CN103959511A - Electrochemical cells comprising nitrogen-containing polymers - Google Patents
Electrochemical cells comprising nitrogen-containing polymers Download PDFInfo
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- CN103959511A CN103959511A CN201280059796.7A CN201280059796A CN103959511A CN 103959511 A CN103959511 A CN 103959511A CN 201280059796 A CN201280059796 A CN 201280059796A CN 103959511 A CN103959511 A CN 103959511A
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- electrochemical cell
- polymer
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- monomeric unit
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- 229920000642 polymer Polymers 0.000 title claims abstract description 60
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 28
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004745 nonwoven fabric Substances 0.000 claims description 40
- 239000000853 adhesive Substances 0.000 claims description 31
- 230000001070 adhesive effect Effects 0.000 claims description 31
- 229920001577 copolymer Polymers 0.000 claims description 25
- 239000011572 manganese Substances 0.000 claims description 21
- 229910052748 manganese Inorganic materials 0.000 claims description 19
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 16
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 13
- 125000000962 organic group Chemical group 0.000 claims description 11
- 150000002736 metal compounds Chemical class 0.000 claims description 9
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- 239000001257 hydrogen Substances 0.000 claims description 5
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- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 4
- 125000004070 6 membered heterocyclic group Chemical group 0.000 abstract 1
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
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- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
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- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 5
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- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
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- 239000003381 stabilizer Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
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- 239000011147 inorganic material Substances 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- 238000004146 energy storage Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Chemical group 0.000 description 1
- 239000011574 phosphorus Chemical group 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000010703 silicon Chemical group 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 150000007984 tetrahydrofuranes Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
-
- 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/463—Separators, membranes or diaphragms characterised by their shape
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- 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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- 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
Abstract
Electrochemical cells comprise: (A) at least one cathode comprising at least one lithium ion-containing transition metal compound, (B) at least one anode, and at least one layer comprising (a) at least one polymer comprising monomer units comprising nitrogen-containing 5- or 6- membered heterocyclic aromatic structural units or comprising an organic radical which derives from a-aminophosphonic acid or from iminodiacetic acid, and (b) optionally at least one binder.
Description
The present invention relates to the electrochemical cell that comprises following assembly:
(A) at least one negative electrode, it comprises at least one containing the transistion metal compound of lithium ion,
(B) at least one anode, and
(C) at least one layer that comprises following component:
(a) at least one polymer that comprises monomeric unit, described monomeric unit comprises nitrogenous 5 Yuans or 6 element heterocycle aromatic structure unit or comprises the organic group derived from α-aminophosphonicacid or iminodiacetic acid, and
(b) at least one adhesive optionally.
The lithium ion battery group that the present invention relates in addition the purposes of electrochemical cell of the present invention and comprises at least one electrochemical cell of the present invention.
Energy storage has for a long time become day by day noticeable object.Electrochemical cell (for example battery pack or storage battery) can be used for store electrical energy.Till recently, so-called lithium ion battery group especially causes concern.It is better than conventional battery pack at some technical elements.For example, it can be used for generating the voltage of the battery pack acquisition that can not utilize based on aqueous electrolyte.
Thus, the material of manufacturing the material of electrode and especially manufacturing negative electrode plays an important role.
Under many situations, use hybrid transition metal oxide containing lithium, especially have layer structure the nickel-cobalt-Mn oxide containing lithium or can be transient metal doped containing galaxite with one or more.Yet the problem of many battery pack is still still to need improved cyclical stability.Specific, under the situation of those battery pack that comprise quite a high proportion of manganese, for example, under the situation having containing the electrochemical cell of galaxite electrode and graphite anode, conventionally relatively in the short time, observing serious capacitance loss.In addition, under the situation of selecting graphite anode as counterelectrode, the deposition of detectable element manganese on anode.It is believed that these are with respect to Li/Li
+the current potential that is less than 1V be deposited on manganese core on anode as catalyst in order to reduction decomposition electrolyte.Also think that this relates to the irreversible combination of lithium, this causes lithium ion battery group to lose gradually electric capacity.
WO2009/033627 openly can be used as the lamella of the separator of lithium ion battery group.It comprises non-woven fabric and embeds in non-woven fabric and the particle being comprised of organic polymer and possibility part inorganic material.Such separator can be avoided the short circuit being caused by Metal tree dendritic crystal.Yet, the unexposed any long-term circulation experiment of WO2009/033627.
WO2011/024149 is disclosed between negative electrode and positive electrode and comprises alkali metal as the lithium ion battery group of lithium, and this alkali metal is as the scavenger of not expecting accessory substance or impurity.In the production process of secondary cell Battery pack and in the later removal process of old and useless battery, owing to there being high response alkali metal, therefore must take suitable safe precaution measure.
Therefore, the object of the present invention is to provide following battery: even if it has, improve the life-span and wherein after some circulations, also do not observe element manganese deposition, or in its production process, can use safety problem degree lower and battery life is extended to the scavenger of expected degree than alkali metal.
The electrochemical cell that this object defines by introductory song place is realized, and this electrochemical cell comprises
(A) at least one negative electrode, it comprises at least one containing the transistion metal compound of lithium ion,
(B) at least one anode, and
(C) at least one layer that comprises following component:
(a) at least one polymer that comprises monomeric unit, described monomeric unit comprises nitrogenous 5 Yuans or 6 element heterocycle aromatic structure unit or comprises the organic group derived from α-aminophosphonicacid or iminodiacetic acid, and
(b) at least one adhesive optionally.
Negative electrode (A) comprises at least one containing the transistion metal compound of lithium ion, and for example those skilled in the art become known for the transistion metal compound (LiCoO in lithium ion battery group technology
2, LiFePO
4or lithium-galaxite).Negative electrode (A) preferably comprises containing the transition metal oxide of lithium ion as the transistion metal compound containing lithium ion, and this transition metal oxide comprises manganese as transition metal.
Comprise manganese as transition metal containing the transition metal oxide of lithium ion, in the context of the invention, be interpreted as not only meaning to have those oxides of at least one transition metal that is cationic form, and also mean to have at least two kinds of transition metal oxides that are cationic form those.In addition, in the context of the invention, term " containing the transition metal oxide of lithium ion " also comprises the compound that those also comprise at least one nontransition metal that is cationic form (for example aluminium or calcium) except lithium.
In preferred embodiments, manganese can+4 form oxidation state appears in negative electrode (A).Manganese in negative electrode (A) more preferably occurs with+3.5 to+4 form oxidation state.
Many elements are ubiquitous.For example, sodium, potassium and the chloride of some minimum ratio in nearly all inorganic material, all can be detected.In the context of the invention, ignore cation or the anion of the ratio that is less than 0.1 % by weight.Therefore, in the context of the invention, be less than to being considered as not containing sodium containing the hybrid transition metal oxide of lithium ion of 0.1 % by weight sodium any comprising.Correspondingly, in the context of the invention by any comprise be less than 0.1 % by weight sulfate ion containing the hybrid transition metal oxide of lithium ion, be considered as not containing sulfate radicals.
In one embodiment of the invention, the transition metal oxide containing lithium ion is the hybrid transition metal oxide that not only comprises manganese and also comprise at least one other transition metal.
In one embodiment of the invention, transistion metal compound containing lithium ion is selected from the iron lithium phosphate containing manganese, and be preferably selected from containing the spinelle of manganese and there is the transition metal oxide containing manganese of layer structure, especially thering is the hybrid transition metal oxide containing manganese of layer structure.
In one embodiment of the invention, the transistion metal compound containing lithium ion is selected from the compound that those have the lithium of hyperstoichiometry ratio.
In one embodiment of the invention, containing the spinelle of manganese, be selected from those of general formula (I):
Li
aM
1 bMn
3-a-bO
4-d (I)
Wherein variable defines by following separately:
0.9≤a≤1.3,0.95≤a≤1.15 preferably,
0≤b≤0.6, for example 0.0 or 0.5,
Wherein at selected M
1under the situation of=Ni, preferably: 0.4≤b≤0.55,
-0.1≤d≤0.4, preferably 0≤d≤0.1.
M
1be selected from the transition metal that one or more are selected from the period 1 of following element: Al, Mg, Ca, Na, B, Mo, W and the periodic table of elements.M
1be preferably selected from Ni, Co, Cr, Zn, Al, and M
1most preferably be Ni.
In one embodiment of the invention, the spinelle containing manganese is selected from formula LiNi
0.5mn
1.5o
4-dand LiMn
2o
4those.
In another embodiment of the present invention, the transition metal oxide containing manganese with layer structure is selected from those of formula (II):
Li
1+tM
2 1-tO
2 (II)
Wherein variable defines by following separately:
0≤t≤0.3 and
M
2be selected from the transition metal of the period 1 of Al, Mg, B, Mo, W, Na, Ca and the periodic table of elements, wherein transition metal or at least one transition metal are manganese.
In one embodiment of the invention, based on M
2total content, at least 30mol%, the preferred M of 35mol% at least
2be selected from manganese.
In one embodiment of the invention, M
2be selected from the combination of Ni, Co and Mn, it does not comprise a large amount of any other elements.
In another embodiment, M
2be selected from the combination of Ni, Co and Mn, it comprises at least one other a large amount of elements, for example Al of 1-10mol%, Ca or Na.
What in one embodiment of the invention, have a layer structure is selected from wherein M containing the transition metal oxide of manganese
2be selected from Ni
0.33co
0.33mn
0.33, Ni
0.5co
0.2mn
0.3, Ni
0.4co
0.3mn
0.4, Ni
0.4co
0.2mn
0.4and Ni
0.45co
0.10mn
0.45those.
In one embodiment, transition metal oxide containing lithium is the primary granule form that agglomerates into spherical secondary granule, the average particulate diameter of primary granule (D50) is 50nm-2 μ m, and the average particulate diameter of secondary granule (D50) is 2-50 μ m.
Negative electrode (A) can comprise a kind of or other composition.For example, negative electrode (A) can comprise and be the polymorphous carbon of conduction, for example, be selected from the mixture of graphite, carbon black, carbon nano-tube, Graphene or at least two kinds of above-mentioned substances.
In addition, negative electrode (A) can comprise one or more adhesives, for example one or more organic polymers.Suitable adhesive is for example organic (being total to) polymer.Suitable (being total to) polymer, be that homopolymers or copolymer for example can be selected from (being total to) polymer that can pass through anion, catalysis or free radical (being total to) polymerization acquisition, especially be selected from polyethylene, polyacrylonitrile, polybutadiene, polystyrene, and at least two kinds be selected from ethene, propylene, styrene, (methyl) acrylonitrile and 1, the copolymer of the comonomer of 3-butadiene, especially Styrene-Butadiene.Polypropylene is also suitable.Polyisoprene and polyacrylate are also suitable.Polyacrylonitrile particularly preferably.
In the context of the invention, polyacrylonitrile is interpreted as not only referring to polyacrylonitrile homopolymers, and refers to acrylonitrile and 1,3-butadiene or cinnamic copolymer.Optimization polypropylene nitrile homopolymers.
In the context of the invention, polyethylene is not only interpreted as referring to ceridust, and refer to the copolymer of ethene, this copolymer comprises at least 50mol% and is the ethene of copolymerized form and at least one other comonomer of 50mol% at the most, as alpha-olefin, as propylene, butylene (1-butylene), 1-hexene, 1-octene, 1-decene, 1-dodecylene, 1-amylene, and isobutene, vinyl-arene, as styrene, and (methyl) acrylic acid, vinyl acetate, propionate, (methyl) acrylic acid C
1-C
10arrcostab, particularly methyl acrylate, methyl methacrylate, ethyl acrylate, EMA, n-butyl acrylate, 2-EHA, n-BMA, 2-Ethylhexyl Methacrylate, and maleic acid, maleic anhydride and itaconic anhydride.Polyethylene can be HDPE or LDPE.
In the context of the invention, polypropylene is not only interpreted as referring to homo-polypropylene, and be interpreted as referring to the copolymer of propylene, this copolymer comprises at least 50mol% and is the propylene of copolymerized form and at least one other comonomer of 50mol% at the most, as ethene and alpha-olefin, as butylene, 1-hexene, 1-octene, 1-decene, 1-dodecylene and 1-amylene.Polypropylene is preferably isotaxy or isotactic polypropylene substantially.
In the context of the invention, polystyrene is not only interpreted as referring to cinnamic homopolymers, and is interpreted as referring to and acrylonitrile 1,3-butadiene, (methyl) acrylic acid, (methyl) acrylic acid C
1-C
10arrcostab, divinylbenzene, particularly 1,3-divinylbenzene, 1, the copolymer of 2-diphenylethlene and AMS.
Another preferred adhesive is polybutadiene.
Other suitable adhesive is selected from polyoxyethylene (PEO), cellulose, carboxymethyl cellulose, polyimides and polyvinyl alcohol.
In one embodiment of the invention, adhesive is selected from mean molecule quantity M
wbe 50000 to 1000000g/mol, preferably to those (being total to) polymer of 500000g/mol.
Adhesive can be crosslinked or uncrosslinked (being total to) polymer.
In particularly preferred embodiment of the present invention, adhesive is selected from (being total to) polymer of halogenation, (being total to) polymer of particularly fluoridizing.Halogenation or (being total to) polymer of fluoridizing are interpreted as referring to those (being total to) polymer that comprise at least one (copolymerization) monomer that is copolymerized form, should have at least one halogen atom or at least one fluorine atom by (copolymerization) monomer per molecule, preferably per molecule has at least two halogen atoms or at least two fluorine atoms.
Example is polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, polyvinylidene fluoride (PVdF), tetrafluoraoethylene-hexafluoropropylene copolymer, vinylidene difluoride-hexafluoropropylene copolymer (PVdF-HFP), vinylidene fluoride-TFE copolymer, perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, vinylidene fluoride-chlorotrifluoroethylene and ethene-chlorine fluoride copolymers.
Suitable adhesive is polyvinyl alcohol and halogenation (being total to) polymer especially, as polyvinyl chloride or polyvinylidene chloride, and (being total to) polymer of particularly fluoridizing, as polyvinyl fluoride, particularly polyvinylidene fluoride and polytetrafluoroethylene.
In addition, negative electrode (A) can have other conventional composition itself, output conductor for example, and it can wire, metal grate, woven wire, drawn metal, sheet metal or metal in foil form structure.Suitable metal paper tinsel is especially aluminium foil.
In one embodiment of the invention, the thickness based on no-output conductor, the thickness of negative electrode (A) is 25-200 μ m, preferred 30-100 μ m.
Electrochemical cell of the present invention comprises at least one anode (B) in addition.
In one embodiment of the invention, the anode that the optional free carbon of anode (B) forms and comprise Sn or the anode of Si.The anode consisting of carbon can be selected from two or more mixture of (for example) hard carbon, soft carbon, Graphene, graphite (especially graphite), intercalated graphite and above-mentioned carbon.The anode that comprises Sn or Si can be selected from (for example) nanoparticle Si or Sn powder, Si or Sn fiber, carbon-Si or carbon-Sn composite material and Si-metal or Sn-metal alloy.
Anode (B) can have one or more adhesives.Selected adhesive can be one or more in the above-mentioned adhesive of appointment in the context that negative electrode (A) illustrates.
In addition, anode (B) can have other conventional composition itself, output conductor for example, and it can wire, metal grate, woven wire, drawn metal or metal forming or sheet metal formal construction.Suitable metal paper tinsel is especially Copper Foil.
In one embodiment of the invention, the thickness based on no-output conductor, the thickness of negative electrode (B) is 15-200 μ m, preferred 30-100 μ m.
Electrochemical cell of the present invention comprises (C) at least one layer (also referred to as layer (C)) in addition, this layer comprises (a) at least one polymer that comprises monomeric unit (also referred to as polymer (a)), and described monomeric unit comprises nitrogenous 5 Yuans or 6 element heterocycle aromatic structure unit or comprises the organic group derived from α-aminophosphonicacid or iminodiacetic acid; And comprise (b) optionally at least one adhesive, also referred to as adhesive (b).
Nitrogenous 5 Yuans or 6 element heterocycle aromatic structure unit are that those skilled in the art are known in principle.The construction unit that it can be unit price or multivalence (for example divalence or trivalent), monocycle or encircles more, is substituted or be unsubstituted.The example of such construction unit is:
Wherein by the atom indicating structure unit of * mark, introduce the site in polymer.Preferably imidazole radicals is as construction unit.Unit price construction unit can be directly or via divalence bond element bond to main polymer chain, divalence construction unit can be introduced in main polymer chain simultaneously.
In a preferred embodiment of the invention, polymer (a) is stored in layer (C) and comprises monomeric unit, described monomeric unit comprises nitrogenous 5 Yuans or 6 element heterocycle aromatic structure unit or comprises the organic group derived from α-aminophosphonicacid or iminodiacetic acid, and those monomeric units are selected from following monomeric unit:
Wherein X is O, S or NR, and R is hydrogen or C
1-C
4alkyl, for example methyl, ethyl, n-pro-pyl or normal-butyl.
In particularly preferred embodiments, monomeric unit is N-vinyl imidazole.
Be stored in the polymer (a) of layer in (C) and can be following homopolymers: under each situation, all only comprise and a kind ofly comprise nitrogenous 5 Yuans or 6 element heterocycle aromatic structure unit or comprise the monomeric unit derived from the organic group of α-aminophosphonicacid or iminodiacetic acid.In addition, be stored in the polymer (a) of layer in (C) and can be following copolymer: except at least one comprises nitrogenous 5 Yuans or 6 element heterocycle aromatic structure unit or comprises the monomeric unit derived from the organic group of α-aminophosphonicacid or iminodiacetic acid, also comprise at least one other monomeric unit.Other monomeric unit of copolymer can be any known monomers unit that can copolymerization together with last monomeric unit in principle.
Can to comprise gross mass ratio based on polymer (a) be comprising of 100 % by weight of 0.5 % by weight-at the most (preferably at least 5 % by weight, more preferably at least 20 % by weight, even more preferably at least 40 % by weight and at least 50 % by weight especially) nitrogenous 5 Yuans or 6 element heterocycle aromatic structure unit or comprise the monomeric unit derived from the organic group of α-aminophosphonicacid or iminodiacetic acid to be stored in the polymer (a) of layer in (C).
In a preferred embodiment of the invention, be stored in the copolymer that the polymer (a) of layer in (C) is the monomeric unit that comprises N-vinyl imidazole and NVP.Known packets is containing the copolymer of N-vinyl imidazole and NVP.For example, the cross-linked copolymer that comprises N-vinyl imidazole and NVP with
hM buys from BASF, and all soluble in all standard solvent.Yet the copolymer solution that comprises NVP and N-vinyl imidazole also has commercially available, for example, from BASF's
hP56K or
hP66K.
According to having discussed the character that is stored in the polymer (a) in layer (C) above, this polymer can multi-formly be stored in layer (C).Preferably by soluble polymer (for example, from the cross-linked copolymer of BASF
hM) with particle form, mix in layer (C), simultaneously corresponding soluble polymer can be processed into film or be uniformly applied in layer (C), for example, put on the carrier material that can be organic or inorganic source or wherein.For example, available packages containing the copolymer solution of NVP and N-vinyl imidazole (for example
hP66K or
vPI55K72W solution) process for example, separator or its composition described in (dipping or spraying) WO2009/033627, to obtain through modification separator, utilize this separator can produce electrochemical cell of the present invention.Also can use the inorganic or organic granular that is used in the polymer (a) of particulate form and WO2009/033627 to produce correspondingly through modification non-woven fabric.Equally also can by crosslinking technology (for example by vinyl imidazole is grafted on aromatic-polyether ketone or by by the copolymer grafted of NVP and N-vinyl imidazole to polyethylene glycol) by the first polymer (a) or comprise nitrogenous 5 Yuans or 6 element heterocycle aromatic structure unit or the monomeric unit chemistry that comprises derived from the organic group of α-aminophosphonicacid or iminodiacetic acid is attached to other polymer, to obtain novel polymeric (a).
In one embodiment of the invention, in electrochemical cell of the present invention, the polymer being stored in layer (C) is particulate form, is form of film or is uniformly distributed in layer (C).Preferably, the polymer being stored in layer (C) is particulate form.In the context of the invention, the average particulate diameter (D50) that is the polymer of particulate form can be 0.05-100 μ m, preferably 0.5-10 μ m, more preferably 2-6 μ m.
The part by weight of polymer (a) in the gross mass of layer (C) can be up to 100 % by weight.Preferably, the part by weight of polymer (a) in the gross mass of layer (C) is at least 5 % by weight, more preferably 40-80 % by weight; The part by weight of polymer (a) in the gross mass of layer (C) is especially 30-50 % by weight.
In one embodiment of the invention, adhesive (b) is selected from those as to the adhesive of being set forth for the adhesive of negative electrode (A).
In a preferred embodiment of the invention, layer (C) comprises adhesive (b), it is selected from and comprises following polymer: polyvinyl alcohol, styrene butadiene rubbers, polyacrylonitrile, carboxymethyl cellulose and fluoridize (being total to) polymer, be especially selected from styrene butadiene rubbers and fluoridize (being total to) polymer.
In one embodiment of the invention, adhesive (b) and for negative electrode and identical separately for the adhesive of anode (if existence).
In another embodiment, adhesive (b) is different from for the adhesive of negative electrode (A) and/or for the adhesive of anode (B), or for the adhesive of anode (B) from different for the adhesive of negative electrode (A).
In one embodiment of the invention, the average thickness of layer (C) is 0.1-250 μ m, preferably 1-100 μ m and more preferably 5-30 μ m.
Layer (C) is preferably the layer of non-conducting electric current, i.e. electrical insulator.Secondly, layer (C) is preferably and allows ion (Li especially
+ion) layer of migration.Preferably, layer (C) space in electrochemical cell of the present invention is arranged between negative electrode and positive electrode.
In electrochemical cell, anode directly contacts and can cause short circuit with negative electrode, and this prevents by introducing separator conventionally.
In another embodiment of the present invention, in electrochemical cell of the present invention, layer (C) is separator.
Except polymer (a) and optional adhesive (b), layer (C) also can have do not damage it must porosity and other composition of ion permeability, for example guarantee the carrier material of the improvement stability of layer (C), for example fiber or non-woven fabric.Or or in addition, layer (C) also can comprise at least one porous polymer layer, for example polyolefin film, especially polyethylene or polypropylene screen.Polyolefin film again can be from one or more layers of formation.Itself can meet the function of separator conventionally porous polyolefin membrane or non-woven fabric.Layer (C) can comprise equally and is essentially particle inorganic or organic and for example, in () WO2009/033627 appointment.
In one embodiment of the invention, in electrochemical cell of the present invention, layer (C) comprises non-woven fabric (c) in addition.
Non-woven fabric (c) can produce from inorganic or organic material.
The example of organic non-woven fabric is polyester nonwoven thing, especially PETG non-woven fabric (PET non-woven fabric), polybutylene terephthalate (PBT) non-woven fabric (PBT non-woven fabric), polyimides non-woven fabric, polyethylene and polypropylene nonwoven, PVdF non-woven fabric and PTFE non-woven fabric.
The example of inorganic non-woven fabric is glass fibre non-woven fabric and ceramic fibre non-woven fabric.
According to the composition of layer (C), its can be only for example, for example, by () polymer (a) (porous membrane of polymer (a) or be the polymer (a) of particulate form) and adhesive (b) forms or the polyester nonwoven thing that is distributed in wherein by polymer (a) uniform particles forms.Under these situations, layer (C) self can be as the separator in electrochemical cell of the present invention and therefore can be at least one side covered cathode (A) or anode (B).In addition, also layer (C) can be applied to available battery pack separator (for example porous polyolefin membrane or non-woven fabric) conventionally, so that layer (C) covers separator at least one side.Also layer (C) can be applied to negative electrode or anode with thin layer form, and consequent electrochemical cell of the present invention can comprise porous polyolefin membrane in addition as separator.
In another embodiment of the present invention, in electrochemical cell of the present invention, layer (C) covered cathode (A) or separator or anode (B) at least one side.
The present invention provides the purposes of polymer (a) as described above in addition, it is for generation of electrochemical cell, especially as described above electrochemical cell of the present invention, this polymer (a) comprises monomeric unit, and described monomeric unit comprises 5 Yuans or 6 element heterocycle aromatic structure unit or comprises the organic group derived from α-aminophosphonicacid or iminodiacetic acid.
Being stored in the assembling that layer (C) in electrochemical cell of the present invention depends on that its structure also can be independent of electrochemical cell of the present invention produces with semi-finished product form, and in later phases part as electrochemical cell in the electrochemical cell between battery pack manufacturer introducing negative electrode and positive electrode, for example, for example, as finished product separator or together with typical battery stack separator (PET non-woven fabric or porous polyolefin membrane).
Electrochemical cell of the present invention also can have itself conventional composition (for example conducting salt, non-aqueous solvent) and cable connection and shell.
In one embodiment of the invention, electrochemical cell of the present invention comprises at least one non-aqueous solvent that at room temperature can be liquid or solid, is at room temperature preferably liquid and be preferably selected from polymer, ring-type or non-annularity ether, ring-type or non-annularity acetal, ring-type or non-annularity organic carbonate and ionic liquid.
The example of suitable polymers is PAG especially, preferably poly-C
1-C
4aklylene glycol, especially polyethylene glycol.Polyethylene glycol can comprise at the most 20mol%, and one or more are the C of copolymerized form
1-C
4aklylene glycol.PAG is preferably the PAG of dimethyl or diethyl end-blocking.
Suitable PAG, the molecular weight M of especially suitable polyethylene glycol
wcan be at least 400g/mol.
Suitable PAG, the molecular weight M of especially suitable polyethylene glycol
wcan be 5000000g/mol at the most, preferably 2000000g/mol at the most.
The example of suitable non-annularity ether is for example diisopropyl ether, di-n-butyl ether, 1,2-dimethoxy-ethane, 1,2-diethoxyethane, preferably 1,2-dimethoxy-ethane.
The example of suitable cyclic ether is oxolane and Isosorbide-5-Nitrae-bis-
alkane.
The example of suitable non-annularity acetal is for example dimethoxymethane, diethoxymethane, 1,1-dimethoxy-ethane and 1,1-diethoxyethane.
The example of suitable cyclic acetal is 1,3-bis-
alkane, especially DOX.
The example of suitable non-annularity organic carbonate is dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate.
The example of suitable cyclic organic carbonates is general formula (X) and compound (XI):
R wherein
1, R
2and R
3can be identical or differently, and be selected from separately hydrogen and C
1-C
4alkyl, as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl and the tert-butyl group, wherein R
2and R
3it is not all preferably the tert-butyl group.
In particularly preferred embodiments, R
1for methyl, R
2and R
3hydrogen or R respectively do for oneself
1, R
2and R
3the hydrogen of respectively doing for oneself.
Another preferred cyclic organic carbonates is the vinylene carbonate of formula (XII).
Preferably use and be called the solvent without aquosity, water content is 1ppm to 0.1 % by weight, and it can pass through Karl Fischer titration measuring.
Electrochemical cell of the present invention further comprises at least one conducting salt.Suitable conducting salt is lithium salts especially.The example of suitable lithium salts is LiPF
6, LiBF
4, LiClO
4, LiAsF
6, LiCF
3sO
3, LiC (C
nf
2n+1sO
2)
3, imidization lithium is as LiN (C
nf
2n+1sO
2)
2, the integer that wherein n is 1-20, LiN (SO
2f)
2, Li
2siF
6, LiSbF
6, LiAlCl
4, and general formula (C
nf
2n+1sO
2)
mthe salt of XLi, wherein m by as give a definition:
When X is selected from oxygen and sulphur, m=1,
When X is selected from nitrogen and phosphorus, m=2,
When X is selected from carbon and silicon, m=3.
Preferred conducting salt is selected from LiC (CF
3sO
2)
3, LiN (CF
3sO
2)
2, LiPF
6, LiBF
4, LiClO
4, LiPF particularly preferably
6and LiN (CF
3sO
2)
2.
Electrochemical cell of the present invention comprises can the have any shape shell of (for example cube or cylindrical) in addition.In another embodiment, electrochemical cell of the present invention has prismatic shape.In a kind of version, shell used is the metal-plastic laminated film that is treated to parcel.
Electrochemical cell of the present invention produce about 4.8V at the most high voltage and because of high-energy-density and excellent stability noticeable.More particularly, electrochemical cell of the present invention is noticeable because only lose few electric capacity in repetitive cycling process.
The present invention provides the purposes of electrochemical cell of the present invention in lithium ion battery group in addition.The present invention provides the lithium ion battery that comprises at least one electrochemical cell of the present invention group in addition.Electrochemical cell of the present invention for example, can be connected in series or be connected in parallel combination with one another in lithium ion battery group of the present invention with ().Be connected in series preferably.
The present invention provides in addition as the purposes of the invention described above electrochemical cell, and it is for motor vehicles, bicycle, aircraft, ship or fixed energies storage device by electric motor operated.
Therefore, the present invention also provides the purposes of lithium ion battery group of the present invention in addition, and it is for device, mobile device especially.The example of mobile device is vehicle, for example automobile, bicycle, aircraft or waterborne vehicles (for example boat or ship).Other example of mobile device is portable those, and for example computer (especially notebook), phone or (for example) are from the electric power tool of building industry, the especially screwdriver of rig, battery driven or the nailing machine of battery driven.
The use of lithium ion battery group of the present invention in device produces following advantage: extend and recharge previous running time and less at the capacitance loss in extending process running time.If wish utilization has compared with the electrochemical cell of low energy densities, realize phase equal travel time, the weight that must accept electrochemical cell is higher.
By not limiting following instance of the present invention, explain the present invention.
Unless clearly indicate in addition, otherwise the numerical value representing with % is all based on % by weight.
I.1 the generation of separator of the present invention (S.1)
The cross-linked copolymer of the vinyl pyrrolidone that is 10:90 by ratio (VP) and N-vinyl imidazole (VI) is (from BASF's
hM) in AFG fluid bed counter-jet mill, be crushed to particle diameter and be less than 8 μ m (* 10=1.2 μ m, * 50=4.7 μ m, * 90=7.9 μ m).By laser diffraction technology utilization from Malvern Instruments GmbH, Herrenberg, Germany Mastersizer with powder type, measure particle size distribution.
From glass fibre non-woven fabric (Whatman, thickness is 260 μ m), stamp out the dish that diameter is 13mm, and it is dried to some hours at 120 ℃ in drying box.Glass fibre non-woven fabric dish be transferred to argon filling glove box thereafter.Each glass fibre non-woven fabric dish is divided into two parts so that the glass fibre non-woven fabric dish that thickness is 260 μ m produce two separately thickness be the glass fibre non-woven fabric dish of approximately 130 μ m.By the cross-linked copolymer of the VI previously having ground and VP (90:10) (
hM) be uniformly distributed on the whole region between two fiberglass disc, to form, there is (for example) about 5-10mg/cm
2's
the glass fibre non-woven fabric of the relative area coverage rate of HM/
hM/ glass fibre non-woven fabric interlayer.
I.2 the generation of separator of the present invention (S.2)
The aqueous solution of no cross-linked copolymer by evaporating cocnentration factor rate is 45:55 yesterday vinyl pyrrolidone and N-vinyl imidazole in drying box at 40 ℃ is (from BASF's
vPI55K72W).With Mortar and pestle pulverize roughly residue and subsequently in vacuumizing drier through P
2o
5dry 2 days.Under argon protective gas, utilize agate mortar fine gtinding dried residue until particle diameter lower than approximately 20 μ m.From glass fibre non-woven fabric (Whatman, thickness is 260 μ m), stamp out the dish that diameter is 13mm, and it is dried to some hours at 120 ℃ in drying box.Glass fibre non-woven fabric dish be transferred to argon filling glove box thereafter.Each glass fibre non-woven fabric dish is divided into two parts so that the glass fibre non-woven fabric dish that thickness is 260 μ m produce two separately thickness be the glass fibre non-woven fabric dish of approximately 130 μ m.By what previously ground
vPI55K72W is uniformly distributed on the whole region between two fiberglass disc, to form, has (for example) about 5-10mg/cm
2's
the glass fibre non-woven fabric of the relative area coverage rate of VPI55K72W
vPI55K72W/ glass fibre non-woven fabric interlayer.
I.3 the generation of separator of the present invention (S.3)
By 1.9 example I .1 produce in advance meticulous
hM and 0.2g50 % by weight styrene butadiene rubbers water-based emulsion (particle mean size: 190nm; Glass transition temperature :-10 ℃; Adhesive 20-01) and 8ml water combination, can stirred suspension to produce, and stir about 1h.By thus obtained suspension equably cutter be applied on the PET non-woven fabric of buying from APODIS Filtertechnik OHG with " PES20 " non-woven fabric, and will be through coated non-woven thing dried overnight under room temperature.After dry, obtain under each situation
hM coverage rate is all about 5-10mg/cm
2non-woven fabric., stamp out dish that diameter be 13mm, and it is again dried to 16 hours at 120 ℃ in vacuum drying chamber thereafter.
Subsequently, these dishes are transferred to argon filling glove box.
I.4 the generation of non-separator of the present invention (C-S.4)
Repeat in a similar manner under the same conditions example I .1 or experiment I.2, difference is now need not
hM or
vPI55K72W filled glass fiber non-woven fabric, is not used but do not change ground, to obtain comparison separator C-S.4.
I.5 the generation of non-separator of the present invention (C-S.5)
Repeat under the same conditions the experiment of example I .3, difference is not use
hM coating PET non-woven fabric, is not used but do not change ground, to obtain comparison separator C-S.5.
II. the generation of electrochemical cell and test thereof
All the time use with bottom electrode:
Negative electrode (A.1): all use lithium-nickel-manganese spinel electrodes under each situation, it produces by following: in band screw lid container, following material is mixed with each other:
85％LiMn
1.5Ni
0.5O
4
6%PVdF, with Kynar
2801 buy from Arkema Group,
6% carbon black, BET surface area is 62m
2/ g, buys from Timcal with " Super P Li ",
3% graphite, buys from Timcal with KS6.
When stirring, add enough 1-METHYLPYRROLIDONEs, to obtain, containing the sticky plaster of agglomerate, do not stick with paste.Mixture is stirred 16 hours.
Subsequently thus obtained cream paste cutter is applied on the aluminium foil that 20 μ m are thick and at 120 ℃ and is dried 16 hours in vacuum drying chamber.After dry, the thickness of coating is 30 μ m.Subsequently, stamp out the disc section that diameter is 12mm.
Anode (B.1): in band screw lid container, following material is mixed with each other:
91% graphite, ConocoPhillips C5,
6%PVdF, with Kynar
2801 buy from Arkema Group,
3% carbon black, BET surface area 62m
2/ g, buys from Timcal with " Super P Li ".
When stirring, add enough 1-METHYLPYRROLIDONEs, to obtain, containing the sticky plaster of agglomerate, do not stick with paste.Mixture is stirred 16 hours.
Subsequently thus obtained cream paste cutter is applied on the Copper Foil that 20 μ m are thick and at 120 ℃ and is dried 16 hours in vacuum drying chamber.After dry, the thickness of coating is 35 μ m.Subsequently, stamp out the disc section that diameter is 12mm.
All the time use following electrolyte:
LiPF
6be stored in the 1M solution in Carbon Dioxide ethyl-ethyl carbonate mixtures of methyl esters (part by weight is 1:1)
Generation and the test of II.1 electrochemical cell EC.1 of the present invention
In argon filling glove box, electrolyte is dropped in upper according to the separator of the present invention (S.1) I.1 producing and is positioned between negative electrode (A.1) and anode (B.1) so that anode and negative electrode the two all directly contact with separator.This produces electrochemical cell EC.1 of the present invention.In Swagelok battery, between 4.25V and 4.8V, carry out electrochemical analysis.
For forming object, the first two circulation moves with 0.2C speed; The 3rd is circulated to the 50th circulation with 1C rate loop, again with 0.2C speed, carries out 2 circulations afterwards, carries out 48 circulations etc. afterwards with 1C speed.Under room temperature, by " MACCOR cell tester ", implement charging and the electric discharge of battery.
Find that battery pack electric capacity keeps stabilizer pole in recharge and discharge process.
Generation and the test of II.2-II.5 electrochemical cell EC.2, EC.3 and C-EC.4, C-EC.5
Be similar to example II .1, use separator S.2, S.3 and C-S.4 and C-S.5 produce electrochemical cell EC.2, EC.3 and C-EC.4 and C-EC.5, and correspondingly it is tested.
Fig. 1 shows the schematic structure of breaking electrochemical cell for testing the present invention and non-separator of the present invention.
Annotation in Fig. 1 means:
1,1' mould
2,2' nut
3,3' sealing ring-all have two in each situation, the second sealing ring less in each situation is not shown herein
4 helical springs
5 nickel output conductors
6 shells
Result:
Electrochemical cell EC.1 charges and discharges in stabilizer pole mode in 160 circulations, and primary capacitance only loses 27% after 130 circulations.
Electrochemical cell EC.2 charges and discharges in stabilizer pole mode in 160 circulations, and primary capacitance only loses 11% after 130 circulations.
Electrochemical cell EC.3 charges and discharges in stabilizer pole mode in 160 circulations, and primary capacitance only loses 14% after 130 circulations.
The electrochemical cell C-EC.4 of comparing embodiment lowers one's standard or status relatively significantly, and primary capacitance loss 46% after approximately 130 circulations.
The electrochemical cell C-EC.5 of comparing embodiment lowers one's standard or status relatively quickly, and the same loss 46% of primary capacitance after approximately 130 circulations.
Claims (15)
1. an electrochemical cell, it comprises:
(A) at least one negative electrode, it comprises at least one containing the transistion metal compound of lithium ion,
(B) at least one anode, and
(C) at least one layer that comprises following component:
(a) at least one polymer that comprises monomeric unit, described monomeric unit comprises nitrogenous 5 Yuans or 6 element heterocycle aromatic structure unit or comprises the organic group derived from α-aminophosphonicacid or iminodiacetic acid, and
(b) at least one adhesive optionally.
2. according to the electrochemical cell of claim 1, wherein containing the transistion metal compound of lithium ion, be selected from containing the spinelle of manganese and there is the transition metal oxide containing manganese of layer structure.
3. according to the electrochemical cell of claim 1 or 2, its Anodic (B) selects the anode of free carbon formation and comprises Sn or the anode of Si.
4. according to the electrochemical cell of any one in claim 1-3, be wherein stored in polymer in layer (C) and comprise and be selected from following monomeric unit:
Wherein X is O, S or NR, and R is hydrogen or C
1-C
4alkyl.
5. according to the electrochemical cell of any one in claim 1-3, be wherein stored in polymer in layer (C) and be the copolymer of the monomeric unit that comprises N-vinyl imidazole and NVP.
6. according to the electrochemical cell of any one in claim 1-5, the polymer being wherein stored in layer (C) is particulate form, is form of film or is uniformly distributed in layer (C).
7. according to the electrochemical cell of any one in claim 1-6, its middle level (C) comprises adhesive (b), and it is selected from and comprises following polymer: polyvinyl alcohol, styrene butadiene rubbers, polyacrylonitrile, carboxymethyl cellulose and fluoridize (being total to) polymer.
8. according to the electrochemical cell of any one in claim 1-7, its middle level (C) has the average thickness of 9-50 μ m.
9. according to the electrochemical cell of any one in claim 1-8, its middle level (C) is separator.
10. according to the electrochemical cell of any one in claim 1-9, its middle level (C) comprises non-woven fabric (c) in addition.
11. according to the electrochemical cell of any one in claim 1-10, and its middle level (C) be covered cathode (A) or separator or anode (B) at least one side.
12. according to the purposes of the electrochemical cell of any one in claim 1-11, and it is for lithium ion battery group.
13. 1 kinds of lithium ion battery groups, it comprises at least one according to the electrochemical cell of any one in claim 1-11.
14. according to the purposes of the electrochemical cell of any one in claim 1-11, and it is for motor vehicles, bicycle, aircraft, ship or fixed energies storage device by electric motor operated.
The purposes of 15. polymer that comprise monomeric unit, for generation of electrochemical cell, described monomeric unit comprises nitrogenous 5 Yuans or 6 element heterocycle aromatic structure unit or comprises the organic group derived from α-aminophosphonicacid or iminodiacetic acid.
Applications Claiming Priority (3)
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|---|---|---|---|
| EP11192262 | 2011-12-07 | ||
| EP11192262.1 | 2011-12-07 | ||
| PCT/IB2012/056819 WO2013084116A1 (en) | 2011-12-07 | 2012-11-29 | Electrochemical cells comprising nitrogen-containing polymers |
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|---|---|
| EP (1) | EP2789031A4 (en) |
| JP (1) | JP5717929B2 (en) |
| KR (1) | KR20140104995A (en) |
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| CN107346818A (en) * | 2016-05-06 | 2017-11-14 | 宁德新能源科技有限公司 | Cathode sheet and preparation method thereof and lithium ion battery |
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| US20130149589A1 (en) * | 2011-12-07 | 2013-06-13 | Oliver Gronwald | Electrochemical cells comprising a nitrogen-containing polymer |
| CN111065658A (en) * | 2017-07-06 | 2020-04-24 | 株式会社村田制作所 | Polymers comprising imidazole derivatives and their use in electrochemical cells |
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- 2012-11-29 JP JP2014545404A patent/JP5717929B2/en not_active Expired - Fee Related
- 2012-11-29 EP EP12854572.0A patent/EP2789031A4/en not_active Withdrawn
- 2012-11-29 WO PCT/IB2012/056819 patent/WO2013084116A1/en active Application Filing
- 2012-11-29 KR KR1020147018619A patent/KR20140104995A/en not_active Application Discontinuation
- 2012-11-29 CN CN201280059796.7A patent/CN103959511A/en active Pending
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| DE10122811A1 (en) * | 2001-05-10 | 2002-11-28 | Dilo Trading Ag Zug | Production of lithium-polymer wound cell battery involves continuous production of separate homogeneous anode mass, cathode mass and polymer gel electrolyte and extrusion on metal lead as core |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107346818A (en) * | 2016-05-06 | 2017-11-14 | 宁德新能源科技有限公司 | Cathode sheet and preparation method thereof and lithium ion battery |
| CN107346818B (en) * | 2016-05-06 | 2020-04-07 | 宁德新能源科技有限公司 | Cathode pole piece, preparation method thereof and lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5717929B2 (en) | 2015-05-13 |
| KR20140104995A (en) | 2014-08-29 |
| WO2013084116A1 (en) | 2013-06-13 |
| EP2789031A1 (en) | 2014-10-15 |
| EP2789031A4 (en) | 2015-08-12 |
| JP2015505122A (en) | 2015-02-16 |
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