WO1999049531A1 - Polymeric gel electrolyte - Google Patents
Polymeric gel electrolyte Download PDFInfo
- Publication number
- WO1999049531A1 WO1999049531A1 PCT/IB1999/000374 IB9900374W WO9949531A1 WO 1999049531 A1 WO1999049531 A1 WO 1999049531A1 IB 9900374 W IB9900374 W IB 9900374W WO 9949531 A1 WO9949531 A1 WO 9949531A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- phase
- gel electrolyte
- polymeric gel
- battery
- lithium
- Prior art date
Links
- 239000011245 gel electrolyte Substances 0.000 title claims abstract description 94
- 239000012071 phase Substances 0.000 claims abstract description 70
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 51
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 239000007790 solid phase Substances 0.000 claims abstract description 22
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 12
- 239000007791 liquid phase Substances 0.000 claims abstract description 10
- 238000005191 phase separation Methods 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 20
- 229920006037 cross link polymer Polymers 0.000 claims description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims description 10
- 159000000002 lithium salts Chemical class 0.000 claims description 10
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 14
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 8
- 238000000635 electron micrograph Methods 0.000 description 8
- -1 naphtphylene Chemical group 0.000 description 8
- 239000011888 foil Substances 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 238000000149 argon plasma sintering Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000002076 thermal analysis method Methods 0.000 description 4
- 229910013872 LiPF Inorganic materials 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000001566 impedance spectroscopy Methods 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 229920000671 polyethylene glycol diacrylate Polymers 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 229940032159 propylene carbonate Drugs 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- HGWZSJBCZYDDHY-UHFFFAOYSA-N 1-prop-2-enoyloxydecyl prop-2-enoate Chemical compound CCCCCCCCCC(OC(=O)C=C)OC(=O)C=C HGWZSJBCZYDDHY-UHFFFAOYSA-N 0.000 description 1
- QEJVHBCEMCODQM-UHFFFAOYSA-N 1-prop-2-enoyloxydodecyl prop-2-enoate Chemical compound CCCCCCCCCCCC(OC(=O)C=C)OC(=O)C=C QEJVHBCEMCODQM-UHFFFAOYSA-N 0.000 description 1
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910003007 LixMnO2 Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GJOITEJHSGWDSJ-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.C1CCOC1 Chemical compound OC(=O)C=C.OC(=O)C=C.C1CCOC1 GJOITEJHSGWDSJ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000002023 wood Substances 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- 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
- H01M10/052—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
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- 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
- 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
- Y02E60/13—Energy storage using capacitors
Definitions
- the invention relates to a polymeric gel electrolyte.
- the invention further relates to a method of preparing such an polymeric gel electrolyte.
- the invention still further relates to a rechargeable lithium battery comprising such a polymeric gel electrolyte.
- a battery having a lithium-based anode, or lithium battery for short is an attractive source of electric energy for portable and/or hand-held electr(on)ic equipment in particular.
- a battery comprises a lithium-based anode, a cathode, and disposed therebetween, an electrolyte.
- an electrolyte In the case of primary lithium batteries, a highly ion-conductive liquid electrolyte can be suitably used.
- a rechargeable (also referred to as secondary) lithium battery such a liquid electrolyte gives, upon charging, rise to dendritic growth which in turn leads to short-circuits. Dendritic growth is less when a solid electrolyte is used.
- US Patent 5,501,921 discloses polymeric gel electrolytes comprising a cross-linked polymer and an ion-conductive liquid.
- the cross-linked polymer is obtained by cross-linking functionalized alkane monomers each having 2 to 100 carbon atoms and each having at least one polymerizable functional group.
- the total number of polymerizable functional groups is selected such that the polymer electrolyte is substantially chemically inert when brought into contact with a lithium anode.
- the polymeric gel electrolyte When employed in a rechargeable lithium battery, the polymeric gel electrolyte should have a high ion-conductivity, should not react with the lithium anode and should effectively suppress the dendritic growth which leads to short-circuits when the battery is repeatedly charged and discharged.
- a multi -phase polymeric gel electrolyte having an ion-conductivity of more than 1 mS/cm and comprising:
- a polymeric gel electrolyte suppresses dendritic growth is measured by repeatedly fully charging and discharging a rechargeable lithium battery having a capacity per unit surface area of at least 3 mAh/cm 2 and comprising said polymeric gel electrolyte disposed between a lithium metal anode and a lithium cobaltate cathode. If the said battery can be fully charged and discharged at least 20 times at at least a 0.2 C rate without short-circuiting, the solid phase of the polymeric gel electrolyte has a suitable microscopic network structure and the suppression of dendritic growth is considered to be effective.
- polymerizing a composition composed of 40 wt.% decanedioldiacrylate and 60 wt.% 1 M LiPF 6 in a 1:1 (v/v) mixture of ethylenecarbonate and diethylcarbonate produces a multi-phase polymeric gel electrolyte having an ion-conductivity of 1.2 mS/cm which, when employed in a lithium metal battery, allows said battery to be fully charged and subsequently discharged more than 40 times at a 0.2 C rate without short- circuiting.
- the invention is based on the recognition that the occurrence of dendritic growth leading to short-circuits is related to a degradation of the polymeric gel electrolyte.
- the degradation is due to a reaction between (neutral) lithium and the polymer occurring at the interface between polymer and liquid.
- the continuous solid phase of the multi-phase polymeric gel electrolyte in accordance with the invention has a microscopic network structure. It extends throughout the entire polymeric gel electrolyte in all directions thus giving the polymeric gel electrolyte a mechanical support similar to that obtained for a one-phase polymeric gel electrolyte. It is emphasized that, in the context of the invention, the term network structure refers to a network of microscopic dimensions and not to the network of covalently bonded atoms of a cross-linked polymer.
- the morphology of the microscopic network structure of the solid phase is an essential parameter with respect to the suppression of dendritic growth leading to short circuits because it determines the morphology of the liquid phase which is the complement to that of the solid phase.
- a suitable network structure is one which is composed of more or less spherical 4 particles having a characteristic diameter of 0.1 to 0.5 ⁇ m.
- network structures of spherical particles having a characteristic diameter of 0.5 ⁇ m to 1.0 ⁇ m or larger have by and large been found unsuitable. Obviously, apart from the size of the particles there should be a sufficient number of them. That is the network structure is to be sufficiently dense. The density of the microscopic network may be simply increased by increasing the weight ratio of solid to liquid phase.
- the liquid phase interpenetrates the solid phase. Because it is continuous, the lithium ions present therein are able to move throughout the polymeric gel electrolyte.
- the considerations regarding the weight ratio of polymer (solid phase) to ion- conductive liquid (liquid phase) in a multi-phase polymeric gel electrolyte are basically the same as those in the case of a one-phase polymeric gel electrolyte.
- the desired ion- conductivity (higher at larger weight ratios) is to be balanced against the desired mechanical strength (higher at smaller weight ratios).
- C 2 - Cioo alkane monomers are employed so as to avoid a chemical reaction between the lithium anode and the polymer.
- the functionalized alkane monomers may form a polydisperse or monodisperse composition. They may each be branched or unbranched, and, if desired, functionalized with a small number of other groups.
- a -CH 2 - unit may occasionally (not more than once per 5 carbon atoms of the alkane monomers in order to minimize reactivity with respect to lithium) be replaced by an -O- unit or an amylene unit such as phenylene, naphtphylene, biphenylene, and 4,4'-isopropylidenediphenyl.
- the alkane monomers are each at least functionalized with one polymerisable group.
- Suitable polymerisable groups include isocyanate, epoxy groups or ethylenically unsaturated groups such as vinyloxy, acrylyl, methacrylyl or styryl groups. Preferred are methacrylyl or acrylyl groups.
- the thiolene system is also suitable.
- the liquid phase predominantly comprises an ion-conductive liquid. Since the electrolyte is to be used in a lithium battery, a lithium salt is used which is dissolved in a solvent. 5
- Lithium salts known per se are suitable and include LiBr, LiSCN, Lil, LiCl, LiClO 4 , LiBF 4 , LiAsF 6 , LiCF 3 COO, LiCF 3 SO 3 , and LiPF 6 .
- Solvents which are non-aqueous, aprotic and polar can be suitably used and include solvents known per se such as 1,3-dioxalane, 2-methyltetrahydrofuran, ⁇ - butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, and, in particular carbonates such as diethylcarbonate, dimethylcarbonate, ethylenecarbonate and propylenecarbonate or mixtures thereof.
- solvents known per se such as 1,3-dioxalane, 2-methyltetrahydrofuran, ⁇ - butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, and, in particular carbonates such as diethylcarbonate, dimethylcarbonate, ethylenecarbonate and propylenecarbonate or mixtures thereof.
- the lithium salt concentration is preferably as large as possible since this will lead to a higher ion-conductivity. However, if the solubility limit is exceeded the ion- conductivity does not increase anymore.
- a suitable weight ratio of lithium salt to solvent is 0.6 to 1.0.
- the multi-phase polymeric gel electrolyte can be moulded into any shape such as a layer, provided on a substrate or prepared as a self-supporting film.
- the layer thickness is suitably selected between 5 - 200 ⁇ m, but is preferably between 25 - 100 ⁇ m, or better still between 30 - 60 ⁇ m.
- US 4,654,279 discloses a solid polymer electrolyte comprising an interpenetrating network of two co-continuous phases, one of these phases being a cross- linked polymer providing a mechanical support matrix, the other being an ion-conductive phase comprising a metal salt and a salt complexing liquid polymer.
- the polymers disclosed therein are not obtained from functionalized C - Cioo alkane monomers as a result of which, in accordance with US 5,501,921, the polymer electrolytes disclosed in US 4,654,279 are not chemically inert with respect to lithium.
- the ion-conductivity of the electrolytes disclosed therein is significantly lower than that of the electrolytes in accordance with the present invention.
- US 4,654,279 is completely silent on the problem of dendritic growth, let alone on solutions which may alleviate said problem.
- a rechargeable lithium battery is not explicitly disclosed.
- the polymer is a cross-linked polymer.
- cross-linked is understood to mean chemically cross-linked by means of chemical bonds as opposed to physically cross-linked due to entanglement of polymer chains.
- a cross- linked polymer provides excellent mechanical strength across a wide range of temperatures and for extended periods of time.
- a film made thereof is sufficiently flexible and compressible to take up changes in shape of the anode or cathode of a battery which may occur as a result of (dis)charging.
- a cross-linked polymer is obtainable by polymerizing monomers of which at 6 least a certain number is provided with more than one polymerizable group. Suitable cross- linked polymers include cross-linked epoxides, polyurethanes, poly(meth)acrylates, polystyrenes, and polyacrylonitriles.
- cross-linked poly(meth)acrylates are used which may be obtained by radiation-polymerizing corresponding (meth)acrylate monomers. Electron and gamma radiation are suitable and have the advantage that they do not require an initiator compound. However, photo-polymerisation using UN radiation in combination with an UN-sensitive initiator compound, examples of which are well known to those skilled in the art, are preferred. In order to obtain an electrolyte comprising a solid phase having a suitable microscopic network structure, the use of cross-linked polyacrylates and in particular polydiacrylates is preferred.
- the multi-phase polymeric gel electrolyte comprises 30 to 65 wt.% of a polymer obtainable by polymerizing alkane monomers represented by the formula (I)
- said polymers are capable of forming a multi-phase polymeric gel electrolyte comprising a solid phase having a microscopic network structure of a suitable morphology. If said alkane monomers are employed in the method in accordance with the invention described hereinbelow, a microscopic network structure in accordance with the invention is obtained.
- the inventor has observed that at least if the polymeric gel electrolyte of this preferred embodiment is used, the limiting factor with respect to service life of the battery in which said electrolyte is employed is the cycling efficiency.
- the ion-conductive liquid is a lithium salt dissolved in an alkane carbonate such as a mixture of diethylcarbonate and ethylenecarbonate.
- the invention further relates to a method of preparing a multi-phase polymeric gel electrolyte in accordance with the invention.
- the method comprises the steps of: (1) providing a one-phase polymerizable composition comprising: 7
- the one-phase polymerizable composition may be formulated as a liquid or paste which may be processed by means of conventional printing and coating techniques thus allowing, for example, self-supporting films and thin coatings to be routinely made.
- the composition undergoes phase separations.
- Phase separation is brought about by selecting alkane monomers which are miscible with the liquid in the monomeric state but not in the (pre)-polymeric state. In the art this is known as reaction- induced phase decomposition.
- reaction- induced phase decomposition In order to arrive at a suitable microscopic network structure, a phase decomposition of the spinodal type is preferred.
- suitable alkane monomers and polymerizable groups have already been described hereinabove. The conditions under which the polymerization is to be carried out depend on the particular polymerizable group used and are well known to those skilled in the art.
- the invention still further relates to a rechargeable lithium battery comprising a multi-phase polymeric gel electrolyte in accordance with the invention.
- a rechargeable lithium battery comprising a multi-phase polymeric gel electrolyte in accordance with the invention.
- suitable polymeric gel electrolytes and methods of manufacturing such suitable electrolytes are described hereinabove.
- Cathodes of a conventional type which include oxidic compounds capable of intercalating and deintercalating lithium may be suitably used.
- Preferred cathodic materials are LiCoO 2 , i.e. lithium cobaltate, LiNiO 2 , LiMn 2 O 4 and Li x MnO 2 (0 ⁇ x ⁇ 0.5).
- Suitable anodic materials are of a conventional type and include lithium alloys such as Li:Al, Li:Hg, Li:Pb, Li:Sn and Wood's alloys, and composite materials of lithium and a carbon compound such as polyacetylene or graphite. Because of its high energy density lithium metal is preferred. 8
- the battery (cell) may be of the cylindrical type, the sheet type, the button type or any other suitable conventional type.
- Fig. 1 shows, schematically, a cross-sectional view of a rechargeable lithium battery
- Fig. 2 shows the capacity C (in mAh) as a function of the number of charge/discharge cycles n (in number of times) of a rechargeable lithium battery in accordance with the invention
- Fig. 3 shows the loss tangent tan( ⁇ ) (in dimensionless units) as a function of the temperature T (in °C) of a multi-phase polymeric gel electrolyte.
- a quantity of said composition is applied between two glass plates, spread so as to form a film, and subsequently irradiated with UN light originating from a ImW/cm 2 TL lamp for 15 min, thereby forming a 100 ⁇ m thick film of a polymeric gel electrolyte.
- said composition becomes turbid and light-scattering, indicating that the 9 composition undergoes a phase separation (spinodal phase decomposition) so as to form a multi-phase polymeric gel electrolyte.
- the polymer of the electrolyte is a cross-linked poly(decandioldiacrylate).
- the ion-conductivity at 20 °C is 2.5 x 10 "3 S/cm as determined by complex impedance spectroscopy .
- Fig. 1 shows, schematically, a cross-sectional view of a rechargeable lithium battery of the button-cell type indicated by the reference sign 1. It is of a conventional design and comprises a laminate 15 of a lithium-based anode 10, a polymeric gel electrolyte 11, a lithium cobaltate cathode 12, a current collector 13 and a stainless steel plate 14.
- the laminate 15 is hermetically sealed from the environment by means of a housing 5 comprising an inner dish 2 and an outer dish 3, the inner and outer dish being electrically insulated from each other by means of the gasket 4.
- the laminate 15 is situated in the housing 5 under pressure, the pressure being provided by the metal dish spring washer 6.
- the curve labelled A in Fig. 2 shows the capacity C (in mAh) as a function of the number of charge/discharge cycles n (in number of times) of the rechargeable lithium 10 battery 1 of the present example.
- the charging current is 1.0 mA
- the charging cut-off voltage is 4.15 V
- the rate of charging is 0.2 C.
- the discharging current is 1.0 mA
- the discharging cut-off voltage is 3.2 V. After every charge and discharge cycle the battery is allowed to rest for 15 min.
- the curve A of Fig. 2 demonstrates that the battery can be fully charged and discharged at least 40 times without short-circuiting.
- the capacity of the battery decreases because the surplus lithium provided by the lithium anode 10 is exhausted, indicating that the service life of the battery is determined by the cycling efficiency. Since within its service life short-circuits are not observed, the operation of the battery is inherently safe. If after 50 cycles the battery is taken apart and the polymeric gel electrolyte inspected, substantial dendritic growth is not observed.
- the lithium metal anode is replaced by a composite carbon lithium anode supported by a copper cu ⁇ ent collector, the number of charge/discharge cycles is even higher, namely at least 80.
- Fig. 3 shows the loss tangent tan( ⁇ ) (in dimensionless units) as a function of the temperature T (in °C) for a number of multi-phase polymeric gel electrolytes.
- the curve labelled A corresponds to the polymeric gel electrolyte of the present example. Two well- separated peaks are observed, which demonstrates that a multi-phase polymeric gel electrolyte is obtained.
- the curve labelled P which corresponds to a sample consisting of pure cross-linked polymer exhibits, as expected, only one peak.
- Morphology of the microscopic network An electron micrograph (magnification factor of 4000) taken of the surface of the film shows a random pattern of bright areas on a continuous dark background characteristic of a multi -phase polymeric gel electrolyte which is phase-separated on a microscopic scale.
- the bright areas which correspond to parts of the microscopic network of the solid phase of the polymeric gel electrolyte, are more or less spherical with a characteristic diameter of 0.1 to 0.5 ⁇ m.
- the continuous dark background corresponds to a continuous liquid phase which interpenetrates the solid phase.
- the performance of the rechargeable lithium battery 1 of the present example demonstrates that the morphology observed in the electron micrograph is that of a microscopic network structure selected in accordance with the invention. 11
- EXAMPLE 1 is repeated with this difference that the one-phase polymerizable composition is composed of:
- a 100 ⁇ m thick film of a polymeric gel electrolyte obtained by polymerizing said polymerizable composition is flexible, self-supporting, turbid and light-scattering.
- the ion-conductivity at 20 °C of the film is 1.1 x 10 "3 S/cm as determined by complex impedance spectroscopy.
- buttons-cell 1 having a capacity of 4.5 mAh and comprising the polymeric gel electrolyte of the present example is manufactured and subsequently cycled in accordance with the method of EXAMPLE 1.
- the curve labelled B in Fig. 2 shows the capacity C (in mAh) as a function of the number of charge/discharge cycles n (in number of times) of the rechargeable lithium battery 1 of the present example.
- the charging current is 1.0 mA
- the charging cut-off voltage is 4.15 V
- the rate of charging is 0.2 C.
- the discharging current is 1.0 mA
- the discharging cut-off voltage is 3.2 V. After every charge and discharge cycle the battery is allowed to rest for 15 min.
- the curve B of Fig. 2 demonstrates that the battery can be fully charged and discharged at least 90 times without short-circuiting.
- the service life of the battery is determined by the cycling efficiency. Within this service life, the battery does not short- 12 circuit. If after 90 cycles the battery is taken apart and the polymeric gel electrolyte inspected, substantial dendritic growth is not observed.
- Fig. 3 shows the loss tangent tan( ⁇ ) (in dimensionless units) as a function of the temperature T (in °C) for a number of multi-phase polymeric gel electrolytes.
- the curve labelled B corresponds to the polymeric gel electrolyte of the example 2. Two well-separated peaks are observed, which demonstrates that a multi-phase polymeric gel electrolyte is obtained.
- the curve labelled P which corresponds to a sample consisting of pure cross-linked polymer exhibits, as expected, only one peak.
- An electron micrograph (magnification factor of 4000) taken of the surface of the film shows a solid phase of more or less spherical particles having a characteristic diameter of about 0.05 - 0.3 ⁇ m. Strands of particles having a length of, typically, a few micrometers are clearly observed. The strands are more or less straight and mutually parallel.
- the performance of the lithium battery demonstrates that the morphology shown in the electron micrograph corresponds to that of a microscopic network structure which is selected such that a multi-phase polymeric gel electrolyte in accordance with the invention is obtained.
- the composition is a one-phase, optically transparent mixture. During polymerisation, the composition undergoes phase separation (spinodal phase decomposition) so as to form a multi-phase polymeric gel electrolyte. At 20 °C, the ion-conductivity is 1.4 mS/cm. A 100 ⁇ m thick film is flexible, light-scattering and self-supporting.
- Rechargeable battery An embodiment of the button-cell 1 having a capacity of 4.5 mAh and comprising the polymeric gel electrolyte of the present example is manufactured and subsequently cycled in accordance with the method of example 1.
- the battery voltage is found to change erratically about a value of 3.95 V which is indicative of short-circuiting. As a result the battery cannot be charged to its full capacity. The battery is then taken apart so as to allow inspection of the polymeric gel electrolyte, said inspection revealing severe dendritic growth.
- the dendrites cause the battery to short-circuit.
- DMT A Dynamical Mechanical Thermal Analysis
- An electron micrograph (magnification factor of 4000) taken of the surface of the film prepared above shows a solid phase of more or less spherical particles having a characteristic diameter of about 0.5 - 5.0 ⁇ m.
- the performance of the lithium battery demonstrates that the microscopic network structure shown in the electron micrograph does not have a suitable mo ⁇ hology.
- the particles are too large to suppress dendritic growth effectively. Consequently, the multi-phase polymeric gel electrolyte of the present example is not in accordance with the invention.
- the polymerizable composition comprises 25 wt.% decandioldiacrylate. If use is made of a composition comprising 60 or 80 wt.% of decandioldimethacrylate the ion-conductivity of the corresponding polymeric gel electrolyte, 0.14 x 10 "3 and 8 x 10 "8 S/cm respectively, is significantly lower than 1 mS/cm rendering these electrolytes unsuitable in the context of the present invention.
- EXAMPLE 1 is repeated with this difference that the one-phase polymerizable composition is composed of:
- the one-phase polymerizable composition is optically transparent.
- a 100 ⁇ m thick film of a polymeric gel electrolyte comprising a cross-linked poly(polyethyleneglycoldiacrylate) is obtained.
- the composition being polymerized remains optically transparent, indicating that a one-phase polymeric gel electrolyte is formed.
- the ion-conductivity of the film is about 1.5 mS/cm.
- Rechargeable battery An embodiment of the button-cell 1 having a capacity of 4.5 mAh and comprising the polymeric gel electrolyte of the present example is manufactured and subsequently cycled in accordance with the method of example 1.
- the battery voltage is found to change erratically about a value of 3.95 V which is indicative of short-circuiting. As a result the battery cannot be charged to its full capacity.
- the battery is then taken apart so as to allow visual inspection of the polymeric gel electrolyte. Severe dendritic growth is observed confirming that the short-circuits are caused by dendritic growth. 15
- DMTA Dynamical Mechanical Thermal Analysis
- the loss tangent tan( ⁇ ) (in dimensionless units) plotted as a function of the temperature T (in °C) of the polymeric gel electrolyte of the present example results in a graph which shows one maximum only at about -80 °C. This demonstrates that the polymeric gel electrolyte of the present example is one-phase.
- An electron micrograph (magnification factor of 4000) of the surface of the film prepared above shows a homogeneous image indicating that the polymeric gel electrolyte of the present example is a one-phase polymeric gel electrolyte.
- the polymer and the ion- conductive liquid do not inte ⁇ enetrate on a microscopic scale but on a molecular scale.
- a 100 ⁇ m thick of a polymeric gel electrolyte obtained by polymerizing said polymerizable composition is flexible, self-supporting, turbid and light-scattering, indicating that the composition undergoes a phase separation so as to form a multi-phase polymeric gel electrolyte.
- the ion-conductivity at 20 °C of the film is 3 x 10 "3 S/cm as determined by complex impedance spectroscopy.
- DMTA shows two well-separated peaks at about -100 °C and -20 °C, which demonstrates that a multi-phase polymeric gel electrolyte is obtained.
Landscapes
- Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Secondary Cells (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99905121A EP0988657A1 (en) | 1998-03-23 | 1999-03-04 | Polymeric gel electrolyte |
JP54797599A JP2002500813A (en) | 1998-03-23 | 1999-03-04 | Polymer gel electrolyte |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP98200915 | 1998-03-23 | ||
EP98200915.1 | 1998-03-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999049531A1 true WO1999049531A1 (en) | 1999-09-30 |
Family
ID=8233502
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/IB1999/000374 WO1999049531A1 (en) | 1998-03-23 | 1999-03-04 | Polymeric gel electrolyte |
Country Status (4)
Country | Link |
---|---|
US (1) | US6406816B2 (en) |
EP (1) | EP0988657A1 (en) |
JP (1) | JP2002500813A (en) |
WO (1) | WO1999049531A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1156547A1 (en) * | 2000-05-15 | 2001-11-21 | Nisshinbo Industries, Inc. | Method of manufacturing a polymer gel electrolyte battery or capacitor |
JP2002190319A (en) * | 2000-12-19 | 2002-07-05 | Furukawa Electric Co Ltd:The | Solid state electrolyte and battery using the electrolyte |
US6686095B2 (en) | 1999-12-28 | 2004-02-03 | Kabushiki Kaisha Toshiba | Gel electrolyte precursor and chemical battery |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040126665A1 (en) * | 2002-12-26 | 2004-07-01 | Luying Sun | Gel polymer electrolyte battery and method of producing the same |
US8367254B2 (en) * | 2003-09-05 | 2013-02-05 | Lg Chem, Ltd. | Electrolyte for a high voltage battery and lithium secondary battery comprising the same |
KR100657225B1 (en) * | 2003-09-05 | 2006-12-14 | 주식회사 엘지화학 | Electrolyte solvent for improving safety of battery and lithium secondary battery comprising the same |
CN101014870B (en) * | 2004-06-25 | 2010-06-16 | 皇家飞利浦电子股份有限公司 | Radio frequency reception coil |
JP2006059635A (en) * | 2004-08-19 | 2006-03-02 | Sanyo Electric Co Ltd | Nonaqueous electrolyte battery |
EP3809510A4 (en) * | 2018-06-15 | 2021-08-11 | Lg Chem, Ltd. | Solid electrolyte membrane and all-solid-state battery comprising same |
CN111554974A (en) * | 2020-04-15 | 2020-08-18 | 中国人民解放军军事科学院防化研究院 | Preparation method of polyethylene glycol diacrylate-based gel electrolyte |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4654279A (en) * | 1986-07-10 | 1987-03-31 | The United States Of America As Represented By The Secretary Of The Navy | Interpenetrating-network polymeric electrolytes |
EP0555114A1 (en) * | 1992-01-20 | 1993-08-11 | Nippon Telegraph And Telephone Corporation | Solid polymer electrolyte and method of manufacture thereof |
US5501921A (en) * | 1994-04-25 | 1996-03-26 | Olsen; Ib I. | Fabrication of alkane polymer electrolyte |
US5593795A (en) * | 1995-05-01 | 1997-01-14 | Minnesota Mining And Manufacturing Company | Polymer electrolyte composition based upon thiol-ene chemistry |
EP0777287A2 (en) * | 1995-11-28 | 1997-06-04 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1991014294A1 (en) * | 1990-03-16 | 1991-09-19 | Ricoh Co., Ltd. | Solid electrolyte, electrochemical element comprising the same, and process for forming said electrolyte |
-
1999
- 1999-03-04 JP JP54797599A patent/JP2002500813A/en not_active Ceased
- 1999-03-04 EP EP99905121A patent/EP0988657A1/en not_active Ceased
- 1999-03-04 WO PCT/IB1999/000374 patent/WO1999049531A1/en not_active Application Discontinuation
- 1999-03-16 US US09/270,439 patent/US6406816B2/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4654279A (en) * | 1986-07-10 | 1987-03-31 | The United States Of America As Represented By The Secretary Of The Navy | Interpenetrating-network polymeric electrolytes |
EP0555114A1 (en) * | 1992-01-20 | 1993-08-11 | Nippon Telegraph And Telephone Corporation | Solid polymer electrolyte and method of manufacture thereof |
US5501921A (en) * | 1994-04-25 | 1996-03-26 | Olsen; Ib I. | Fabrication of alkane polymer electrolyte |
US5593795A (en) * | 1995-05-01 | 1997-01-14 | Minnesota Mining And Manufacturing Company | Polymer electrolyte composition based upon thiol-ene chemistry |
EP0777287A2 (en) * | 1995-11-28 | 1997-06-04 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6686095B2 (en) | 1999-12-28 | 2004-02-03 | Kabushiki Kaisha Toshiba | Gel electrolyte precursor and chemical battery |
US7267910B2 (en) | 1999-12-28 | 2007-09-11 | Kabushiki Kaisha Toshiba | Chemical battery containing gel electrolyte based on crosslinked epoxy compound having an alicyclic structure |
EP1156547A1 (en) * | 2000-05-15 | 2001-11-21 | Nisshinbo Industries, Inc. | Method of manufacturing a polymer gel electrolyte battery or capacitor |
KR20010104682A (en) * | 2000-05-15 | 2001-11-26 | 모치즈키 아키히로 | Electric components and methods for producting the same |
EP1300904A1 (en) * | 2000-05-15 | 2003-04-09 | Nisshinbo Industries, Inc. | Polymer gel electrolyte battery or double-layer capacitor and method for manufacturing the same |
SG100695A1 (en) * | 2000-05-15 | 2003-12-26 | Nisshin Spinning | Electrical component and method for manufacturing the same |
US6793692B2 (en) | 2000-05-15 | 2004-09-21 | Nisshinbo Industries, Inc. | Electrical component and method for manufacturing the same |
JP2002190319A (en) * | 2000-12-19 | 2002-07-05 | Furukawa Electric Co Ltd:The | Solid state electrolyte and battery using the electrolyte |
Also Published As
Publication number | Publication date |
---|---|
EP0988657A1 (en) | 2000-03-29 |
JP2002500813A (en) | 2002-01-08 |
US20010008732A1 (en) | 2001-07-19 |
US6406816B2 (en) | 2002-06-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0528557B1 (en) | Carbon/polymer composite electrode for use in a lithium battery | |
EP3261164B1 (en) | Gel polymer electrolyte, method for preparing same, and electrochemical device comprising same | |
US5834136A (en) | Method of preparing polymeric electrolytes | |
JP2003518172A (en) | Polymer electrolyte, battery cell containing polymer electrolyte, and method for producing polymer electrolyte | |
AU2001295953A1 (en) | Gel-type polymer electrolyte and use thereof | |
WO2002033765A2 (en) | Gel-type polymer electrolyte and use thereof | |
KR100371954B1 (en) | Vinylidene fluoride copolymer for gel-form solid electrolyte formation, solid electrolyte, and battery | |
JPH11176452A (en) | Solid battery | |
US6406816B2 (en) | Polymeric gel electrolyte | |
JP3580523B2 (en) | Ion conductive polymer gel electrolyte and battery containing the gel electrolyte | |
KR100444134B1 (en) | Polymer electrolyte and nonaqueous battery containing the same | |
JP4559587B2 (en) | Solid lithium polymer battery | |
JP2002359006A (en) | Secondary battery | |
JP4169134B2 (en) | Electrochemical element separator and its use | |
JP4152279B2 (en) | Negative electrode for lithium ion secondary battery and lithium ion secondary battery | |
JP3855288B2 (en) | Binder for electrode of secondary battery using non-aqueous electrolyte | |
JPH11130821A (en) | Vinylidene fluoride-based copolymer for forming gelatinous solid electrolyte, solid electrolyte and battery | |
SE518109C2 (en) | Polymer gel electrolyte, polymer battery cell with polymer electrolyte and use of polymer gel electrolyte and polymer battery cell | |
US7192675B2 (en) | Lithium polymer secondary battery | |
JP2005235683A (en) | Gel polymer electrolyte and lithium secondary battery | |
JP4465781B2 (en) | Polymer electrolyte and battery using the same | |
JP4427853B2 (en) | Secondary battery | |
JP3036492B2 (en) | Polymer gel electrolyte, method for producing the same, and polymer battery | |
KR100708213B1 (en) | Gel electrolyte and its gel electrolyte battery | |
KR20240035529A (en) | Copolymer electrolyte, method for producing same and solid state lithium secondary battery |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): JP |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1999905121 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref country code: JP Ref document number: 1999 547975 Kind code of ref document: A Format of ref document f/p: F |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWP | Wipo information: published in national office |
Ref document number: 1999905121 Country of ref document: EP |
|
WWR | Wipo information: refused in national office |
Ref document number: 1999905121 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1999905121 Country of ref document: EP |