this barrier film is a porous, even if therefore after the superimposed processing of high temperature, also can adsorb and keep a large amount of electrolyte, thereby in wide long term storage of temperature range rechargeable battery and use, it still can have high ionic conductivity and charge and discharge cycles stability.
Be fit to electrolyte battery of the present invention and comprise United States Patent (USP) 5,460, the lithium ion of 904 described types is inlayed battery, and as United States Patent (USP) 5,418,091 is described, and it preferably includes isolated component, and these patent references are incorporated into this.This battery is to be made by independent positive pole and negative pole element, and described positive pole and negative pole element comprise that respectively the active material that is dispersed in the segmentation in the polymer substrate is (as lithium source substance LiMn
2O
4And carbon), form flexible layers (being electrode film).On the superimposed electric insulation diaphragm of between being placed in one, usually making by the same polymer material of these electrode members.Described barrier film finally contains equally distributed lithium salts organic solution, the effect of this solution be in the charging and discharging of accumulator cyclic process as the ion guide electric bridge electrolyte between the electrode, and the lithium ion of inlaying reversibly flowed into and flow out these electrode active materials.At last, can flow in order to make the electron stream that produces in the battery circuit thereupon, each positive pole and negative pole element have corresponding current collector element.This current collector element is connected with the conductor of guiding the storage battery operative installations into also as electrode terminal during use.
In the manufacturing of those above-mentioned storage batterys and using, used the diaphragm element composition that contains with the plasticizer compounds of polymer-compatible, adding electrolyte when making it to have activity, these compounds of part can be separated out from final battery isolated component.When the unique distinction of these polymer isolated component compositions (and similar polymer electrode composition) is to separate out the compatible plasticizer of (usually by the solvent extraction to the polymer inertia) blending, can in polymer substrate, not produce hole, but this matrix is carried out preliminary treatment so that adsorption activity electrolyte.
On the other hand, United States Patent (USP) 3,351,495 have described existing polymer storage battery isolated component relies on matrix pores to promote the absorption of electrolyte.But the preparation of this isolated component is to rely on a similar solvent extraction to operate the inert filler particle of removing inconsistent what is called " plasticizer " component and be mingled with from cured compositions to obtain final hole.
Battery diaphragm element of the present invention has certain middle cell size, can produce the electrolyte absorption property that improves thereby form high ionic conductivity, and its preparation need not expensive extracting operation consuming time.On the contrary, the preparation of cell device of the present invention only simple barrier film coating of need be the curtain coating step, its later differential evaporation formation hole preferably by each component of coating composition fluid carrier.
The general introduction of invention
The invention provides the preparation method of a kind of porous polymer hypothallus (being film), inlay at the lithium ion of lamination that this film all can be well as isolator and electrode member in the storage battery.This film can be made by polymer composition by a simple coating or the operation of film curtain coating, described composition comprises polymer is solvent and is not the mixture of the coating vehicles component of solvent (hereinafter referred to as non-solvent) to polymer, in basic solvent evaporation operating process, because both different evaporation rates, thereby the low volatility non-solvent is dispersed in the whole cured polymer hypothallus well.After evaporation is removed solvent composition and is made the polymer substrate gelling or solidify, final evaporation and this non-solvent component of diffusion form the matrix structure of mesopore from polymer substrate, this structure is Electolyte-absorptive easily, forms high ionic conductivity in storage battery.
Except matrix polymer and coating vehicles mixture, coating composition preferably also comprises the inert filler (as silicon dioxide) of segmentation.This particle is evenly dispersed in the coating at first, but in matrix membrane gelatinization, these particles can obviously partly move, and is condensed into the aggregate in the non-solvent carrier drop that disperses.Therefore equally distributed filler particles not only provides structural strength to final layer, and after the diffusion of non-solvent carrier, provide support, the open-celled structure that is kept mesopore, and under the compression force of the thermal polymerization operation that isolated component and electrode member is overlapped into whole accumulator structure, further enlarge this additional support subsequently.
Except the mixture of matrix polymer and solvent/non-solvent, the electrode compound composition also comprises electrolysis active component separately, as powder carbon and embedding compound (as LiMn
2O
4Spinelle).Although these active components are dispersed in the coating composition with finely divided state, they can obviously not disturb the formation of mesopore, because its particle diameter is normally greater than the order of magnitude of mesopore pore-size.
After the isolated component and electrode member that form mesopore, basically as described in the above-mentioned patent specification, with the current-collector thermal polymerization of each electrode member and woven wire or metal forming together, in the middle of these electrode assemblies, insert isolated component subsequently, it is superimposed together.The preparation work of finishing battery also comprises with conventional method and adds electrolyte and make the mesopore barrier film absorb this electrolyte activating, and final packaging it.
The accompanying drawing summary
The present invention is described below with reference to accompanying drawings:
Fig. 1 is the schematic diagram that has the compound storage battery of lithium ion of isolated component of the present invention and electrode film element;
Fig. 2 is the profile of one section barrier film of the present invention, shows the relative deployment conditions of membrane polymer gelling early stage non-solvent carrier drop and inert filler particle;
Fig. 3 is the profile of one section barrier film of the present invention, shows the relative deployment conditions of membrane polymer gelling final stage non-solvent carrier drop and inert filler particle;
Fig. 4 is the profile of one section barrier film of the present invention, shows that membrane polymer is subjected to after lamination temperature and the pressure effect, replaces the mesopore hole of non-solvent carrier drop and the relative deployment conditions of inert filler particle;
Fig. 5 is the electrolyte absorption comparison diagram of the same polymer barrier film sample that makes of the inventive method and existing method;
Fig. 6 is the electrolyte absorption comparison diagram of the mesopore barrier film that makes with different component and stand medium and high lamination temperature.
The description of invention
The present invention comprises mainly and is used to prepare the porous polymer isolated component that the rechargeable electrolyte battery uses and the preparation method of electrode member that it need not solvent extraction operation expensive and consuming time.The present invention also comprises the isolated component and the electrode member of formation, and the rechargeable battery that makes by the thermal polymerization assembling of this isolated component and electrode member and conductivity current collection element.The method step that this assembly and being used to prepares storage battery is described in United States Patent (USP) 5,470 mostly, 357,5,540,741 and relevant patent disclosure in.
The representative accumulator cell assembly 10 that a kind of the present invention makes as shown in Figure 1, it comprises cathode film element 13, negative electrode film element 17, places two isolated components 15 between the electrode, wherein will finally adsorb lithium salt electrolyte.Electrode 13 and 17 comprise respectively contain lithium compound (as LiMn
2O
4) and can reversibly inlay the other material (as the carbon of petroleum coke or graphite-like) of lithium ion.The current-collector 11,19 (being preferably aluminium and copper or nickel) of conductivity preferably earlier by preliminary superimposed operation attached on each electrode member 13,17, become electrode assemblie, be close to isolated component 15 then therebetween,, form whole battery 10 in conjunction with (for example by thermal polymerization) these assemblies.For ease of the processing subsequently of battery, especially, have one in the current collector element at least for adding electrolyte, better two all have permeability, for example are the paper tinsel of perforation or the form that the woven wire of mesh is arranged.
Although the polymeric material that is used to prepare isolated component of the present invention and electrode member can be selected from the polymer or the copolymer of various previous uses, for example vinyl chloride, acrylonitrile, vinyl acetate, PVF, vinylidene chloride and vinylidene fluoride; And acrylonitrile and vinyl chloride or vinylidene chloride, vinylidene fluoride and tetrafluoroethene, trifluoro-ethylene, chlorotrifluoroethylene or hexafluoropropylene, but be more preferably the copolymer of about 75-97 weight % vinylidene fluoride (VDF) and 3-25 weight % hexafluoropropylene (HFP).The preparation of VDF monomer is generally different with the difference of its molecular weight.
Polymer composition also can comprise an amount of compatible organic plasticizer, as dibutyl phthalate, this is in order to obtain best flexible and thermal viscosity in lamination process, although this prescription and processing to isolated component of the present invention and electrode member is not very crucial.Anodal and cathode composition generally also all comprises the electrolysis active component that is generally finely divided state, and this material is the main material that can provide and inlay lithium ion in final battery charging and discharging circulation.
The main difference of the inventive method and existing battery preparation method is to be used for the preparation of the coating composition of curtain coating isolated component and electrolytic element, barrier film.Although existing method need be prepared matrix polymer and coating vehicles solvent (if necessary, add plasticizer) uniform coating liquid, but the coating composition that the present invention uses is except basic polymer solvent (for example acetone or oxolane), also comprise the lower liquid coating carrier component (as lower alcohol) of volatility, it is the non-solvent of polymer basically, but to a great extent can be miscible with basic solvent.This mixed dissolution matter coating vehicles can initial curtain coating go out the transparent and uniform layer of polymer solution, but remove and make in the coating after the non-solvent enrichment in a large amount of evaporations of basic solvent, local gelling or coalescent takes place in polymer in coating, surrounds the small droplet of countless non-solvent component.The low volatility of non-solvent is being kept its uniform droplet distribution always, removes up to this non-solvent evaporation subsequently, and polymer film is able to abundant gelling and obtains central hole structure.
In a preferred embodiment of the invention, coating composition comprises a large amount of inert particle filler (as silicon dioxide or aluminium oxide), and originally these fillers are evenly distributed in the whole cast layer body.As the filler of prior art compositions, these fillers have physical strength to the film that forms and play great role.But the present invention adopts granular filler also to increase the effect of a uniqueness; be exactly at the basic solvent carrier of evaporation; thereby take place in the coalescent process of polymer substrate; evaporation along with solvent carrier; filler particles can accumulate in the mobile bigger non-solvent drop; finally reunite in the space that is originally occupied, thereby support and keep cell size in barrier film final by the non-solvent drop with bigger size.
This beneficial effect that the special TDS disequilibrium of granular filler and coating composition combines can be referring to Fig. 2 and Fig. 3.In Fig. 2, barrier film coating profile 15 comprises continuous polymer solution matrix 22, and this polymer solution is by with basic solvent evaporation to the degree that is enough to isolate each non-solvent drop 26 gelling taking place.Filler particles 24,25 is dispersed in the whole coated substance, promptly is dispersed in polymer substrate 22 and the non-solvent drop 26, and the uniformity of the uniformity of its distribution during with the initial uniform composition of curtain coating is substantially the same.But as shown in Figure 3 along with basic solvent evaporation makes the further gelling of polymer, the viscosity of polymer substrate 22 increases, the wherein distribution of filler particles 24 is fixed, and the filler particles 25 in the bigger non-solvent drop 36 of flowability can be reunited with the evaporation of non-solvent.Further reunion take place up to polymer substrate solidify be enough to keep the size of hole 36 till.
In discussing, these should notice that in the rough schematic diagram of Fig. 2 and Fig. 3 be out-of-proportion, just clearer in order to represent.Be about the easier realization of situation of 10nm from the silica dioxide granule actual grain size by the relative distribution of granular filler (as pyrogenic silica) in the hole that non-solvent produced that in polymer substrate, disperses, and demonstration is measured in little photograph, and the diameter of contained hole gap structure is about 1 micron.
Hole and granular filler shown in Fig. 4 is further, be intended to illustrate under extreme condition with heat and the superimposed manufacturing storage battery of pressure, the configuration of filler particles aggregate is the effect in its support membranes pores gap structure finally, if there be not the support of particle cluster to the membranes pores gap structure, heating and pressurized conditions are easy to destroy hole and the greatly key absorption of limit electrolysis liquid in the barrier film.Shown in during as maximum compression, particle cluster keeps the open communication network of hole, provides to continue firm mesopore in isolated component 15.On the other hand, complete mesopore mainly is that the particle of large-size in these compositions is kept in the electrode film 13,17.
Although the present invention can be applicable to above-mentioned patent specification and described any battery terminal of similar publication and electrolyte components, for simplicity, some representative component that the present invention will use the following example to comprise are described.
Embodiment 1
The following coating composition that makes a better embodiment barrier film 15 according to the present invention: with 3.0g88: 12 VDF: HFP copolymer (molecular weight about 380 * 10
3, Atochem Kynar FLEX 2801) be dissolved in about 20ml acetone, in this solution, add about 10ml ethanol (described copolymer is insoluble to ethanol substantially) and 2.0g pyrogenic silica (SiO while stirring
2), form the transparent uniform composition of denseness.With said composition with about 250 microns wet thickness curtain coatings on antiseized PETG film, remove the coating vehicles component at the air evaporations of about 30 ℃ of appropriateness circulations and make it dry.The barrier film of peeling off about 50 micron thickness that the back forms from the curtain coating substrate is from supporting, and looks it is uniform.Microphotograph is observed and is shown that circular holes and silica dioxide granule are evenly distributed in the whole polymer substrate in this film, and this grain density in the pore boundary is generally greater than the grain density in the matrix, with shown in Figure 2 closely similar.
Embodiment 2
Make the duplicate of the general embodiment of the invention described above with the method identical with embodiment 1, different is obsolete silica component in coating composition, so gained is the mesoporous film of not disperseing inert filler, for increase mobile of compensating compositions and obtain comparable thickness, with the coating curtain coating into about 350 microns.Microphotograph is observed and is shown that the barrier film of formation has the physical strength that scrapes through, and looks to have and the identical central hole structure of embodiment 1 sample, but does not have the filler particles of dispersion.
Embodiment 3
Make another film sample with the method identical with embodiment 1, different is to replace ethanol as non-solvent with isopropyl alcohol.Visualization shows that the film of film that obtains and embodiment 1 is as broad as long.
Make another kind of film with the method identical with embodiment 1, different is to replace ethanol as non-solvent with methyl alcohol.Visualization shows that the film of film that obtains and embodiment 1 is as broad as long.
Embodiment 5
Make the control film sample with the component identical with embodiment 1, different is with about 8ml acetone replacement ethanol, thereby coating vehicles only is made up of polymer solvent.With identical method curtain coating and dry said composition, form and the similar film of embodiment 1 film outward appearance.But microphotograph is observed and is shown that this film is evenly distributed on the whole polymer substrate by silica dioxide granule and forms, and does not have central hole structure.
In order to test effectiveness of the present invention, with with above-mentioned United States Patent (USP) 5,418,091 embodiment 13 essentially identical methods make a kind of comparative barrier film sample of prior art, be curtain coating FLEX 2801 VDF: the solvent dispersions of HFP copolymer compositions, above-mentioned composition comprise about 20% silicon dioxide and 25% dibutyl phthalate plasticizer.After the step of described prior art, with ether the flexible diaphragm that forms is extracted to remove plasticizer components, it is can adsorb electrolyte for barrier film that this extraction is handled.Show that to observing through the barrier film of extraction silica dioxide granule is dispersed in the whole polymer substrate, but do not see identifiable hole, this description with above-mentioned patent itself is consistent.
Embodiment 7
The 4 pairs of barrier film samples of the present invention and prior art barrier film sample that each free embodiment 1 and 6 is made carry out the electrolyte adsorption capacity relatively.At this moment, sample weighed and in propylene carbonate (PC) (a kind of lithium salts solvent is usually as the active electrolyte carrier of storage battery), soaked several minutes.After the immersion, the flush away sample shows the propylene carbonate that gathers, and weighs once more, measures the adsorbance of propylene carbonate.The right relatively absorption figure of these samples as shown in Figure 5, mesoporous film of the present invention has higher adsorptivity generally for simulation electrolyte.
Embodiment 8
Each of experimental example 1-5 barrier film of the present invention and contrast barrier film are transferred the adsorptivity of postpone to simulation electrolyte in all temps condition, run into this temperature when thermal polymerization barrier film and electrode member manufacturing storage battery possibly.Improve this lamination temperature and can reduce voidage and electrolyte adsorption capacity.Temperature superimposed pressure and 100 ℃ and 170 ℃ is transferred postpone, uses method test its adsorptivity to propylene carbonate identical with embodiment 7.The absorption comparative result of each embodiment barrier film as shown in Figure 6.These result of the tests be it needs to be noted mesoporous film of the present invention initially presents high electrolyte adsorptivity, and contain the embodiment 1,3 of structural support granular filler and the adsorptivity that 4 these better embodiments obviously keep.Learn easily that by these results the mesopore of packless film when being higher than the polymer substrate melting temperature (as the film of embodiment 2) is easy to collapse.Certainly this film with good initial adsorption is applicable to low temperature or non-laminated accumulator purposes.This figure shows that also the non-porous structure of embodiment 5 control film is temperature influence seldom, all presents minimum electrolyte adsorptivity under any condition.
Embodiment 9
The mesopore barrier film that the present invention is made and the final effectiveness of electrode film are tested, usefulness be that the laminated accumulator that Fig. 4 method of above-mentioned United States Patent (USP) 5,460,904 makes compares.As described in the embodiment 15 of this United States Patent (USP), make the storage battery of plasticizer extraction, and storage battery of the present invention makes with following method: shown in this Figure of description 1, by containing 2.5g FLEX 2801 VDF: HFP copolymer, 1g SP conductive carbon, 5g LiMn
2O
4, 40ml acetone and 15ml ethanol the composition curtain coating go out about 375 microns cathode film 13.In about 150 ℃ heat roller device with on the superimposed aluminium foil current collection element 11 that mesh arranged of the mesoporous film that forms.By containing 2.5g FLEX 2801 VDF: the composition curtain coating of HFP copolymer, 1g SP conductive carbon, 5g carbosphere, 40ml acetone and 15ml ethanol goes out about 450 microns negative electrode film 17.In about 150 ℃ heat roller device with on the superimposed Copper Foil current collection element 19 that mesh arranged of the mesoporous film that forms.The mesopore isolated component 15 that top embodiment 1 is made places between these two electrode member assemblies 13 and 17 and with it and contacts, in this about 120 ℃ heat roller device superimposed it, form whole storage battery 10, subsequently as described in the cited patent, it is immersed in EC: PC; LiPF
6Activate in the electrolyte.
Adopt and the United States Patent (USP) of quoting 5,460,904 embodiment 13 described methods, under the 10mA constant current, carry out cyclic test to the storage battery of prior art with the storage battery that said elements of the present invention makes, circulation rate at C/5,3.0V with the cut-ff voltage of 4.5V, the performance of two kinds of batteries is all similar to Fig. 2 situation of this patent, its discharge capacity is about 20-25mAh.
The foregoing description only is used for explanation and non-limiting the present invention.Under the situation of the scope of the invention that does not depart from the claims qualification, those of ordinary skill in the art is book according to the above description, can obtain producing other polymer of identical result and the mixture of solvent/non-solvent by routine experimentation.
Claims (10)
- One kind in chargeable storage as the preparation method of the porous polymer film of isolated component between the ionic conductivity electrode, it is characterized in that described method comprises:A) prepare the composition that can apply, it comprises the volatile fluid solvent of polymeric material, described polymeric material, and second fluid compatible with described solvent but that volatility is lower, described second fluid is a non-solvent, and described polymeric material is not had tangible dissolubility;B) with described composition curtain coating stratification;C) the rate of volatilization of described solvent under the condition of the rate of volatilization of described non-solvent from described layer the described solvent of volatilization, thereby described layer mainly be that the zone of non-solvent makes described polymeric material gelling, and described non-solvent is isolated into the drop that is evenly distributed in substantially in the whole matrix of polymer material;D) continue the described solvent of volatilization finishing the gelatinization of described polymer substrate, thereby make the described film can be from supporting;E) continue to finish the described non-solvent of volatilization from described drop subsequently, in whole described membrane matrix, form and the similar mesopore distribution of pores of droplet distribution.
- 2. the method for claim 1, it also comprises the filler particles to the basic inertia of other component of coating composition is evenly distributed in the described coating composition, thereby makes described distribution of particles in described hole and in the whole described membrane matrix.
- 3. method as claimed in claim 2, it also comprises makes described mesopore barrier film contact with fluid electrolyte, the time of contact is enough to by described electrolyte is adsorbed on electrolyte is distributed in the described film, makes the described ionic conductivity that do not have.
- One kind in chargeable storage as the porous polymer film of isolated component between the ionic conductivity electrode, it is characterized in that described film comprises the polymer substrate that wherein is distributed with many holes and many inert filler particles, be arranged in described hole to the described particle of small part.
- 5. film as claimed in claim 4 is characterized in that the space density that described particle distributes is higher than the space density that distributes in described matrix in described hole.
- 6. film as claimed in claim 4 is characterized in that described polymer substrate comprises the copolymer of vinylidene fluoride and 3-25 weight % hexafluoropropylene.
- 7. chargeable accumulator structure, it comprise anodal element, negative pole element and be placed in one between diaphragm element, it is characterized in that described barrier film comprises the polymer substrate that wherein is distributed with many holes and many inert filler particles, be arranged in described hole to the described particle of small part.
- 8. chargeable accumulator structure as claimed in claim 7 is characterized in that the space density that described particle distributes is higher than the space density that distributes in described matrix in described hole.
- 9. chargeable accumulator structure as claimed in claim 7 is characterized in that described polymer substrate comprises the copolymer of vinylidene fluoride and 3-25 weight % hexafluoropropylene.
- 10. chargeable accumulator structure as claimed in claim 7 is characterized in that each electrode member comprises polymer substrate, and each described electrode member and isolated component combine with adjacent elements on the interface separately at it, forms flexible whole laminated construction.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/689,170 | 2000-10-12 | ||
| US09/689,170 US6537334B1 (en) | 1998-11-12 | 2000-10-12 | Polymeric mesoporous separator elements for laminated lithium-ion rechargeable batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1349263A true CN1349263A (en) | 2002-05-15 |
| CN1280929C CN1280929C (en) | 2006-10-18 |
Family
ID=24767327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011249145A Expired - Fee Related CN1280929C (en) | 2000-10-12 | 2001-06-29 | Porous polymer isolation element used for lithium ion laminated accumulator |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2002134092A (en) |
| KR (1) | KR100790039B1 (en) |
| CN (1) | CN1280929C (en) |
| SG (1) | SG129214A1 (en) |
| TW (1) | TW508855B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102163741A (en) * | 2010-02-12 | 2011-08-24 | 通用汽车环球科技运作有限责任公司 | Lithium-ion batteries with coated separators |
| CN108023049A (en) * | 2007-09-07 | 2018-05-11 | 卡尔·弗罗伊登伯格公司 | With particles filled non-woven material |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5485741B2 (en) * | 2010-02-12 | 2014-05-07 | 株式会社巴川製紙所 | Manufacturing method of separator for electronic parts |
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|---|---|---|---|---|
| US3953241A (en) * | 1970-03-12 | 1976-04-27 | Westinghouse Electric Corporation | Heat resistant substrates and battery separators made therefrom |
| CA1233621A (en) * | 1984-12-28 | 1988-03-08 | Harlan B. Johnson | Battery separator |
| GB8517571D0 (en) * | 1985-07-11 | 1985-08-14 | Raychem Ltd | Polymer composition |
| US5418091A (en) * | 1993-03-05 | 1995-05-23 | Bell Communications Research, Inc. | Polymeric electrolytic cell separator membrane |
| KR0115725Y1 (en) * | 1995-06-22 | 1998-04-21 | 김태구 | The fixing device of an engine hood |
| JPH1116561A (en) * | 1997-06-23 | 1999-01-22 | Elf Atochem Japan Kk | Battery separator, its manufacture and nonaqueous secondary battery |
| FR2766295B1 (en) * | 1997-07-17 | 1999-09-24 | Alsthom Cge Alcatel | POLYMERIC SEPARATOR, MANUFACTURING PROCESS AND ELECTROCHEMICAL GENERATOR INCLUDING IT |
| US5962162A (en) * | 1997-10-10 | 1999-10-05 | Ultralife Batteries Inc. | Lithium ion polymer cell separator |
| JPH11152366A (en) * | 1997-11-19 | 1999-06-08 | Asahi Chem Ind Co Ltd | Porous membrane of vinylidene fluoride-based resin |
| FR2777698B1 (en) * | 1998-04-16 | 2000-05-12 | Alsthom Cge Alcatel | SEPARATOR COMPRISING A MACROPOROUS MATRIX AND A POROUS POLYMER, ITS MANUFACTURING METHOD, ELECTROCHEMICAL GENERATOR COMPRISING SAME AND THE MANUFACTURING METHOD THEREOF |
| EP1086506A1 (en) * | 1998-05-12 | 2001-03-28 | Ecole Polytechnique Federale De Lausanne (Epfl) | Primary or secondary electrochemical generator |
-
2001
- 2001-06-29 SG SG200103985A patent/SG129214A1/en unknown
- 2001-06-29 CN CNB011249145A patent/CN1280929C/en not_active Expired - Fee Related
- 2001-07-04 JP JP2001203606A patent/JP2002134092A/en active Pending
- 2001-07-13 KR KR1020010042231A patent/KR100790039B1/en not_active IP Right Cessation
- 2001-07-19 TW TW090117720A patent/TW508855B/en active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108023049A (en) * | 2007-09-07 | 2018-05-11 | 卡尔·弗罗伊登伯格公司 | With particles filled non-woven material |
| CN108023049B (en) * | 2007-09-07 | 2021-10-29 | 卡尔·弗罗伊登伯格公司 | Nonwoven material filled with particles |
| CN102163741A (en) * | 2010-02-12 | 2011-08-24 | 通用汽车环球科技运作有限责任公司 | Lithium-ion batteries with coated separators |
| CN102163741B (en) * | 2010-02-12 | 2016-03-16 | 通用汽车环球科技运作有限责任公司 | There is the lithium-ions battery of coated spacer body |
Also Published As
| Publication number | Publication date |
|---|---|
| TW508855B (en) | 2002-11-01 |
| KR100790039B1 (en) | 2008-01-02 |
| JP2002134092A (en) | 2002-05-10 |
| KR20020029295A (en) | 2002-04-18 |
| SG129214A1 (en) | 2007-02-26 |
| CN1280929C (en) | 2006-10-18 |
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