CA2245048C - Method of preparing lithium ion polymer battery - Google Patents
Method of preparing lithium ion polymer battery Download PDFInfo
- Publication number
- CA2245048C CA2245048C CA002245048A CA2245048A CA2245048C CA 2245048 C CA2245048 C CA 2245048C CA 002245048 A CA002245048 A CA 002245048A CA 2245048 A CA2245048 A CA 2245048A CA 2245048 C CA2245048 C CA 2245048C
- Authority
- CA
- Canada
- Prior art keywords
- composite
- cathode
- anode
- lithium
- lithium ion
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- 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
- 229920000642 polymer Polymers 0.000 title claims abstract description 58
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 43
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 83
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 36
- 239000011244 liquid electrolyte Substances 0.000 claims abstract description 24
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 238000010030 laminating Methods 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 7
- 238000009461 vacuum packaging Methods 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000004014 plasticizer Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 238000005266 casting Methods 0.000 claims description 11
- 239000004020 conductor Substances 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 230000003213 activating effect Effects 0.000 claims description 9
- -1 lithium hexafluoroarsenate Chemical compound 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000006183 anode active material Substances 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- 239000006182 cathode active material Substances 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000010 aprotic solvent Substances 0.000 claims description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 239000006256 anode slurry Substances 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 239000006257 cathode slurry Substances 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 2
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000011325 microbead Substances 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- 239000002006 petroleum coke Substances 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims 1
- 229910032387 LiCoO2 Inorganic materials 0.000 claims 1
- 229910003005 LiNiO2 Inorganic materials 0.000 claims 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims 1
- 239000000571 coke Substances 0.000 claims 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims 1
- 239000011149 active material Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229920000131 polyvinylidene Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910014549 LiMn204 Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910013462 LiC104 Inorganic materials 0.000 description 1
- 229910013021 LiCoC Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- DZUDZSQDKOESQQ-UHFFFAOYSA-N cobalt hydrogen peroxide Chemical compound [Co].OO DZUDZSQDKOESQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- LQKOJSSIKZIEJC-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+2].[Mn+2].[Mn+2] LQKOJSSIKZIEJC-UHFFFAOYSA-N 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MRHPUNCYMXRSMA-UHFFFAOYSA-N nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Ni++] MRHPUNCYMXRSMA-UHFFFAOYSA-N 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
-
- 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
- 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
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0409—Methods of deposition of the material by a doctor blade method, slip-casting or roller coating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a method of preparing a lithium ion polymer battery which has a high capacity and a good cyclability as well as no exudation of liquid electrolyte. The lithium ion polymer battery according to the present invention is prepared by the steps of forming electrode films, laminating the electrode films on both surfaces of a grid or expanded metal sa as to improve the interfacial adhesion between the electrode films, forming a polymer electrolyte film composed of a polymer, an electrolyte solution, and a filler, and laminating the composite amode, the polymer electrolyte and the composite cathode. The activated composite anode/polymer electrolyte film/activated composite cathode is laminated to obtain a lithium ion polymer battery structure. The lithium ion polymer batter is vacuum-packaged using a vacuum packaging apparatus.
Description
Method of Preparing Lithium Ion polymer Battery Field of the Invention The present invention relates to a method of preparing a lithium ion polymer battery which has high energy density and good cyclability.
More particularly, the present invention relates to a method of preparing a lithium ion polymer battery composed of a carbon composite anode, a polymer electrolyte and a metallic oxide composite cathode, which prevents the exudation of liquid electrolyte by using a polymer matrix highly compatible with liquid electrolyte and improves interfacial adhesion between an electrolyte and electrodes.
Background of the Invention The lithium ion polymer batteries fabricated with a solid polymer electrolyte having a high ionic conductivity have advantages to solve the problems of the exudation of electrolyte solution and explosion, which have occurred in the lithium ion cell using liquid electrolyte. Also, if a solid polymer electrolyte is employed, it is possible to design various shapes of cell as well as to simplify the process of manufacturing the lithium ion polymer batteries. Since the lithium ion polymer battery has little self-discharge up to 5 % and no memory effect, it is spotlighted as a next generation battery. A method of preparing a lithium ion polymer battery has been developed in many ways.
US Patent No. 5,491,041 discloses a solid state rechargeable electrochemical cell comprising a Li intercalating composite cathode, a solid polymer electrolyte separator, and a composite anode containing graphite, a polymer electrolyte and 12-crown-4-ether. The electrodes of the US patent above are prepared by coating a current collector layer such as aluminium or copper foil with a cathode or an anode active material. However, the cell has a poor cyclability due to being separated the active material from the current collector layer during charge/discharge cycles. Further, the capacity of the cell per unit area cannot be increased due to the limitation to the thickness of electrodes.
US Patent No. 5,540,741 discloses a method of making a battery structure comprising forming a solid state positive electrode of a polymer, a plasticizes and an active material, forming a solid state negative electrode of the same polymer, a plasticizes and an active material, forming a separator membrane of the same polymer and a plasticizes, bonding said electrodes and said separator membrane to form a unitary cell structure, extracting a portion of said plasticizes from at least said separator membrane, and activating said battery by reswelling at least said separator membrane by contacting said unitary battery structure with an electrolytic salt solution. This method of the patent has an advantage that most of the steps for preparing the battery structure can be carried out under the atmosphere so as to avoid using an electrolyte solution which is sensitive to the moisture, and that the activating step is carried out under the anhydrous atmosphere.
However, the battery prepared by the method has an exudation problem of liquid electrolyte, because the polymer electrolyte does not retain the liquid electrolyte for a long period. Also, it is not easy to retain a sufficient amount of the liquid electrolyte in the microporous polymer membrane.
Therefore, the present inventors have developed a lithium ion polymer battery to overcome the shortcomings of the conventional batteries and a method of preparing the same.
Obj ects of the Invention An object of the present invention is to provide a method of preparing a lithium ion polymer battery which can prevent the exudation of liquid electrolyte.
Another obj ect of the invention is to provide a method of preparing a lithium ion polymer battery which has a high capacity.
A further object of the invention is to provide a method of preparing a lithium ion polymer battery which has a good cyclability.
More particularly, the present invention relates to a method of preparing a lithium ion polymer battery composed of a carbon composite anode, a polymer electrolyte and a metallic oxide composite cathode, which prevents the exudation of liquid electrolyte by using a polymer matrix highly compatible with liquid electrolyte and improves interfacial adhesion between an electrolyte and electrodes.
Background of the Invention The lithium ion polymer batteries fabricated with a solid polymer electrolyte having a high ionic conductivity have advantages to solve the problems of the exudation of electrolyte solution and explosion, which have occurred in the lithium ion cell using liquid electrolyte. Also, if a solid polymer electrolyte is employed, it is possible to design various shapes of cell as well as to simplify the process of manufacturing the lithium ion polymer batteries. Since the lithium ion polymer battery has little self-discharge up to 5 % and no memory effect, it is spotlighted as a next generation battery. A method of preparing a lithium ion polymer battery has been developed in many ways.
US Patent No. 5,491,041 discloses a solid state rechargeable electrochemical cell comprising a Li intercalating composite cathode, a solid polymer electrolyte separator, and a composite anode containing graphite, a polymer electrolyte and 12-crown-4-ether. The electrodes of the US patent above are prepared by coating a current collector layer such as aluminium or copper foil with a cathode or an anode active material. However, the cell has a poor cyclability due to being separated the active material from the current collector layer during charge/discharge cycles. Further, the capacity of the cell per unit area cannot be increased due to the limitation to the thickness of electrodes.
US Patent No. 5,540,741 discloses a method of making a battery structure comprising forming a solid state positive electrode of a polymer, a plasticizes and an active material, forming a solid state negative electrode of the same polymer, a plasticizes and an active material, forming a separator membrane of the same polymer and a plasticizes, bonding said electrodes and said separator membrane to form a unitary cell structure, extracting a portion of said plasticizes from at least said separator membrane, and activating said battery by reswelling at least said separator membrane by contacting said unitary battery structure with an electrolytic salt solution. This method of the patent has an advantage that most of the steps for preparing the battery structure can be carried out under the atmosphere so as to avoid using an electrolyte solution which is sensitive to the moisture, and that the activating step is carried out under the anhydrous atmosphere.
However, the battery prepared by the method has an exudation problem of liquid electrolyte, because the polymer electrolyte does not retain the liquid electrolyte for a long period. Also, it is not easy to retain a sufficient amount of the liquid electrolyte in the microporous polymer membrane.
Therefore, the present inventors have developed a lithium ion polymer battery to overcome the shortcomings of the conventional batteries and a method of preparing the same.
Obj ects of the Invention An object of the present invention is to provide a method of preparing a lithium ion polymer battery which can prevent the exudation of liquid electrolyte.
Another obj ect of the invention is to provide a method of preparing a lithium ion polymer battery which has a high capacity.
A further object of the invention is to provide a method of preparing a lithium ion polymer battery which has a good cyclability.
Other objects and advantages of this invention will be apparent from the ensuing disclosure and appended claims.
Summary of the Invention The present invention relates to a method of preparing a lithium ion polymer battery which has a high capacity and a good cyclability as well as no exudation of liquid electrolyte. The lithium ion polymer battery according to the present invention is prepared by the steps of forming electrode films, laminating the electrode films on both surfaces of a grid or expanded metal so as to improve the interfacial adhesion between the electrode films, forming a polymer electrolyte film composed of a polymer, an electrolyte solution, and a filler, and laminating the composite anode, the polymer electrolyte and the composite cathode.
The lithium ion polymer batter according to the present invention comprises a carbon composite anode, a polymer electrolyte and a metallic oxide composite cathode.
The composite anode is prepared by forming an anode film by casting a composite anode slurry composed of an active material, a conducting material, a binder, a plasticizer and a solvent, laminating said anode film on both sides of a copper grid or a copper expanded metal to 2 0 prepare a composite anode, extracting plasticizer from the composite anode by immersing in a solvent, and activating the composite anode by immersing in an electrolyte solution to prepare an activated composite anode.
The polymer electrolyte film is made by casting a polymer electrolyte slung composed of a polymer matrix, a liquid electrolyte solution of a lithium salt and an aprotic solvent, a filer and a solvent.
The composite cathode is prepared by forming a cathode film by casting a composite cathode slurry composed of an active material, a conducting material, a binder, a plasticizer and a solvent, laminating said 3 0 cathode film on both sides of an aluminum grid or an aluminum expanded metal to prepare a composite cathode, extracting plasticizer from the composite cathode by immersing in a solvent, and activating the composite cathode by immersing in an electrolyte solution to prepare an activated composite cathode.
The activated composite anode/polymer electrolyte film/activated composite cathode is laminated to obtain a lithium ion polymer battery structure. The lithium ion polymer battery is vacuum-packaged using a vacuum packaging apparatus.
The present invention has an advantage that most of the steps for preparing the battery structure can be carried out under the atmosphere so as to avoid using an electrolyte solution which is sensitive to the moisture, and that the activating step is carried out under the anhydrous atmosphere. Also, this invention is to provide a lithium ion polymer battery having a high capacity and a good cyclability, which can prevent the exudation of liquid electrolyte.
Brief Description of the Drawings The present invention will be described with reference to the accompanying drawings of which:
Fig. 1 is a schematic diagram of the preparation process of a lithium ion polymer battery in accordance with the present invention.
Fig. 2 shows charge/discharge curves for a lithium ion polymer battery composed of a carbon composite anode/polymer electrolyte/metallic oxide composite cathode (electrolyte solution: 1M
lithium hexafluoroarsenate, ethylene carbonate/dimethyl carbonate) according to the present invention at a current density of 0.5 mA/cai .
Fig. 3 shows charge/discharge curves for a lithium ion battery composed of a carbon composite anode/polymer electrolyte/metallic oxide composite cathode (electrolyte solution: 1M lithium hexafluorophosphate, ethylene carbonate/dimethyl carbonate) according to the present invention at a current density of 0.25 mA/c~i .
Detailed Description of the Preferred Embodiment The important factors characterizing the performance of a secondary battery are energy density and cycle life. The energy density can be increased by effectivE:ly filling active material per unit weight or volume in a battery. The cycle life depends upon not only constituent elements of a battery, but also interfacial contacts between electrode materials.
In this invention, in on~er to maximize the amount of active material to be loaded in the Electrodes, electrode films are prepared by casting a composite electrode slurry composed of an active material, a conducting material, a binder°, a plasticizes and a solvent, and each electrode film is laminated under high pressure to prepare a composite l0 electrode. In order to improve the interfacial adhesion of the electrode films, the films are laminated on a metal grid or an expanded metal, but not on a metal foil. And, in order to prevent the exudation of liquid electrolyte, a polymer having a good compatibility with liquid electrolyte is employed.
The method of preparing a lithium ion polymer battery in accordance with the present invention comprises processes of preparing a composite anode, a polymer electrolyte and a composite cathode, fabricating a cell from the components, and packaging the cell.
The composite anode is prepared by forming an anode film by 2 0 casting a composite anode slurry composed of an active material, a conducting material, a binder, a plasticizes and a solvent, laminating said anode film on both sides of a~ copper grid or a copper expanded metal to prepare a composite anode, extracting plasticizes from the composite anode by immersing in a solvent, and activating the composite anode by 2 5 immersing in an electrolyte solution to prepare an activated composite anode.
The polymer electrolyte film is made by casting a polymer electrolyte slurry composed of a polymer matrix, a liquid electrolyte solution of a lithium salt and an aprotic solvent, a filler and a solvent.
3 o The composite cathode is prepared by forming a cathode film by casting a composite cathode slurry composed of an active material, a conducting material, a binder, a plasticizes and a solvent, laminating said cathode film on both sides of an aluminum grid or an aluminium expanded metal to prepare a composite cathode, extracting plasticizer from the composite cathode by immersing in a solvent, and activating the composite cathode by immersing in an electrolyte solution to prepare an activated composite cathode.
The activated composite anode/polymer electrolyte film/activated composite cathode is laminated to obtain a lithium ion polymer battery structure. The lithium ion polymer battery is vacuum-packaged using a vacuum packaging apparatus.
The anode active material used for preparing the composite anode l0 in the present invention is selected from the group consisting of petroleum coke, microbead carbon code, synthetic graphite, natural graphite and mixtures thereof. The cathode active material used for preparing the composite cathode in the present invention is selected from the group consisting of lithiated manganese tetraoxide (LiMnz04), 15 lithiated cobalt dioxide (LiCoC> z) and lithiated nickel dioxide (LiNi02), Polymer matrices used for preparing the polymer electrolyte according to the present invention are polyacrylonitrile, poly (vinylidene fluoride), poly (methyl methacrylate), poly (ethylene oxide), poly (vinyl chloride), poly (vinyl acetate), polystyrene and copolymers thereof. These 2 0 polymer matrices have a good compatibility with the liquid electrolyte which is used in this invention. The polymer electrolyte is prepared by mixing a polymer matrix with a liquid electrolyte, adding a ceramic filler to the polymer electrolyte solution, stirring the solution to be completely dissolved, and finally casting the obtained polymer electrolyte solution on 2 5 a glass plate.
The liquid electrolyte fior preparing the polymer electrolyte is composed of a lithium salt for an aprotic solvent. Examples of the lithium salt are lithium perchlorate ((LiC104), lithium trifluoromethansufonimide (LiN(CF3S02), lithium hexafluorophosphate 3 0 (LiPFs), lithium tetrafluorobor,ate (LiBF4), lithium trifluoromethansulfonate (LiCF2 S03), lithium hexafluoroarsenate (LiASFs) and mixtures thereof.
Examples of the aprotic solvent are ethylene carbonate, diethoxy ethane, dimethoxy ethane, dipropyl carbonate and mixtures thereof.
Ceramic fillers used for preparing the polymer electrolyte are silica, alumina, lithium aluminate, zeolite and mixtures thereof.
As the polymer matrices which have been employed in conventional methods of preparing a lithium ion polymer battery have a poor compatibility with a liquid electrolyte, the polymer matrices could cause the exudation of liquid electrolyte and low interfacial adhesion between electrodes and polymer electrolyte. By contrast, the present invention uses a polymer matrix which has a good compatibility with a liquid electrolyte, so that the interfacial adhesion between electrodes and electrolyte is improved. The lithium ion polymer battery in accordance with the present invention has a high capacity and a good cyclability as well as a safety of battery.
The present invention may be better understood by reference to the following examples which are intended for purposes of illustration and are not to be confined in any way limiting the scope of the present invention, which is defined in the claims appended hereto.
Examples Fig. 1 shows a schematic diagram of the preparation method of the lithium ion polymer battery according to the present invention. The method of preparing the lithium ion polymer battery comprises processes of preparing a composite anode, a polymer electrolyte, and a composite cathode, fabricating a cell from the components, and packaging the cell.
The detailed description of each process follows as below.
Preparation of Composite Anode Film:
A composite anode slurry for the lithium ion polymer battery was composed of an anode active material, a conducting material, a binder, a plasticizer and a solvent. A synthetic graphite was used as anode active material, and Super P battery carbon was used as conducting material, and poly(vinylidene fluoride-co-hexafluropropylene) was used as binder.
The process of preparing a composite anode from the components was _8_ shown in Fig. 1. The poly(vinylidene fluoride-co-hexafluropropylene) of 9.3 parts by weight was completely dissolved in acetone, thereafter, dibutyl phthalate of 22.7 parts by weight was added as plasticizer and stirred to give a homogeneous solution. To the solution, 2.6 parts by weight of Super P battery carbon and 65.4 parts by weight of graphite were added, thereby a black anode slurry with a high viscosity being prepared. The slurry was poured on a glass plate and cast with a doctor blade, and then the cast film was exposed to the atmosphere at room temperature for 30 minutes to evaporate acetone, thereafter, to give l0 a composite anode film.
Preparation of Composite Cathode Film:
A composite cathode ;slurry was also composed of a cathode active material, a conducting material, a binder, a plasticizer and a solvent. As cathode active material, LirvIn204 was used. Super P battery carbon was used as conducting material, and poly (vinylidene fluoride-co-hexafluropropylene) was used as binder. The process of preparing a composite cathode by using the components is shown in Fig.
1. The poly (vinylidene fluoride-co-hexafluropropylene) of 10.0 parts by weight was completely dissolved in acetone, and dibutyl phthalate of 19.5 2 0 parts by weight was added aind stirred to give a homogeneous solution.
To the solution, 5.5 parts by weight of Super P battery carbon and 65.1 parts by weight of LiMn204 in powder were added and mixed, a cathode slurry being prepared. The slurry was poured on a glass plate and coated with a doctor blade. 'f he coated film was exposed to the 2 5 atmosphere at room temperature for 30 minutes to give a composite cathode film.
Lamination of Electrodes:
The composite anode film and composite cathode film were 3 0 layer-built to form electrode/c:urrent collector electrode, to prepare a composite anode and a composite cathode, respectively. The current collector for the composite anode was a copper expanded metal and the _g_ current collector for the composite cathode was an aluminium expanded metal. The layer-built samples were passed through a laminator. The samples were reversed and passed again. The lamination was repeated at least twice. The capacity of graphite used as anode active material was 280mAH/g, and the capacity of LiMn204 used as cathode active material was 110mAH/g. For balancing the capacities, the ratio of the anode active material to the cathode active material was kept in the range of 1 : 2.2-2.3.
I0 Extraction of Plasticizes and Activation of Electrodes:
Dibutyl phthalate which had been employed as plasticizes was extracted to form a micropore on the composite anode or cathode. The laminated electrodes were placed in a beaker, and ether was poured therein until the electrode was sunk. The first extraction was carried out over 30 minutes, and the second extraction was repeated in a fresh solvent. The electrodes in which plasticizes was removed were dried in a vacuum oven for 1 hour. After vacuum-drying, the electrodes were immersed in an electrolyte solution. The liquid electrolyte was impregnated into the mircropores of the electrodes. The liquid electrolytes having various compositions as shown in the following Examples were used to activate the electrodes. The activation time was longer than 1 hour.
Preparation of Polymer Electrolyte:
A terpolymer of 11 % by weight, which is composed of acrylonitrile, methyl methacrylate and styrene of 54%, 32%, 14% by mole, respectively, was dissolved in tetrahydrofuran, and a liquid electrolyte of 89 % by weight was added. To 100 parts by weight of the electrolyte solution was 6 parts by weight of silica added and the 3 0 solution was stirred to be completely dissolved. The resultant sticky polymer electrolyte solution was cast on a glass plate. The tetrahydrofuran solvent was completely removed to give a polymer electrolyte.
Preparation and Packa~in~ of Battery:
A polymer electrolyte film was sandwiched between an activated composite anode and an activated composite cathode, and the cell was laminated to obtain a lithium ion polymer battery. Finally, the lithium ion polymer battery was vacuum-packaged.
Example 1 An electrolyte solution was prepared by dissolving a lithium hexafluoroarsenate (LiAsFs) in the mixture of ethylene carbonate and dimethyl carbonate having the ratio by volume of 2 : 1, of which concentration was 1 M. A charge/discharge curves as shown in Fig. 2 were obtained by charging/discharging the lithium ion polymer battery at the current density of 0.5 mA/cai . The average voltage of the cell was about 3.8 V, and the capacity of the cell was 16.2 mAh (4.lmAh/c~ri ), and the decrease of capacities depending on charge/discharge cycles was low, which means that the cell has a good cyclability.
Example 2 A lithium ion polymer battery was prepared in the same manner as Example 1, except using an electrolyte solution composed of 1 M lithium hexafluorophosphate (LiPF6) and the ethylene carbonate/dimethyl carbonate having the ratio by volume of 2 : 1. Charge/discharge curves as shown in Fig. 3 were obtained by charging/discharging the lithium ion polymer battery at the current density of 0.25 mA/cai . The capacity of the cell was 20.1 mAh (S.OmAh/cni ).
Example 3 A lithium ion polymer battery was prepared in the same manner as Example 1, except using an electrolyte solution composed of 1 M lithium tetrafluoroborate (LiBF4) and the ethylene carbonate/dimethyl carbonate having the ratio by volume of 1 : 1. By charging/discharging the lithium ion polymer battery at a current density of 0.2 mA/cr~i , the capacity of the cell was measured to be 11.9 mAh (3.OroAh/cai ).
The present invention can be easily carried out by an ordinary skilled person in the art. Many modifications and changes may be deemed to be within the scope of the present invention as defined in the following claims.
Summary of the Invention The present invention relates to a method of preparing a lithium ion polymer battery which has a high capacity and a good cyclability as well as no exudation of liquid electrolyte. The lithium ion polymer battery according to the present invention is prepared by the steps of forming electrode films, laminating the electrode films on both surfaces of a grid or expanded metal so as to improve the interfacial adhesion between the electrode films, forming a polymer electrolyte film composed of a polymer, an electrolyte solution, and a filler, and laminating the composite anode, the polymer electrolyte and the composite cathode.
The lithium ion polymer batter according to the present invention comprises a carbon composite anode, a polymer electrolyte and a metallic oxide composite cathode.
The composite anode is prepared by forming an anode film by casting a composite anode slurry composed of an active material, a conducting material, a binder, a plasticizer and a solvent, laminating said anode film on both sides of a copper grid or a copper expanded metal to 2 0 prepare a composite anode, extracting plasticizer from the composite anode by immersing in a solvent, and activating the composite anode by immersing in an electrolyte solution to prepare an activated composite anode.
The polymer electrolyte film is made by casting a polymer electrolyte slung composed of a polymer matrix, a liquid electrolyte solution of a lithium salt and an aprotic solvent, a filer and a solvent.
The composite cathode is prepared by forming a cathode film by casting a composite cathode slurry composed of an active material, a conducting material, a binder, a plasticizer and a solvent, laminating said 3 0 cathode film on both sides of an aluminum grid or an aluminum expanded metal to prepare a composite cathode, extracting plasticizer from the composite cathode by immersing in a solvent, and activating the composite cathode by immersing in an electrolyte solution to prepare an activated composite cathode.
The activated composite anode/polymer electrolyte film/activated composite cathode is laminated to obtain a lithium ion polymer battery structure. The lithium ion polymer battery is vacuum-packaged using a vacuum packaging apparatus.
The present invention has an advantage that most of the steps for preparing the battery structure can be carried out under the atmosphere so as to avoid using an electrolyte solution which is sensitive to the moisture, and that the activating step is carried out under the anhydrous atmosphere. Also, this invention is to provide a lithium ion polymer battery having a high capacity and a good cyclability, which can prevent the exudation of liquid electrolyte.
Brief Description of the Drawings The present invention will be described with reference to the accompanying drawings of which:
Fig. 1 is a schematic diagram of the preparation process of a lithium ion polymer battery in accordance with the present invention.
Fig. 2 shows charge/discharge curves for a lithium ion polymer battery composed of a carbon composite anode/polymer electrolyte/metallic oxide composite cathode (electrolyte solution: 1M
lithium hexafluoroarsenate, ethylene carbonate/dimethyl carbonate) according to the present invention at a current density of 0.5 mA/cai .
Fig. 3 shows charge/discharge curves for a lithium ion battery composed of a carbon composite anode/polymer electrolyte/metallic oxide composite cathode (electrolyte solution: 1M lithium hexafluorophosphate, ethylene carbonate/dimethyl carbonate) according to the present invention at a current density of 0.25 mA/c~i .
Detailed Description of the Preferred Embodiment The important factors characterizing the performance of a secondary battery are energy density and cycle life. The energy density can be increased by effectivE:ly filling active material per unit weight or volume in a battery. The cycle life depends upon not only constituent elements of a battery, but also interfacial contacts between electrode materials.
In this invention, in on~er to maximize the amount of active material to be loaded in the Electrodes, electrode films are prepared by casting a composite electrode slurry composed of an active material, a conducting material, a binder°, a plasticizes and a solvent, and each electrode film is laminated under high pressure to prepare a composite l0 electrode. In order to improve the interfacial adhesion of the electrode films, the films are laminated on a metal grid or an expanded metal, but not on a metal foil. And, in order to prevent the exudation of liquid electrolyte, a polymer having a good compatibility with liquid electrolyte is employed.
The method of preparing a lithium ion polymer battery in accordance with the present invention comprises processes of preparing a composite anode, a polymer electrolyte and a composite cathode, fabricating a cell from the components, and packaging the cell.
The composite anode is prepared by forming an anode film by 2 0 casting a composite anode slurry composed of an active material, a conducting material, a binder, a plasticizes and a solvent, laminating said anode film on both sides of a~ copper grid or a copper expanded metal to prepare a composite anode, extracting plasticizes from the composite anode by immersing in a solvent, and activating the composite anode by 2 5 immersing in an electrolyte solution to prepare an activated composite anode.
The polymer electrolyte film is made by casting a polymer electrolyte slurry composed of a polymer matrix, a liquid electrolyte solution of a lithium salt and an aprotic solvent, a filler and a solvent.
3 o The composite cathode is prepared by forming a cathode film by casting a composite cathode slurry composed of an active material, a conducting material, a binder, a plasticizes and a solvent, laminating said cathode film on both sides of an aluminum grid or an aluminium expanded metal to prepare a composite cathode, extracting plasticizer from the composite cathode by immersing in a solvent, and activating the composite cathode by immersing in an electrolyte solution to prepare an activated composite cathode.
The activated composite anode/polymer electrolyte film/activated composite cathode is laminated to obtain a lithium ion polymer battery structure. The lithium ion polymer battery is vacuum-packaged using a vacuum packaging apparatus.
The anode active material used for preparing the composite anode l0 in the present invention is selected from the group consisting of petroleum coke, microbead carbon code, synthetic graphite, natural graphite and mixtures thereof. The cathode active material used for preparing the composite cathode in the present invention is selected from the group consisting of lithiated manganese tetraoxide (LiMnz04), 15 lithiated cobalt dioxide (LiCoC> z) and lithiated nickel dioxide (LiNi02), Polymer matrices used for preparing the polymer electrolyte according to the present invention are polyacrylonitrile, poly (vinylidene fluoride), poly (methyl methacrylate), poly (ethylene oxide), poly (vinyl chloride), poly (vinyl acetate), polystyrene and copolymers thereof. These 2 0 polymer matrices have a good compatibility with the liquid electrolyte which is used in this invention. The polymer electrolyte is prepared by mixing a polymer matrix with a liquid electrolyte, adding a ceramic filler to the polymer electrolyte solution, stirring the solution to be completely dissolved, and finally casting the obtained polymer electrolyte solution on 2 5 a glass plate.
The liquid electrolyte fior preparing the polymer electrolyte is composed of a lithium salt for an aprotic solvent. Examples of the lithium salt are lithium perchlorate ((LiC104), lithium trifluoromethansufonimide (LiN(CF3S02), lithium hexafluorophosphate 3 0 (LiPFs), lithium tetrafluorobor,ate (LiBF4), lithium trifluoromethansulfonate (LiCF2 S03), lithium hexafluoroarsenate (LiASFs) and mixtures thereof.
Examples of the aprotic solvent are ethylene carbonate, diethoxy ethane, dimethoxy ethane, dipropyl carbonate and mixtures thereof.
Ceramic fillers used for preparing the polymer electrolyte are silica, alumina, lithium aluminate, zeolite and mixtures thereof.
As the polymer matrices which have been employed in conventional methods of preparing a lithium ion polymer battery have a poor compatibility with a liquid electrolyte, the polymer matrices could cause the exudation of liquid electrolyte and low interfacial adhesion between electrodes and polymer electrolyte. By contrast, the present invention uses a polymer matrix which has a good compatibility with a liquid electrolyte, so that the interfacial adhesion between electrodes and electrolyte is improved. The lithium ion polymer battery in accordance with the present invention has a high capacity and a good cyclability as well as a safety of battery.
The present invention may be better understood by reference to the following examples which are intended for purposes of illustration and are not to be confined in any way limiting the scope of the present invention, which is defined in the claims appended hereto.
Examples Fig. 1 shows a schematic diagram of the preparation method of the lithium ion polymer battery according to the present invention. The method of preparing the lithium ion polymer battery comprises processes of preparing a composite anode, a polymer electrolyte, and a composite cathode, fabricating a cell from the components, and packaging the cell.
The detailed description of each process follows as below.
Preparation of Composite Anode Film:
A composite anode slurry for the lithium ion polymer battery was composed of an anode active material, a conducting material, a binder, a plasticizer and a solvent. A synthetic graphite was used as anode active material, and Super P battery carbon was used as conducting material, and poly(vinylidene fluoride-co-hexafluropropylene) was used as binder.
The process of preparing a composite anode from the components was _8_ shown in Fig. 1. The poly(vinylidene fluoride-co-hexafluropropylene) of 9.3 parts by weight was completely dissolved in acetone, thereafter, dibutyl phthalate of 22.7 parts by weight was added as plasticizer and stirred to give a homogeneous solution. To the solution, 2.6 parts by weight of Super P battery carbon and 65.4 parts by weight of graphite were added, thereby a black anode slurry with a high viscosity being prepared. The slurry was poured on a glass plate and cast with a doctor blade, and then the cast film was exposed to the atmosphere at room temperature for 30 minutes to evaporate acetone, thereafter, to give l0 a composite anode film.
Preparation of Composite Cathode Film:
A composite cathode ;slurry was also composed of a cathode active material, a conducting material, a binder, a plasticizer and a solvent. As cathode active material, LirvIn204 was used. Super P battery carbon was used as conducting material, and poly (vinylidene fluoride-co-hexafluropropylene) was used as binder. The process of preparing a composite cathode by using the components is shown in Fig.
1. The poly (vinylidene fluoride-co-hexafluropropylene) of 10.0 parts by weight was completely dissolved in acetone, and dibutyl phthalate of 19.5 2 0 parts by weight was added aind stirred to give a homogeneous solution.
To the solution, 5.5 parts by weight of Super P battery carbon and 65.1 parts by weight of LiMn204 in powder were added and mixed, a cathode slurry being prepared. The slurry was poured on a glass plate and coated with a doctor blade. 'f he coated film was exposed to the 2 5 atmosphere at room temperature for 30 minutes to give a composite cathode film.
Lamination of Electrodes:
The composite anode film and composite cathode film were 3 0 layer-built to form electrode/c:urrent collector electrode, to prepare a composite anode and a composite cathode, respectively. The current collector for the composite anode was a copper expanded metal and the _g_ current collector for the composite cathode was an aluminium expanded metal. The layer-built samples were passed through a laminator. The samples were reversed and passed again. The lamination was repeated at least twice. The capacity of graphite used as anode active material was 280mAH/g, and the capacity of LiMn204 used as cathode active material was 110mAH/g. For balancing the capacities, the ratio of the anode active material to the cathode active material was kept in the range of 1 : 2.2-2.3.
I0 Extraction of Plasticizes and Activation of Electrodes:
Dibutyl phthalate which had been employed as plasticizes was extracted to form a micropore on the composite anode or cathode. The laminated electrodes were placed in a beaker, and ether was poured therein until the electrode was sunk. The first extraction was carried out over 30 minutes, and the second extraction was repeated in a fresh solvent. The electrodes in which plasticizes was removed were dried in a vacuum oven for 1 hour. After vacuum-drying, the electrodes were immersed in an electrolyte solution. The liquid electrolyte was impregnated into the mircropores of the electrodes. The liquid electrolytes having various compositions as shown in the following Examples were used to activate the electrodes. The activation time was longer than 1 hour.
Preparation of Polymer Electrolyte:
A terpolymer of 11 % by weight, which is composed of acrylonitrile, methyl methacrylate and styrene of 54%, 32%, 14% by mole, respectively, was dissolved in tetrahydrofuran, and a liquid electrolyte of 89 % by weight was added. To 100 parts by weight of the electrolyte solution was 6 parts by weight of silica added and the 3 0 solution was stirred to be completely dissolved. The resultant sticky polymer electrolyte solution was cast on a glass plate. The tetrahydrofuran solvent was completely removed to give a polymer electrolyte.
Preparation and Packa~in~ of Battery:
A polymer electrolyte film was sandwiched between an activated composite anode and an activated composite cathode, and the cell was laminated to obtain a lithium ion polymer battery. Finally, the lithium ion polymer battery was vacuum-packaged.
Example 1 An electrolyte solution was prepared by dissolving a lithium hexafluoroarsenate (LiAsFs) in the mixture of ethylene carbonate and dimethyl carbonate having the ratio by volume of 2 : 1, of which concentration was 1 M. A charge/discharge curves as shown in Fig. 2 were obtained by charging/discharging the lithium ion polymer battery at the current density of 0.5 mA/cai . The average voltage of the cell was about 3.8 V, and the capacity of the cell was 16.2 mAh (4.lmAh/c~ri ), and the decrease of capacities depending on charge/discharge cycles was low, which means that the cell has a good cyclability.
Example 2 A lithium ion polymer battery was prepared in the same manner as Example 1, except using an electrolyte solution composed of 1 M lithium hexafluorophosphate (LiPF6) and the ethylene carbonate/dimethyl carbonate having the ratio by volume of 2 : 1. Charge/discharge curves as shown in Fig. 3 were obtained by charging/discharging the lithium ion polymer battery at the current density of 0.25 mA/cai . The capacity of the cell was 20.1 mAh (S.OmAh/cni ).
Example 3 A lithium ion polymer battery was prepared in the same manner as Example 1, except using an electrolyte solution composed of 1 M lithium tetrafluoroborate (LiBF4) and the ethylene carbonate/dimethyl carbonate having the ratio by volume of 1 : 1. By charging/discharging the lithium ion polymer battery at a current density of 0.2 mA/cr~i , the capacity of the cell was measured to be 11.9 mAh (3.OroAh/cai ).
The present invention can be easily carried out by an ordinary skilled person in the art. Many modifications and changes may be deemed to be within the scope of the present invention as defined in the following claims.
Claims (7)
1. A method for preparing a lithium ion polymer battery comprising:
a) providing an activated carbon composite anode by forming an anode film by casting a composite anode slurry comprising an anode active material, a conducting material, a binder, a plasticizer and a solvent;
laminating said anode film on both sides of a copper grid or a copper expanded metal to prepare a composite anode;
extracting plasticizer from the composite anode by immersing in a solvent;
and activating the composite anode by immersing in an electrolyte solution to prepare an activated composite anode;
b) providing a polymer electrolyte film by casting a polymer electrolyte slurry comprising a polymer matrix, a liquid electrolyte solution of a lithium salt and an aprotic solvent, a filler and a solvent, and removing the solvent;
c) providing an activated metallic oxide composite cathode by forming a cathode film by casting a composite cathode slurry comprising a cathode active material, a conducting material, a binder, a plasticizer and a solvent;
laminating said cathode film on both sides of an aluminum grid or an aluminum expanded metal to prepare a composite cathode;
extracting plasticizer from the composite cathode by immersing in solvent;
and activating the composite cathode by immersing in an electrolyte solution to prepare an activated composite cathode;
d) laminating said activated composite anode, polymer electrolyte and activated composite cathode; and e) vacuum packaging said lithium ion polymer battery using a vacuum packaging apparatus.
a) providing an activated carbon composite anode by forming an anode film by casting a composite anode slurry comprising an anode active material, a conducting material, a binder, a plasticizer and a solvent;
laminating said anode film on both sides of a copper grid or a copper expanded metal to prepare a composite anode;
extracting plasticizer from the composite anode by immersing in a solvent;
and activating the composite anode by immersing in an electrolyte solution to prepare an activated composite anode;
b) providing a polymer electrolyte film by casting a polymer electrolyte slurry comprising a polymer matrix, a liquid electrolyte solution of a lithium salt and an aprotic solvent, a filler and a solvent, and removing the solvent;
c) providing an activated metallic oxide composite cathode by forming a cathode film by casting a composite cathode slurry comprising a cathode active material, a conducting material, a binder, a plasticizer and a solvent;
laminating said cathode film on both sides of an aluminum grid or an aluminum expanded metal to prepare a composite cathode;
extracting plasticizer from the composite cathode by immersing in solvent;
and activating the composite cathode by immersing in an electrolyte solution to prepare an activated composite cathode;
d) laminating said activated composite anode, polymer electrolyte and activated composite cathode; and e) vacuum packaging said lithium ion polymer battery using a vacuum packaging apparatus.
2. The method as defined in claim 1 wherein said polymer matrix is selected from the group consisting of polyacrylonitrile, poly (vinylidene fluoride), poly (methyl methacrylate), poly (ethylene oxide), poly (vinyl chloride), poly (vinyl acetate), polystyrene and copolymers thereof.
3. The method as defined in claim 1 wherein said lithium salt is selected from the group consisting of lithium perchlorate (LiC1O4), lithium hexaflurophosphate (LiPF6), lithium tetrafluroborate (LiBF4), lithium trifluoromethansulfonate (LiCF3SO3), lithium hexafluoroarsenate (LiA S F6) and mixtures thereof.
4. The method as defined in claim 1 wherein said aprotic solvent is selected from the group consisting of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, diethoxy ethane, dimethoxy ethane, dipropyl carbonate, and mixtures thereof.
5. The method as defined in claim 1 wherein said filler is selected from the group consisting of silica, alumina, lithium aluminate, zeolite and mixtures thereof.
6. The method as defined in claim 1 wherein said cathode active material is selected from the group consisting of LiMn2O4, LiCoO2 and LiNiO2.
7. The method as defined in claim 1 wherein said anode active material is selected from the group consisting of petroleum coke, microbead carbon coke, synthetic graphite and natural graphite.
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| KR1019970039079A KR100220449B1 (en) | 1997-08-16 | 1997-08-16 | Lithium ion polymer secondary battery manufacturing method |
| KR97-39079 | 1997-08-16 |
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| JP4016464B2 (en) * | 1997-09-30 | 2007-12-05 | ソニー株式会社 | Gel electrolyte secondary battery |
| KR100428971B1 (en) * | 1999-04-21 | 2004-04-28 | 삼성에스디아이 주식회사 | Lithium polymer secondary battery and method for manufacturing the same |
| DE19952335B4 (en) * | 1999-10-29 | 2007-03-29 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | In electrochemical components usable pasty mass, thus formed layers, films, laminations and rechargeable electrochemical cells and methods for producing the layers, films and laminations |
| JP3611765B2 (en) * | 1999-12-09 | 2005-01-19 | シャープ株式会社 | Secondary battery and electronic device using the same |
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| US5540741A (en) | 1993-03-05 | 1996-07-30 | Bell Communications Research, Inc. | Lithium secondary battery extraction method |
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| US5894656A (en) * | 1997-04-11 | 1999-04-20 | Valence Technology, Inc. | Methods of fabricating electrochemical cells |
| US6020087A (en) * | 1998-01-30 | 2000-02-01 | Valence Technology, Inc. | Polymer electrolytes containing lithiated fillers |
-
1997
- 1997-08-16 KR KR1019970039079A patent/KR100220449B1/en not_active Expired - Lifetime
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1998
- 1998-07-30 US US09/126,487 patent/US6268087B1/en not_active Expired - Lifetime
- 1998-08-03 JP JP10218944A patent/JP3080227B2/en not_active Expired - Fee Related
- 1998-08-14 CA CA002245048A patent/CA2245048C/en not_active Expired - Fee Related
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| CA2245048A1 (en) | 1999-02-16 |
| KR100220449B1 (en) | 1999-09-15 |
| US6268087B1 (en) | 2001-07-31 |
| KR19990016509A (en) | 1999-03-05 |
| JP3080227B2 (en) | 2000-08-21 |
| JPH11111338A (en) | 1999-04-23 |
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