EP2399263A1 - High safety lithium-ion battery - Google Patents
High safety lithium-ion batteryInfo
- Publication number
- EP2399263A1 EP2399263A1 EP10708596A EP10708596A EP2399263A1 EP 2399263 A1 EP2399263 A1 EP 2399263A1 EP 10708596 A EP10708596 A EP 10708596A EP 10708596 A EP10708596 A EP 10708596A EP 2399263 A1 EP2399263 A1 EP 2399263A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lithium
- group
- battery
- ethyl
- ionic liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 31
- 239000002608 ionic liquid Substances 0.000 claims abstract description 44
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000003949 imides Chemical class 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 7
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 7
- 150000001450 anions Chemical class 0.000 claims abstract description 6
- 125000002091 cationic group Chemical group 0.000 claims abstract description 5
- 125000000129 anionic group Chemical group 0.000 claims abstract description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical compound C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 claims abstract description 3
- 125000004429 atom Chemical group 0.000 claims abstract description 3
- NQRYJNQNLNOLGT-UHFFFAOYSA-O Piperidinium(1+) Chemical compound C1CC[NH2+]CC1 NQRYJNQNLNOLGT-UHFFFAOYSA-O 0.000 claims abstract 2
- 125000003545 alkoxy group Chemical group 0.000 claims abstract 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000012528 membrane Substances 0.000 claims description 27
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000003792 electrolyte Substances 0.000 claims description 19
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 18
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 4
- WILFKSVSWSOFBW-UHFFFAOYSA-N 1-(2-methoxyethyl)piperidine Chemical compound COCCN1CCCCC1 WILFKSVSWSOFBW-UHFFFAOYSA-N 0.000 claims description 2
- LCAUYAVEBKFAKD-UHFFFAOYSA-N 1-butan-2-yl-1-ethylpiperidin-1-ium Chemical compound CCC(C)[N+]1(CC)CCCCC1 LCAUYAVEBKFAKD-UHFFFAOYSA-N 0.000 claims description 2
- VGLXNNQUTZDJIR-UHFFFAOYSA-N 1-butyl-1-ethylpiperidin-1-ium Chemical compound CCCC[N+]1(CC)CCCCC1 VGLXNNQUTZDJIR-UHFFFAOYSA-N 0.000 claims description 2
- JKTKRGGERCVMMW-UHFFFAOYSA-N 1-ethyl-1-(2-methylpropyl)piperidin-1-ium Chemical compound CC(C)C[N+]1(CC)CCCCC1 JKTKRGGERCVMMW-UHFFFAOYSA-N 0.000 claims description 2
- HGTFFQGAGPYARH-UHFFFAOYSA-N 1-ethyl-1-propan-2-ylpiperidin-1-ium Chemical compound CC[N+]1(C(C)C)CCCCC1 HGTFFQGAGPYARH-UHFFFAOYSA-N 0.000 claims description 2
- WQJAOAVHWUDVMV-UHFFFAOYSA-N 1-ethyl-1-propylpiperidin-1-ium Chemical compound CCC[N+]1(CC)CCCCC1 WQJAOAVHWUDVMV-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910013753 LiCO-MnPO4 Inorganic materials 0.000 claims description 2
- 229910013757 LiCo-NiO2 Inorganic materials 0.000 claims description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 2
- 229910011279 LiCoPO4 Inorganic materials 0.000 claims description 2
- 229910000668 LiMnPO4 Inorganic materials 0.000 claims description 2
- 229910003005 LiNiO2 Inorganic materials 0.000 claims description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910008063 SnC Inorganic materials 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- MPDDDPYHTMZBMG-UHFFFAOYSA-N butyl(triethyl)azanium Chemical compound CCCC[N+](CC)(CC)CC MPDDDPYHTMZBMG-UHFFFAOYSA-N 0.000 claims description 2
- ZKMHIBVJYBMHNM-UHFFFAOYSA-N butyl-diethyl-methylazanium Chemical compound CCCC[N+](C)(CC)CC ZKMHIBVJYBMHNM-UHFFFAOYSA-N 0.000 claims description 2
- HWGWYOIABCECRH-UHFFFAOYSA-N butyl-diethyl-propylazanium Chemical compound CCCC[N+](CC)(CC)CCC HWGWYOIABCECRH-UHFFFAOYSA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical class [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- WGYXSYLSCVXFDU-UHFFFAOYSA-N triethyl(propyl)azanium Chemical compound CCC[N+](CC)(CC)CC WGYXSYLSCVXFDU-UHFFFAOYSA-N 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical class [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- 239000000654 additive Substances 0.000 abstract description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003063 flame retardant Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 16
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 150000001875 compounds Chemical group 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 239000006193 liquid solution Substances 0.000 description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- -1 Poly(methyl methacrylate) Polymers 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 description 3
- 238000013021 overheating Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- DZMOLBFHXFZZBF-UHFFFAOYSA-N prop-2-enyl dihydrogen phosphate Chemical compound OP(O)(=O)OCC=C DZMOLBFHXFZZBF-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- YXJSMCZTRWECJF-UHFFFAOYSA-N 1-butyl-1-ethylpyrrolidin-1-ium Chemical compound CCCC[N+]1(CC)CCCC1 YXJSMCZTRWECJF-UHFFFAOYSA-N 0.000 description 1
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910011956 Li4Ti5 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910014715 LixTiO2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical group C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical class C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- 125000004848 alkoxyethyl group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
Definitions
- the present invention refers to the technical field of Lithium-Ion batteries and more in particular to safety and to ameliorate efficiency of this type of batteries. Thanks to their high energy content, Lithium-Ion batteries prevail in the consumer electronics area and promote spreading of cellular phones, lap-top computers, digital audio players and so on. However, Lithium-Ion batteries need improved efficiency to be applied in the expanding markets of power stations fed by discontinuous sources or power systems for electric or hybrid vehicles.
- Safety is one of the unsolved problems affecting said batteries, due to the instability of the battery's components. More in particular, the use of electrolyte solutions of lithium salts in volatile organic solvents is dangerous. Vaporization of solvents, which is triggered by local overheating and/or by electrochemical decomposition of the same solvents, may produce gaseous side products which increase the internal pressure. This event may cause not only cell breaking, but also to violent side-reactions or fires and explosions. These risks are related to battery abuse, such as high working temperatures or mechanical shock.
- Patent US 6,413,678 suggests solving safety problems of said type of batteries by using a gas evolving system.
- a carbonyl compound subject to temperature increasing, decomposes and produces gaseous products, which are insoluble, or poorly soluble in the electrolyte.
- a suitable breaking valve stably and safely increases the pressure within the battery.
- ionic liquids namely salts in the liquid state at room or sub-room or at least at the battery's working temperature.
- the ionic liquids are composed by several combinations of different anions and cations.
- Patent application US 2007/026318 discloses some of said ionic liquids and their drawbacks due to their reactivity with the electrodes (see for example patent applications JP 4-349365, JP 11 -86905). Said document disclose the technical solution of inserting allyl phosphate in the ionic liquid.
- the compounds bearing the quaternary ammonium cation pyrrolidinium derivatives are mentioned, all characterised by a methyl on the quaternary nitrogen residue, which are useful to counteract side reactions on the electrodes.
- imidazole derivatives are preferred since they lower the viscosity of the ionic liquid and enhance battery performances, as suggested in patent application US 2008/0076030.
- Allyl phosphate is preferred as essential component to enhance safety and avoid explosions by acting as a flame retardant.
- Examples of Lithium-Ion batteries using non-aqueous electrolytes, like ionic liquids, are disclosed in EP 1 906 841 , US 2007/023801 , WO 2005/104288.
- the ionic liquid was disclosed for uses different from those being object of the present patent and precisely for a Lithium-metal battery.
- the organic electrolyte becomes unstable for cyclation and reacts giving a solid product, which, in a small extent, protects the electrode (passivation), then the solid deposition proceeds and a non-uniform layer forms stacked structures (dendrites) which can cause short-circuits.
- safety problem is mainly linked to accidental overheating of the battery above a threshold temperature.
- the solution proposed by the present invention consists of ionic liquids as electrolytic components being non-volatile, non-flammable and stable compared with the material for electrodes proposed in the cells combinations herein disclosed.
- a Lithium-Ion battery with a particular configuration of electrodes and the ionic liquid of the invention shows particularly advantageous features.
- one object of the present invention is a Lithium-Ion battery characterised in that the ionic liquid comprises a) an ionic liquid consisting of a cationic portion of quaternary ammonium of formula
- R1 is a linear or branched alkyl with from 2 to 5 carbon atoms, optionally substituted with an alkoxyethyl group with from 1 to 3 carbon atoms;
- R2, R3 e R4, being the same or different, are a linear or branched alkyl with from 2 to 5 carbon atoms, or R3 and R4, together with the nitrrogen atom to which they are bound form a pyrrolidinium or piperidinium group; b) an anionic part, wherein the anion is selected form the group consisting of: N, N- bis(trifluoromethanesulphonyl)imide tetrafluoborate, and N,N-bis(trifluoromethanesulphonyl)imide esafluophosphate;
- a lithium salt selected form the group consisting of lithium N, N-
- the Lithium-Ion battery according to the present invention has the advantage of maintaining satisfactory performance, despite the absence of a solvent and of maintaining the increase of viscosity due to the ionic liquid and in particular of ensuring compatibility with electrodes.
- the battery is safe thanks to the high thermal stability of the ionic liquid as used in the present invention. Furthermore, opposite to the batteries known in the art which use ionic liquids-based electrolytes, the combination of said ionic liquid with the proposed electrolytes ensure the stability of each component without using additives, as flame retardant or other additives.
- the invention is herein disclosed in detail also referring to the figures and examples.
- Figure 1 shows TGA (Thermo Gravimetric Analysis) curves of pure ionic liquid Py 24 -TFSI and of its solutions with LiTFSI.
- Figure 2 shows conductivity of pure ionic liquid Py 24 -TFSI and of its solutions with LiTFSI.
- Figure 3 shows a charge-discharge cycle of the Li 4 Ti 5 O 12 / Py 24 TFSI - LiTFSI /LiFePO 4 Lithium-Ion battery.
- Figure 4 shows charge-discharge cycles of SnC/ Py 24 TFSI-LiTFSI / LiFePO 4 battery.
- Figure 5 shows charge-discharge cycles Of TiO 2 / Py 24 TFSI-LiTFSI / LiFePO 4 battery.
- Figure 6 show conductivity at room temperature of a hybrid gel-like membrane assembled by the Py 24 TFSI-LiTFSI solution on the PVdF-HFP matrix, compared with a similar membrane containing LiPF 6 - PC-EC.
- the ionic liquid is made of a cationic portion as disclosed in the above formula (I).
- a first group of preferred compounds consists of: N-n-butyl-N-ethylpirrolidinium, N-ethyl-N-propylpirrolidinium, N-ethyl-N-pethylpirrolidinium, N-ethyl-N- propoxyethylpirrolidinium, N-ethyl-N-propylpiperidinium, N-ethyl-N-isopropylpiperidinium, N-butyl-N- ethylpiperidinium, N-isobutyl-N-ethylpiperidinium, N-secbutyl-N-ethylpiperidinium, N-methoxyethyl-N- piperidinium, N-ethyl-N-etoxyethylpiperidinium, N-butyl-N,N,N-triethylammonium, N,N,N-triethyl-N- propy
- the anionic portion of the ionic liquid is N,N-(bis(methantrifluoridesul- phonyl)imide.
- the ionic liquid is N-n-butyl-N-ethylpirrolidinium, N,N-(bis(methantri- fluoridesulphonyl)imide.
- the compound N-n-butyl-N-ethylpirrolidinium, N,N-(bis(methantrifluoridesulphonyl)imide being the ionic liquid of the best embodiment for the Lithium-Ion battery, its preparation and investigation on its possible use as a ionic liquid and herein indicated as Py 24 TFSI have been disclosed in the above mentioned A. Fernicola, F. Croce, B. Scrosati, T. Watanabe, H. Ohno; Journal of Power Sources 174 (2007) 342-348,.
- the ionic liquid of the invention is prepared as disclosed in the paper of Fernicola et al, as summarised in the following scheme:
- Said method of preparation can be used for anyone of the compounds of the above formula (I) wherein R 3 and R 4 with the nitrogen atom to which they are bound form a pirrolidinic or piperidinic ring.
- the heterocyclic compound with an alkyl chain on the nitrogen atom is available on the market or can be prepared following known methods.
- the alkyl halide of the required length, according to the above definition of R 2, is also available on the market or can be prepared with the known methods.
- the reaction between nitrogen heterocycle and the alkyl halide is well-known to the organic chemist with ordinary skills in the art, said reaction is carried out in an organic solvent under time and temperature conditions which can easily set also looking at similar reactions known in the art.
- the isolation of the reaction product is made conventionally for example by solvent crystallization or by chromatography or by equivalent methods.
- the intermediate product reacts with a salt of the anion which forms the final ionic liquid.
- Helpful reference, disclosing the synthesis of ionic liquids similar to these herein disclosed are: D. R. MacFarlane, P. Meakin, J. Sun, N. Amini, M. Forsyth J. Phys. Chem. B 103 (1999) 4164-4170; e G. B. Appetecchi, S. Scaccia, C. Tizzani, F. Alessandrini, S. Passerini, J. Electrochem. Soc. 153 (2006) A1685-A1691.
- Py 24 TFSI ionic liquid is added to a lithium salt, LiTFSI, to ensure an appropriate carriage of the lithium ion in the battery. It has been experimentally proved that, being the anion of the salt the same used in ionic liquid, the components are compatible. In a further preferred embodiment, said ionic liquid is engulfed in a membrane as herein disclosed in details.
- the battery according to the present invention comprises an anode-cathode system.
- Anode- cathode systems known in the art may be used.
- the cathode in selected in the group consisting of: lithium phosphates and metals, metal oxides intercalated by lithium ions, lithium oxides and manganese.
- said cathode is selected in the group consisting of: LiFePO 4 , LiCoPO 4 , LiMnPO 4 , LiCO-MnPO 4 ; LiCoO 2 , LiNiO 2 , LiCo-NiO 2 ; LiMn 2 O 4 , LiNio ,5 Mni ,5 04, LiCo 1Z3 Mn 1Z3 Ni 1Z3 O 2 .
- the anode is selected in the group consisting of: graphite, titanium oxides containing lithium or MC alloys, wherein M is selected in the group consisting of silicon, antimony, aluminium or a combination thereof.
- the anode is selected in the group consisting of Li 4 Ti 5 O 12 , SnC, TiO 2 .
- the material of the anode SnC is prepared starting form a tin-based organometallic, which is engulfed in a resorcinol-formaldehyde gel.
- the product is calcinated in argon flux to reduce the tin content in the tin metallic precursor and carbonization of the gel. Said procedure allows obtaining a final material with a nominal composition Sn / C 1 :1.
- the synthesis has been disclosed in G. Derrien, J. Hassoun, S. Panero, B. Scrosati, Adv. Mater. 19 (2007) 2336.
- TiO 2 is an electrod ic material in P . Ku biak, J . Gesereick, N. H ⁇ sing, M. Wohlfahrt-Mehrens Electrochemical performance of mesoporous TiO2 anatase Journal of Power Sources, 175 (1 ) pp. 510- 516 (2008).
- Li 4 Ti 5 O 12 is a material known in the field of Lithium-Ion batteries.
- anode negative electrode
- cathode positive electrode
- LiFePO 4 LiFePO 4
- electrolyte Li 4 Ti 5 O 12
- Figure 1 shows the thermal stability in a thermogravimetric analysis of the ionic liquid and of the two solutions with LiTFSI, the results are shown in figure 1. It has to be underlined that the high thermal stability of the pure ionic liquid rises up to 368 0 C, similar values can be obtained with its solution with the lithium salt. Said feature is responsible for the better safety grade of the battery using said system.
- Figure 2 shows the conductivity of the tested systems. The conductivity of the solution decreases when the salt concentration increases (for the corresponding increase of the viscosity) the values are in the range of mS/cm, thus high enough to allow their use in the Lithium-Ion batteries and in the Lithium batteries, being comparable with those of the electrolytic solutions currently used in said devices.
- Said membranes are stable up to 325 0 C, and maintain the high thermal stability of the solution making the ionic liquid.
- the conductivity is a 6,4 x 10 '4 Scnrf 1 , said value is similar in the electrolytic solutions used in the Lithium-Ion batteries available on the market.
- the Py 24 TFSI-LiTFSI, PVdF-HFP membranes can be thus applied in new designed lithium batteries having high thermal stability, safety, reliability and modular development geometry. Like the Py 24 TFSI-LiTFSI solution of which they are made, said membranes can be used as electrolytic walls in batteries using the electrolytic materials of the present invention.
- Polymeric matrix based on several polymers including polyvinylydene fluoride (PVdF), a co-polymeric polyvinylidene fluoride exafluoropropylene (PVdF-HFP), polyacrylonitrile (PAN), Poly(methyl methacrylate) (PMMA), Polyvinyl alcohol (PVA) and combinations thereof can be used in the preparation of the ionic liquid engulfed in a membrane.
- PVdF polyvinylydene fluoride
- PVdF-HFP co-polymeric polyvinylidene fluoride exafluoropropylene
- PAN polyacrylonitrile
- PMMA Poly(methyl methacrylate)
- PVA Polyvinyl alcohol
- said membranes can include several liquid solutions comprising a lithium salt which can be selected in the families of lithium tetrafluoroborate, lithium esafluorophosphate and lithium bis(trifluoromethansulphonyl)imide dissolved in mixtures of aprotic organic solvents which be selected in the families of carbonates, as ethylene carbonate, EC, propylene carbonate, PC, dimethylcarbonate, DMC e diethylcarbonate, DEC.
- a lithium salt which can be selected in the families of lithium tetrafluoroborate, lithium esafluorophosphate and lithium bis(trifluoromethansulphonyl)imide dissolved in mixtures of aprotic organic solvents which be selected in the families of carbonates, as ethylene carbonate, EC, propylene carbonate, PC, dimethylcarbonate, DMC e diethylcarbonate, DEC.
- the battery according to the present invention can be manufactured according to the common general knowledge in the field and any specific description is required. As an example, see Gold Peak Industries Ltd. Lithium Ion Technical Handbook and the references cited thereof.
- the battery according to the present invention can have different manufacturing configurations as, for example, disclosed in US 2008/0076030, US 2007/0026318, US 2003/0054254.
- a battery with the following configuration has been prepared: anode (negative electrode): Li 4 Ti 5 Oi 2 cathode (positive electrode): LiFePO 4 electrolyte: Py 24 TFSI-LiTFSI
- the operative process is the lithium ion exchange from one electrode to the other, where the electrolyte acts as a lithium ions transporter.
- Figure 3 shows a charge cycle:
- Figure 3 shows a charge-discharge cycle of the above disclosed battery.
- a battery with the following configuration has been prepared: anode (negative electrode): SnC cathode (positive electrode): LiFePO 4 electrolyte: Py 24 TFSI-LiTFSI
- the operative process is the reversible lithium ion exchange from the cathode to the anode.
- Figure 4 shows charge-discharge cycles of SnC/ Py 24 TFSI-LiTFSI / LiFePO 4 battery.
- a battery with the following configuration has been prepared: anode (negative electrode): TiO 2 cathode (positive electrode): LiFePO 4 electrolyte: Py 24 TFSI-LiTFSI
- the cell reaction is the following: LiFePO 4 + TiO 2 ⁇ Li- ⁇ x FePO 4 + Li x TiO 2 .
- Figure 5 shows charge-discharge cycles of said battery.
- Said membranes have been prepared by casting the liquid solutions commonly used in the Lithium-Ion batteries (as control example a exafluorophosphate solution has been LiPF 6 used) in a mixture of aprotic organic solvents (for example a solution of ethylene carbonate and EC-PC) in a polymeric matrix (for example the same PVdF-HFP matrix above disclosed).
- aprotic organic solvents for example a solution of ethylene carbonate and EC-PC
- a polymeric matrix for example the same PVdF-HFP matrix above disclosed.
- Figure 6 shows conductivity at room temperature of a hybrid gel-like membrane prepared by assembling the LiPF 6 -PC-EC (• - upper line) and the LiTFSI-Py 24 TFSI (• - lower line) solution in the PVdF-HFP matrix.
- Figure 6 shows that conductivity at room temperature of the hybrid gel-like membrane prepared by assembling the LiPF 6 -PC-EC solution in the PVdF-HFP matrix is ,7 x 10 3 Scnrf 1 , at room temperature, similar to the conductivity of the liquid solution of which it is made.
- the conductivity of the membrane stays in a range of interesting values for the use in batteries in a wide range of temperature, which is around 10 '4 Scm '1 at 0 0 C to around 10 '3 Scm '1 at 60 0 C.
- the advantage of said membrane is that they maintain the same operational features of the liquid solution even in a polymeric configuration.
- the hybrid membranes can be applied in Lithium-Ion batteries with a new polymeric configuration and with high safety, reliability and modular development geometry. Similarly with the configurations previously disclosed, said membranes can be used as electrolytic walls in batteries using the electrodic materials disclosed in the present invention. Industrial applicability of the present invention is clear. As an example mobile electronic, last generation mobile phones, sustainable transportation and Renewable energy.
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ITRM2009A000072A IT1393271B1 (it) | 2009-02-18 | 2009-02-18 | Batteria litio-ione con elevato grado di sicurezza |
PCT/IB2010/050655 WO2010095082A1 (en) | 2009-02-18 | 2010-02-12 | High safety lithium-ion battery |
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US20160307349A1 (en) * | 2015-04-15 | 2016-10-20 | Canon Kabushiki Kaisha | Communication support system, information processing apparatus, control method, and storage medium |
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KR102501474B1 (ko) | 2015-09-25 | 2023-02-22 | 삼성전자주식회사 | 리튬공기전지용 전해질 및 이를 포함하는 리튬공기전지 |
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US5340670A (en) | 1992-06-01 | 1994-08-23 | Kabushiki Kaisha Toshiba | Lithium secondary battery and method of manufacturing carbonaceous material for negative electrode of the battery |
JP3556270B2 (ja) | 1994-06-15 | 2004-08-18 | 株式会社東芝 | リチウム二次電池 |
JP4053630B2 (ja) | 1997-09-12 | 2008-02-27 | 株式会社東芝 | 非水電解質二次電池 |
US6413678B1 (en) | 1999-03-03 | 2002-07-02 | Ube Industries, Inc. | Non-aqueous electrolyte and lithium secondary battery using the same |
US7153609B2 (en) | 2001-09-05 | 2006-12-26 | Kabushiki Kaisha Toshiba | Rechargeable battery with nonaqueous electrolyte |
DE102004018929A1 (de) | 2004-04-20 | 2005-11-17 | Degussa Ag | Elektrolytzusammensetzung sowie deren Verwendung als Elektrolytmaterial für elektrochemische Energiespeichersysteme |
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US20160307349A1 (en) * | 2015-04-15 | 2016-10-20 | Canon Kabushiki Kaisha | Communication support system, information processing apparatus, control method, and storage medium |
US10057315B2 (en) * | 2015-04-15 | 2018-08-21 | Canon Kabushiki Kaisha | Communication support system, information processing apparatus, control method, and storage medium that display an output image obtained by superposing a reference image over a captured image |
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