CN1423363A - 制备包含多相隔膜的锂二次电池的方法 - Google Patents
制备包含多相隔膜的锂二次电池的方法 Download PDFInfo
- Publication number
- CN1423363A CN1423363A CN02152803A CN02152803A CN1423363A CN 1423363 A CN1423363 A CN 1423363A CN 02152803 A CN02152803 A CN 02152803A CN 02152803 A CN02152803 A CN 02152803A CN 1423363 A CN1423363 A CN 1423363A
- Authority
- CN
- China
- Prior art keywords
- solvent
- gel polymer
- barrier film
- battery
- weight
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 55
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 238000007789 sealing Methods 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims description 44
- 230000004888 barrier function Effects 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 15
- -1 polyethylene Polymers 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 7
- 159000000002 lithium salts Chemical class 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 238000004381 surface treatment Methods 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 2
- 229910012097 LiSbF Inorganic materials 0.000 claims description 2
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims 1
- 239000000499 gel Substances 0.000 description 39
- 238000002360 preparation method Methods 0.000 description 15
- 239000004014 plasticizer Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- 229920005609 vinylidenefluoride/hexafluoropropylene copolymer Polymers 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000005030 aluminium foil Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000002003 electrode paste Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011094 fiberboard Substances 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 238000009954 braiding Methods 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- 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
- H01M10/052—Li-accumulators
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
-
- 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
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- 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
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/42—Acrylic resins
-
- 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
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/426—Fluorocarbon polymers
-
- 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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
-
- 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- 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
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
-
- 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
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
-
- 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
-
- 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
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
- Y10T29/49115—Electric battery cell making including coating or impregnating
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Cell Separators (AREA)
Abstract
一种制备包含多相隔膜的锂二次电池的方法,所述隔膜中含有在其中均匀浸渍的胶凝聚合物。该方法包括通过把多孔薄膜浸渍到按有机溶剂重量计含有5重量%或更少的胶凝聚合物的胶凝聚合物溶液中对一种多孔隔膜进行表面处理,使得胶凝聚合物的涂敷重量为20mg/cm2或更小。把该隔膜放入阴极和阳极之间来制备一种电极组合。把该电极组合放入一种外壳中,向该外壳中注入电解质溶液,然后密封并固化所得的结构,从而制备了锂二次电池。
Description
要求2001年11月24日提出的韩国专利申请No.01-73572的优先权,其内容引入本文作为参考。
发明领域
本发明涉及锂电池,更特别地涉及一种制备包含多相隔膜的锂二次电池的方法。
技术背景
随着小型化、轻量和无线电子设备如蜂窝电话、摄像机、膝上型电脑等的快速持续发展,高能量密度的锂二次电池作为驱动这些电子设备的能源是广泛研究的焦点。根据所用电解质种类,锂二次电池可以分为使用液体电解质的锂离子电池,或使用固体电解质的锂离子聚合物电池。使用固体电解质的锂离子聚合物电池较不容易泄漏并且有适用于电池组的优异加工性能。
作为在锂离子电池中所用的聚合物电解质,一般使用凝胶聚合物电解质或混合聚合物电解质。凝胶电解质电池是指通过固化含有大量溶剂和/或增塑剂、锂盐和聚合物电解质的溶液所制备的电池。由于凝胶聚合物电解质电池机械强度差,电解质层的厚度通常为75微米或更大,这与锂离子电池相比太厚,导致能量密度下降。为了克服这一缺点,有一种已知的技术,其中使用具有良好机械强度的多孔隔膜,并且用能吸收电解质(具体是锂盐)的凝胶聚合物处理该隔膜。
在一种传统技术中,使用辅助溶剂把聚合物电解质涂敷在电极上,来制备电池。但是,根据这种技术,必须严格控制该过程中的湿度,并且对于阴极和阳极需要单独的涂敷步骤。
另一种传统技术包括把含有盐的胶凝聚合物涂敷在多孔隔膜上,但是,这也存在应该严格控制湿度的缺点。
还有一种已知的技术,即把胶凝聚合物涂敷在多孔隔膜上并把电解质溶液注入多孔隔膜中,然后固化。但是,这种方法有若干缺点。即延长了电解质溶液注入过程中电解质溶液均匀浸渍所需的时间。同时在堆叠型电池的情况下,其中,电极糊应该紧密结合到隔膜上,在多孔隔膜的微孔不发生结构变形的温度和压力条件下,紧密地结合电极糊是相当困难的。
另外,另一种传统方法包括制备一种电池使得使用EC和PC的二元溶剂作为增塑剂来堆叠阴极、阳极和隔膜。但是,当该二元溶剂用于阴极或阳极时,在该过程中难以把电解质溶液注入电极中,并且机械强度降低,导致内部短路。
发明简述
为了解决上述问题,本发明提供了一种制备包含隔膜的锂二次电池的方法,其不需要湿度控制并且即使隔膜用胶凝聚合物处理后也能保持其中的孔隙,导致电解质溶液的快速浸渍,改善了电池性能。
在本发明的一个方面,制备锂二次电池的方法包括通过把多孔隔膜浸入按有机溶剂重量计含有5重量%或更少的胶凝聚合物的胶凝聚合物溶液中,把多孔隔膜表面处理,使得胶凝聚合物的涂敷量为20mg/cm2,把该隔膜放在阴极和阳极之间,以制备一种电极组合,并把该电极组合放入外壳中,注入电解质溶液,密封并固化所得的结构。
附图简述
通过参考附图详细描述其优选的实施方案,本发明的以上目的和优点将变得更清楚,其中:
图1是根据本发明的隔膜的示意图;
图2表示一种制备根据本发明的隔膜的方法;
图3A是根据本发明的隔膜的扫描电子显微镜(SEM)照片,图3B是未经表面处理的隔膜的SEM照片;
图4是表示根据本发明的锂电池的标准充电/放电容量的图;
图5是表示根据本发明的锂电池的平均高速(2C)放电容量的图;
图6是表示根据本发明的锂电池的循环的图;和
图7是表示根据本发明的锂电池的循环依赖性充电/放电效率(1C)的图。
发明详述
在本发明中所用的胶凝聚合物溶液不含锂盐,但是含有按有机溶剂的重量计含量为5重量%或更少的胶凝聚合物。由于锂盐是高度吸湿的,电池制备过程必须是无水过程,但是在本发明中不必如此。换言之,根据本发明,电池制备过程不必是无水过程,从而简化了该过程。如果胶凝聚合物含量为5重量%或更多,则多孔隔膜的大多数孔隙被胶凝聚合物堵塞,因此不能均匀浸渍电解质溶液,导致电池性能恶化。本发明的胶凝聚合物还包含一种增塑剂。增塑剂使得可以在低温和减压下进行叠层。换言之,增塑剂是在室温下为固相且在高于室温的温度下为液相的电解质溶剂。当在高于室温的温度进行叠层时,增塑剂转变成液相,使得电极糊和隔膜在较低温度下相互结合。
其次,把多孔隔膜浸入本发明中所用的胶凝聚合物溶液中并进行表面处理,使得胶凝聚合物量为20mg/cm2或更少,然后把隔膜插在阴极和阳极之间,从而制备一种电极组合。如果胶凝聚合物的量大于20mg/cm2,则多孔隔膜的孔隙被胶凝聚合物堵塞,导致电池性能恶化。
可以使用本领域熟知的任何浸渍方法,并且浸渍时间优选的是不大于20分钟。
把如此制备的电极组合用金属箔密封,以防潮气或水蒸汽渗入,然后注入含有锂盐的电解质溶液来生产电池,通过施加压力和加热来固化电池。在该步骤中,胶凝聚合物溶解在电解质溶液中并且通过冷却而胶凝,用于提供在电极与隔膜之间的结合性。
本发明中所用的多孔隔膜优选的是选自聚乙烯、聚丙烯、和聚丙烯/聚乙烯/聚丙烯的一种,其是一种不能吸收电解质溶液而作为隔膜的主要支撑的聚合物。
本发明中所用的胶凝聚合物优选的是选自聚偏二氟乙烯(PVdF)、聚偏二氟乙烯-六氟丙烯共聚物(PVdF-HFP)、聚环氧乙烷(PEO)、聚丙烯酸甲酯(PMA)和聚丙烯腈(PAN)的一种。胶凝聚合物分布在多孔隔膜的表面上并与第一种溶剂一起进入孔隙,使得隔膜和电极可以相互结合。
根据本发明,可用的锂盐包括LiPF6、LiBF4、LiClO4、Li(CF3SO2)2、LiSbF3和LiAsF6。
在优选的实施方案中,有机溶剂的第一种溶剂的实例包括选自聚碳酸乙二酯、碳酸乙二酯、碳酸丙二酯的环状碳酸酯和选自碳酸二甲酯和碳酸二乙酯的的链型碳酸酯的化合物。即使在组装电池后仍然保持在电池中的第一种溶剂与电解质溶液电化学上相容。因此,第一种溶剂促进电解质溶液向电池中的注入,并促进在电极板与隔膜在低温低压下的结合。第二种溶剂是一种低沸点溶剂,其优选的是选自丙酮、乙腈、n-甲基-2-吡咯烷酮(NMP)的一种及其混合物。第二种溶剂的沸点低于第一种溶剂,并且用来与第一种溶剂共同溶解胶凝聚合物。当应用到多孔隔膜的胶凝聚合物和第一种溶剂被干燥时,排出第二种溶剂。换言之,第二种溶剂用于精细均匀地分布并浸渍胶凝聚合物和第一种溶剂进入多孔隔膜中。第一种溶剂和第二种溶剂按1∶2-1∶20的重量比混合。如果混合比在该范围之外,不希望地把过大或过小量的聚合物涂敷在隔膜上。
在本发明中所用的电解质溶液中含有的第三种溶剂优选的是与第一种溶剂相同,目的是通过解决在电解质溶液注入过程中由于不同材料之间的表面张力产生的问题,短时间内均匀活化电极板内的电解质溶液。另一个优点是没有必要单独分离第一种溶剂。
在本发明的一个实施方案中,固化步骤优选的是在约50℃-约80℃进行,其中,不影响隔膜的微孔。如果固化温度低于50℃,则不能充分进行固化。如果固化温度高于80℃,则不利地影响多孔隔膜的微孔结构。
这样制备的隔膜示意表示在图1中。如图1所示,由于胶凝聚合物和第一种溶剂微细地结合到多孔隔膜2的孔隙1的微孔结构中,可以解决在电解质溶液注入过程中由于不同材料之间的表面张力产生的问题,从而使得电解质溶液在短时间内均匀活化进入电极板中。还由于第一种溶剂存在于胶凝聚合物中,所以在干燥该溶剂时不发生多孔隔膜的收缩。另外,在堆叠型电池的情况下,第一种溶剂可以降低结合阴极和阳极的温度和压力,因为第一种溶剂在室温为固相并且在高于室温的温度为液相,所以,这是可能的。即在叠层过程中,甚至在较低温度下,第一种溶剂转变成液相,使得阴极与阳极相互结合。
具体实施方式
下面参考典型的实施例更详细描述本发明。但是,这些典型的实施例仅用于说明,应该理解本发明不限于这些实施例。
实施例1
1-(1)电极的制备
把20g的偏二氟乙烯/六氟丙烯共聚物(含有15重量%的六氟丙烯)作为结合剂加入到通过混合250ml环己酮和250ml丙酮制备的有机溶剂中,并使用球磨机混合2小时进行溶解。把1000g作为阴极活性材料的LiCoO2和20g作为导电剂的炭黑加入到所得的混合物中,然后混合8小时,以形成阴极活性材料组合物。然后,把20g偏二氟乙烯/六氟丙烯共聚物(含有15重量%六氟丙烯)和20g炭黑加入到通过混合250ml环己酮和250ml丙酮制备的有机溶剂中,并混合8小时以制备预处理组合物。通过喷涂把该预处理组合物涂敷在厚147微米、宽4.9cm的铝箔上,进行铝箔的预处理。最后,使用间隙为320微米的流延法把阴极活性材料组合物涂敷在该铝箔上并干燥形成阴极板。
阳极板制备如下。
把20g的偏二氟乙烯/六氟丙烯共聚物(含有15重量%的六氟丙烯)作为结合剂加入到通过混合300ml N-甲基吡咯烷酮和100ml丙酮制备的有机溶剂中,并使用球磨机混合2小时进行溶解。把1000g作为阳极活性材料的中碳纤维(MCF)加入到所得的混合物中,然后混合3小时,以形成阳极活性材料组合物。然后,把50g偏二氟乙烯/六氟丙烯共聚物(含有15重量%六氟丙烯)和5g炭黑加入到通过混合300mlN-甲基吡咯烷酮和100ml丙酮制备的有机溶剂中,并混合2小时以制备预处理组合物。通过喷涂把该预处理组合物涂敷在厚178微米、宽5.1cm的铜箔上,进行铜箔的预处理。最后,使用间隙为420微米的流延法把阳极活性材料组合物涂敷在该铜箔上并干燥形成阳极板。
1-(2)隔膜的制备
根据本发明的隔膜制备如下:使用一种基材非编织聚乙烯(PE)纤维板(Web Dynamics,Px 0074)。该制造商的材料说明包括2.5密耳的厚度且孔隙尺寸不大于0.1mm。该产品在一侧具有粗糙的表面,在另一侧具有光滑的表面。材料密度实验测定为28g/m2。这些纤维板由STET制造。使用聚碳酸丙二酯作为第一种溶剂,乙腈作为第二种溶剂,混合比按重量计为10∶165。如图2所示,把5g作为胶凝聚合物的PEO溶解在500g该有机溶剂中,以制备1重量%的胶凝聚合物溶液,放入容器7中。然后,把非编织PE纤维板从隔膜退绕机4供给到容器7中并浸渍约1秒,然后使用隔膜重绕机5缠绕,利用厚度调节狭缝6调节其厚度。然后,干燥第二种溶剂乙腈,从而制成隔膜。这里,胶凝聚合物的涂敷重量为10mg/cm2。图3A是所制备的隔膜的扫描电子显微(SEM)照片。为了比较,未表面处理的隔膜的SEM照片表示于图3B中。
1-(3)电池的组装
通过分别冲切(blanking)阴极和阳极板制备阴极和阳极,并且把隔膜放入其间,然后在约50℃结合隔膜和电极,装入多层薄膜制成的外壳中,向该外壳中注入电解质溶液,从而制备了一种电池。该电池通过按如下顺序堆叠7片阳极和6片阴极制成:阳极、隔膜、阴极、隔膜和阳极;阳极用作两个最外层的电极。作为电池壳所用的外壳是厚度为115微米的多层薄膜。
实施例2
用与实施例1相同的方法制备电池,但是使用1.5重量%的PEO溶液作为胶凝聚合物溶液。胶凝聚合物的涂敷重量为0.1mg/cm2。
实施例3
用与实施例1相同的方法制备电池,但是使用2重量%的PEO溶液作为胶凝聚合物溶液。胶凝聚合物的涂敷重量为0.5mg/cm2。
实施例4
用与实施例1相同的方法制备电池,但是使用4重量%的PEO溶液作为胶凝聚合物溶液。胶凝聚合物的涂敷重量为1mg/cm2。
实施例5
用与实施例1相同的方法制备电池,但是使用5g PVdF代替PEO。胶凝聚合物的涂敷重量为1mg/cm2。
对比实施例1
用与实施例1相同的方法制备电池,但是使用10重量%的PEO溶液作为胶凝聚合物溶液。胶凝聚合物的涂敷重量为750mg/cm2。
对比实施例2
用与实施例1相同的方法制备电池,但是把隔膜浸渍在胶凝聚合物溶液中约1小时。胶凝聚合物的涂敷重量为800mg/cm2。
评价实施例:电池性能测试
评价实施例1-5和对比实施例1-2的电池并且其结果表示如下:
表1
平均标准放电容量(mAh) | 相对于标准放电容量的平均高速(2C)放电容量(%) | 相对于标准放电容量的平均1C放电容量(%) | |
实施例1 | 555 | 97.4 | 99.6 |
实施例2 | 540 | 95.2 | 99.0 |
实施例3 | 548 | 93.1 | 97.4 |
实施例4 | 510 | 87.2 | 95.1 |
实施例5 | 511 | 82 | 94.1 |
对比实施例1 | 300 | 1.2 | 9.1 |
对比实施例2 | 300 | 0 | 10.0 |
参见表1,证明了根据本发明的电池的标准放电容量优于传统电池。
图4-7分别表示标准充电/放电容量曲线,由速度表示的放电曲线、循环特性、由循环表示的效率。
根据本发明的隔膜包含微孔,用于促进电解质溶液的浸渍。还由于该隔膜不含盐,所以,在注入电解质溶液之前不必严格控制湿度,即简化了隔膜的处理过程。此外,该隔膜在低温和减压下堆叠,不会不利地影响微孔结构。根据本发明制备的锂二次电池性能良好,耐泄漏性良好,并且可以减少内部短路的发生。
虽然参考其优选的实施方案具体表示和描述了本发明,本领域技术人员应该理解,其中可以在形式和细节方面进行各种变化而不脱离由所附权利要求书限定的本发明的实质和范围。
Claims (12)
1.一种制备锂二次电池的方法,其包括:
通过把多孔薄膜浸渍到按有机溶剂重量计含有5重量%或更少的胶凝聚合物的胶凝聚合物溶液中对一种多孔隔膜进行表面处理,使得胶凝聚合物的涂敷重量为20mg/cm2或更小;
把该隔膜放入阴极和阳极之间来制备一种电极组合;和
把该电极组合放入一种外壳中,注入电解质溶液,密封并固化所得的结构。
2.根据权利要求1的方法,其中,所述多孔隔膜是选自聚乙烯、聚丙烯、和聚丙烯/聚乙烯/聚丙烯的一种。
3.根据权利要求1的方法,其中,所述胶凝聚合物是选自聚偏二氟乙烯(PVdF)、聚偏二氟乙烯-六氟丙烯共聚物(PVdF-HFP)、聚环氧乙烷(PEO)、聚丙烯酸甲酯(PMA)和聚丙烯腈(PAN)的一种。
4.根据权利要求1的方法,其中,所述锂盐是选自LiPF6、LiBF4、LiClO4、Li(CF3SO2)2、LiSbF3和LiAsF6的一种。
5.根据权利要求1的方法,其中,所述有机溶剂包含第一种溶剂和第二种溶剂,并且第一种溶剂的沸点高于第二种溶剂的沸点。
6.根据权利要求5的方法,其中,所述第一种溶剂即使在组装电池后仍然保持在带有胶凝聚合物的隔膜的孔隙中。
7.根据权利要求5的方法,其中,所述第二种溶剂在浸渍胶凝聚合物之后排出。
8.根据权利要求5的方法,其中,所述第一种溶剂是选自聚碳酸乙二酯、碳酸乙二酯、碳酸丙二酯的环状碳酸酯与选自碳酸二甲酯和碳酸二乙酯的链型碳酸酯的混合物。
9.根据权利要求5的方法,其中,所述第二种溶剂是选自丙酮、乙腈、n-甲基-2-吡咯烷酮(NMP)之一和它们的混合物。
10.根据权利要求5的方法,其中,所述第一种溶剂与第二种溶剂按1∶2-1∶20的重量比混合。
11.根据权利要求1的方法,其中,在所述电解质溶液中含有与第一种溶剂相同的第三种溶剂。
12.根据权利要求1的方法,其中,在约50℃-约80℃的温度进行所述固化步骤。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR73572/2001 | 2001-11-24 | ||
KR73572/01 | 2001-11-24 | ||
KR10-2001-0073572A KR100440930B1 (ko) | 2001-11-24 | 2001-11-24 | 세퍼레이터의 제조방법 및 이를 채용한 리튬2차 전지의제조방법 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1423363A true CN1423363A (zh) | 2003-06-11 |
CN1302575C CN1302575C (zh) | 2007-02-28 |
Family
ID=19716282
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB021528039A Expired - Lifetime CN1302575C (zh) | 2001-11-24 | 2002-11-22 | 制备包含多相隔膜的锂二次电池的方法 |
Country Status (4)
Country | Link |
---|---|
US (1) | US7381500B2 (zh) |
JP (1) | JP4243096B2 (zh) |
KR (1) | KR100440930B1 (zh) |
CN (1) | CN1302575C (zh) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1917276B (zh) * | 2005-07-29 | 2011-08-03 | 索尼株式会社 | 电池 |
CN104684732A (zh) * | 2012-10-08 | 2015-06-03 | 特里奥凡德国有限公司及两合公司 | 具有均匀的孔隙度和增强的耐击穿性的微孔隔膜-薄膜 |
CN108780926A (zh) * | 2016-03-31 | 2018-11-09 | 株式会社Lg化学 | 制备二次电池的方法 |
CN108808083A (zh) * | 2018-08-28 | 2018-11-13 | 江苏双登富朗特新能源有限公司 | 固态电解质膜制备方法 |
CN110444803A (zh) * | 2018-05-03 | 2019-11-12 | 苏州华骞时代新能源科技有限公司 | 一种半固态的锂离子电池结构及其制备方法 |
TWI829635B (zh) * | 2017-04-06 | 2024-01-21 | 日商旭化成股份有限公司 | 用於鋰離子二次電池之分隔件 |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6347051B2 (en) | 1991-11-26 | 2002-02-12 | Hitachi, Ltd. | Storage device employing a flash memory |
KR100740548B1 (ko) * | 2005-12-27 | 2007-07-18 | 주식회사 나래나노텍 | 리튬폴리머전지용 겔폴리머전해질 조성물 및 이를 이용한리튬폴리머전지 |
EP2001073B1 (en) | 2007-06-06 | 2012-02-22 | Nissan Motor Co., Ltd. | Secondary battery and method of producing the secondary battery |
JP5526481B2 (ja) * | 2007-06-06 | 2014-06-18 | 日産自動車株式会社 | 二次電池およびその製造方法 |
US8697273B2 (en) * | 2007-08-21 | 2014-04-15 | A123 Systems Llc | Separator for electrochemical cell and method for its manufacture |
CN102097647B (zh) * | 2009-12-09 | 2014-03-26 | 微宏动力系统(湖州)有限公司 | 锂离子电池 |
CN103155220B (zh) | 2011-04-08 | 2016-01-20 | 帝人株式会社 | 非水系二次电池用隔膜及非水系二次电池 |
GB2526312B (en) | 2014-05-20 | 2018-10-17 | Dyson Technology Ltd | Method of manufacturing an electrochemical cell |
KR20170041470A (ko) * | 2015-10-07 | 2017-04-17 | 주식회사 엘지화학 | 전극조립체를 구성하는 분리막의 기공 내에 겔화 전해액 성분을 포함하고 있는 전지셀 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1194278A (zh) * | 1997-01-20 | 1998-09-30 | 松下电器产业株式会社 | 聚合物电解质和使用该电解质的锂-聚合物电池 |
JPH1167273A (ja) * | 1997-08-21 | 1999-03-09 | Toshiba Corp | リチウム二次電池 |
FR2777698B1 (fr) | 1998-04-16 | 2000-05-12 | Alsthom Cge Alcatel | Separateur comprenant une matrice macroporeuse et un polymere poreux, son procede de fabrication, generateur electrochimique le comprenant et le procede de fabrication de celui-ci |
EP1096591A1 (en) * | 1999-10-26 | 2001-05-02 | MERCK PATENT GmbH | Polymer electrolyte membrane for use in lithium batteries |
JP2001176554A (ja) * | 1999-12-16 | 2001-06-29 | Nitto Denko Corp | 電気化学素子の製造方法 |
KR100515572B1 (ko) * | 2000-02-08 | 2005-09-20 | 주식회사 엘지화학 | 중첩 전기화학 셀 및 그의 제조 방법 |
KR100362283B1 (ko) * | 2000-05-12 | 2002-11-23 | 삼성에스디아이 주식회사 | 리튬 2차 전지의 제조방법 |
JP2001319690A (ja) * | 2000-05-12 | 2001-11-16 | Hitachi Maxell Ltd | ポリマー電解質電池およびその製造方法 |
US6881515B2 (en) | 2001-05-08 | 2005-04-19 | Celgard Inc. | Separator for polymer battery |
-
2001
- 2001-11-24 KR KR10-2001-0073572A patent/KR100440930B1/ko active IP Right Grant
-
2002
- 2002-11-22 CN CNB021528039A patent/CN1302575C/zh not_active Expired - Lifetime
- 2002-11-22 US US10/301,813 patent/US7381500B2/en not_active Expired - Lifetime
- 2002-11-25 JP JP2002341466A patent/JP4243096B2/ja not_active Expired - Lifetime
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1917276B (zh) * | 2005-07-29 | 2011-08-03 | 索尼株式会社 | 电池 |
CN104684732A (zh) * | 2012-10-08 | 2015-06-03 | 特里奥凡德国有限公司及两合公司 | 具有均匀的孔隙度和增强的耐击穿性的微孔隔膜-薄膜 |
CN108780926A (zh) * | 2016-03-31 | 2018-11-09 | 株式会社Lg化学 | 制备二次电池的方法 |
CN108780926B (zh) * | 2016-03-31 | 2021-05-28 | 株式会社Lg化学 | 制备二次电池的方法 |
TWI829635B (zh) * | 2017-04-06 | 2024-01-21 | 日商旭化成股份有限公司 | 用於鋰離子二次電池之分隔件 |
CN110444803A (zh) * | 2018-05-03 | 2019-11-12 | 苏州华骞时代新能源科技有限公司 | 一种半固态的锂离子电池结构及其制备方法 |
CN108808083A (zh) * | 2018-08-28 | 2018-11-13 | 江苏双登富朗特新能源有限公司 | 固态电解质膜制备方法 |
Also Published As
Publication number | Publication date |
---|---|
US7381500B2 (en) | 2008-06-03 |
US20030118895A1 (en) | 2003-06-26 |
JP2003187872A (ja) | 2003-07-04 |
KR100440930B1 (ko) | 2004-07-21 |
KR20030042793A (ko) | 2003-06-02 |
CN1302575C (zh) | 2007-02-28 |
JP4243096B2 (ja) | 2009-03-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1302575C (zh) | 制备包含多相隔膜的锂二次电池的方法 | |
CN1320685C (zh) | 有机电解液以及使用该有机电解液的锂二次电池 | |
CN1218416C (zh) | 可充电锂电池的包括电解质的颗粒电极 | |
KR100399788B1 (ko) | 졸 형태의 고분자 전해질 및 이를 채용한 리튬 전지 | |
JP5687496B2 (ja) | LiF系化合物でコーティングされた負極及びその製造方法、並びにその負極を含むリチウムイオン二次電池 | |
US6503661B1 (en) | Lithium secondary battery | |
CN1324728C (zh) | 电解液分解受到抑制的锂二次电池及其制备方法 | |
CN1215594C (zh) | 锂电池的制备方法 | |
CN1349273A (zh) | 固体电解质电池 | |
CN1193822A (zh) | 锂二次电池 | |
CN1860629A (zh) | 锂离子二次电池及其制造方法 | |
KR100547085B1 (ko) | 고분자 다공성 분리막 및 리튬이온 고분자 전지의 제조방법 | |
CN1452794A (zh) | 多微孔无机固体电解质及其制备方法 | |
CN1229889C (zh) | 锂电池 | |
CN1392625A (zh) | 用于制备非水电解质电池的方法 | |
CN1442926A (zh) | 非水电解质电池 | |
CN1341675A (zh) | 聚合物凝胶电解质和应用它制成的锂电池 | |
KR100522685B1 (ko) | 겔 형태의 고분자 전해질 및 이를 채용한 리튬 전지 | |
CN1167165C (zh) | 非水电解质二次电池及其制造方法 | |
KR100627331B1 (ko) | 리튬 이차 전지 및 리튬 이차 전지의 제조 방법 | |
CN1295809C (zh) | 制备锂离子聚合物电池的方法以及由该方法制得的电池 | |
KR100357960B1 (ko) | 리튬 2차전지 | |
US20040137331A1 (en) | Separator for lithium battery and lithium battery employing the same and method of manufacture thereof | |
US20230411686A1 (en) | Layered gel-polymer electrolytes and methods of forming thereof | |
CN1169254C (zh) | 具有自粘性高分子电解质的锂电池及其制造方法 |
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 | ||
CX01 | Expiry of patent term | ||
CX01 | Expiry of patent term |
Granted publication date: 20070228 |