CN103579697A - Battery package and/or battery fireproof device - Google Patents
Battery package and/or battery fireproof device Download PDFInfo
- Publication number
- CN103579697A CN103579697A CN201310310357.5A CN201310310357A CN103579697A CN 103579697 A CN103579697 A CN 103579697A CN 201310310357 A CN201310310357 A CN 201310310357A CN 103579697 A CN103579697 A CN 103579697A
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- CN
- China
- Prior art keywords
- battery
- phosphate
- lithium
- packages
- firebreak device
- 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.)
- Pending
Links
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 48
- 239000010452 phosphate Substances 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 35
- 239000011159 matrix material Substances 0.000 claims description 52
- 239000000463 material Substances 0.000 claims description 40
- 229910052744 lithium Inorganic materials 0.000 claims description 39
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 38
- 238000012856 packing Methods 0.000 claims description 25
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 24
- 239000005955 Ferric phosphate Substances 0.000 claims description 22
- 229940032958 ferric phosphate Drugs 0.000 claims description 22
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 22
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 22
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical group [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 19
- 239000003792 electrolyte Substances 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- -1 polypropylene Polymers 0.000 claims description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000004698 Polyethylene Substances 0.000 claims description 11
- 239000004743 Polypropylene Substances 0.000 claims description 11
- 229920000573 polyethylene Polymers 0.000 claims description 11
- 229920001155 polypropylene Polymers 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 229920001169 thermoplastic Polymers 0.000 claims description 7
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 claims description 6
- 150000005677 organic carbonates Chemical class 0.000 claims description 5
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 4
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 229910000152 cobalt phosphate Inorganic materials 0.000 claims description 3
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 claims description 3
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- 239000010408 film Substances 0.000 claims 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims 1
- 239000010409 thin film Substances 0.000 claims 1
- 239000005486 organic electrolyte Substances 0.000 abstract description 2
- 239000011877 solvent mixture Substances 0.000 description 22
- ZWOYKDSPPQPUTC-UHFFFAOYSA-N dimethyl carbonate;1,3-dioxolan-2-one Chemical compound COC(=O)OC.O=C1OCCO1 ZWOYKDSPPQPUTC-UHFFFAOYSA-N 0.000 description 21
- 238000000354 decomposition reaction Methods 0.000 description 19
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 16
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 15
- 229910013870 LiPF 6 Inorganic materials 0.000 description 11
- RFGNMWINQUUNKG-UHFFFAOYSA-N iron phosphoric acid Chemical compound [Fe].OP(O)(O)=O RFGNMWINQUUNKG-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000010406 cathode material Substances 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000002648 laminated material Substances 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 5
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 4
- 229910010710 LiFePO Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- WNEODWDFDXWOLU-QHCPKHFHSA-N 3-[3-(hydroxymethyl)-4-[1-methyl-5-[[5-[(2s)-2-methyl-4-(oxetan-3-yl)piperazin-1-yl]pyridin-2-yl]amino]-6-oxopyridin-3-yl]pyridin-2-yl]-7,7-dimethyl-1,2,6,8-tetrahydrocyclopenta[3,4]pyrrolo[3,5-b]pyrazin-4-one Chemical compound C([C@@H](N(CC1)C=2C=NC(NC=3C(N(C)C=C(C=3)C=3C(=C(N4C(C5=CC=6CC(C)(C)CC=6N5CC4)=O)N=CC=3)CO)=O)=CC=2)C)N1C1COC1 WNEODWDFDXWOLU-QHCPKHFHSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002926 oxygen Chemical class 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910003548 Li(Ni,Co,Mn)O2 Inorganic materials 0.000 description 1
- 229910008416 Li-Ti Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910006861 Li—Ti Inorganic materials 0.000 description 1
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 description 1
- 229910006025 NiCoMn Inorganic materials 0.000 description 1
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 description 1
- ZSYNKHJUSDFTCQ-UHFFFAOYSA-N [Li].[Fe].P(O)(O)(O)=O Chemical compound [Li].[Fe].P(O)(O)(O)=O ZSYNKHJUSDFTCQ-UHFFFAOYSA-N 0.000 description 1
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- VROAXDSNYPAOBJ-UHFFFAOYSA-N lithium;oxido(oxo)nickel Chemical compound [Li+].[O-][Ni]=O VROAXDSNYPAOBJ-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the 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
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/574—Devices or arrangements for the interruption of current
- H01M50/581—Devices or arrangements for the interruption of current in response to temperature
-
- 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
- H01M2200/00—Safety devices for primary or secondary batteries
- H01M2200/10—Temperature sensitive devices
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Mounting, Suspending (AREA)
Abstract
The invention relates to a battery package and/or a battery fireproof device (10) composed of a primary battery (1) containing organic electrolyte. In order to improve the safety of the battery, the battery package and/or the battery fireproof device (10) comprises at least one phosphate-containing compound. In addition, the invention also relates to a battery equipped with the above battery package and/or the battery fireproof device (10).
Description
The present invention relates to battery packages and/or battery firebreak device and be equipped with these battery.
Prior art
Lithium-ions battery (being also referred to as lithium ion battery (LIB)) at present in a large amount of products (for example mobile phone) be used as energy storage device.For lithium ion battery is used for to Automobile drive, must be manufactured very large size.
Lithium ion battery contains organic bath conventionally.
In the situation that being damaged, may there is lithium ion battery and lighted, emit poisonous gas and dust and even may blast by organic bath.
Therefore,, particularly for driving enough large-sized lithium ion batteries of automobile, stop or reduce to damage or the fail safe concept of its consequence is to make us especially interested.
In document DE 10 2,009 053 186 A1, the extinguishing chemical for putting out a fire has been described.
Summary of the invention
The object of the invention is to improve the primary cell contain organic bath or the fail safe of battery.
Battery packages and/or the battery firebreak device of the primary cell of this object by containing organic bath at least one are accomplished, and this packing or device comprise at least one phosphatic compound.
Battery packages can refer to especially for packing the device of one or more primary cells.Substantially, battery packages can be designed for (independent) primary cell of packing or for packing two or more primary cells, i.e. so-called battery module (Modul) or battery pack (Pack).For example, battery packages can be designed for independent primary cell of packing or the two or more primary cells for packing, the battery module for example being formed by two or more primary cells, or the battery pack being formed by two or more battery modules.
Battery firebreak device can refer to particularly except primary cell or the device separated with primary cell, this device is designed for the in the situation that of temperature rising and/or electrolyte decomposition with before particularly also catching fire electrolyte is contacted with described at least one phosphatic compound, and it does not particularly participate in the electrochemical reaction of primary cell itself.
Have been found that, there is the lithium ion battery of organic bath and the so-called thermal runaway (Durchbrennen of other battery, English: thermal runaway) to be mainly the oxidation due to the organic bath accelerating at elevated temperatures, these organic baths mainly include machine carbonic ester, for example ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC) and/or carbonic acid two ethyls (DEC).Wherein, the oxidation of organic bath in addition can the electrolyte by the electrolyte polymerization reaction form due to heat release be decomposed the heat that be produced and is promoted forward.By the heat producing when the polymerization of organic bath, may there is the normally decomposition of the cathode material of metal oxide, when this decomposition, can produce oxygen, this oxygen can again cause electrolytical oxidation and therefore cause the autoacceleration that electrolyte decomposes and cathode material decomposes of heat release and cause catching fire.
In addition have been found that, the decomposition of organic bath, particularly polymerization be for example, in the temperature lower than 200 ℃, can occur the temperature range of 180-230 ℃, and can be for example the temperature of 150-160 ℃ the optional (lithium hexafluoro phosphate (LiPF for example of the conducting salt by containing in organic bath
6)) decomposition and cause.At this, the electrolyte that the decomposition of conducting salt can promote forward heat release more tempestuously decomposes.
Have been found that advantageously, by phosphatic compound, ferric phosphate (FePO for example
4) and/or iron lithium phosphate (LiFePO
4), can stop and optionally even calm down electrolytical decomposition.The energy minimization that the electrolyte reaction due to heat release can be discharged like this.The autoacceleration of heat release and the thermal runaway therefore occurring be can stop by this way, and combustion reaction or or even blast avoided.Can again advantageously improve the fail safe of battery or battery pack thus.
By adiabatic calorimeter, can prove the rate of heat addition of exothermic heat release in the time of can being reduced in tempestuously electrolyte decomposition by phosphatic compound.Wherein, measurement based on adiabatic calorimeter shows, by phosphatic compound, can be prevented or stop electrolytical decomposition and therefore reduce consumingly the energy of emitting thus with the coefficient of 30 times nearly.
By using described at least one phosphatic compound of appropriate amount, even can calm down because electrolyte decomposes the heat producing.Can finally prevent or at least delay thermal runaway like this.
Described at least one phosphatic compound can be caught the catabolite particularly producing in electrolyte decomposition reaction and prevented thus the temperature of heat release to raise, otherwise the temperature meeting of rising promotes the autoacceleration of heat release optional until battery burning.
In addition, the advantage of phosphatic compound is, its common low price.In addition, phosphatic compound can be nontoxic and mutually environment amenable.
Described at least one phosphatic compound can refer to one or more inorganic or organic compound or their combination or mixtures substantially.For example, described at least one phosphatic compound can be metal phosphate, hydrophosphate, ammonium phosphate or their combination or mixture.
In the scope of a preferred implementation, described at least one phosphatic compound is metal phosphate.For example, described at least one phosphatic compound can be selected from ferric phosphate, lithium phosphate, iron lithium phosphate, manganese phosphate, cobalt phosphate and/or manganese phosphate and their mixture.For example, described at least one phosphatic compound can be selected from ferric phosphate, iron lithium phosphate, manganese phosphate, cobalt phosphate, manganese phosphate and their combination, for example Li (Fe/Ni/Co/Mn) PO
4, and their mixture.Described at least one phosphatic compound can be the compound of phosphoric acid iron especially.For example, described at least one phosphatic compound can comprise or ferric phosphate and/or iron lithium phosphate.For example, described at least one phosphatic compound can comprise or partially or completely go iron lithium phosphate (optional ferric phosphate, the FePO of lithiumation/charged
4) and/or lithiumation/uncharged iron lithium phosphate (LiFePO partially or completely
4).According to electriferous state (Ladezustand), can be wherein in the iron lithium phosphate (LiFePO of electriferous state not
4) or the ferric phosphate (FePO in complete electriferous state
4).Advantageously can prove, stop electrolyte to decompose and do not rely on state of charge or lithiumation degree.Wherein particularly by synthetic primary cell, can prepare partially or completely lithiumation or remove phosphoric acid (lithium) iron of lithiumation.
Organic bath can refer to liquid organic electrolyte especially, and for example it comprises at least one organic solvent (for example organic carbonate) and optional at least one conducting salt.
Described at least one primary cell that contains organic bath can refer to particularly the have intercalation anode lithium battery (for example lithium ion battery) of (for example anode based on graphite) especially, or refer to the lithium metal battery particularly with lithium anodes, and/or refer to lithium-sulfur cell or lithium-oxygen battery.For example, described at least one primary cell that contains organic bath can refer to lithium ion battery.
Described battery packages and/or battery firebreak device particularly can have phosphatic material, and this material comprises described at least one phosphatic compound.Except described at least one phosphatic compound, this phosphatic material can comprise other for example not phosphatic compound.
In the scope of a preferred implementation, described phosphate-containing material comprises or polymer-phosphate composite material, for example polymer-ferric phosphate composite material.Wherein, this polymer-phosphate composite material can be to form with netted form or with the form of netted formation (Netzgebilde).Like this, described battery packages and/or battery firebreak device can be equipped with described at least one phosphatic compound in simple especially mode.Described polymer-phosphate composite material particularly can comprise at least one thermoplasticity and/or otherwise and heat-labile polymer as polymer.
Thermally labile can refer to a kind of material, particularly a kind of polymer especially, its fusing, cracking (Aufreissen), decomposition when the temperature surpassing particularly higher than conventional operating temperature range, evaporates or otherwise destroyed at least partly.Heat-labile material (for example polymer) can be particularly when surpassing certain temperature (for example 130 ℃ or 140 ℃ or 150 ℃ or 160 ℃ or 170 ℃ or 180 ℃) melt at least partly or be thermoplastic and/or cracking at least partly.Wherein said thermally labile material can comprise or at least one thermoplastic polymer, for example, refer at least one polyolefin, for example polypropylene (PP) and/or polyethylene (PE).Substituting or extraly, described heat-labile material can contain specified breakpoint or the specified knick point of the material thickness with minimizing, for example, with the form of perforation or cutting.
Described polymer-phosphate composite material particularly can comprise at least one polyolefin (for example polypropylene (PP) and/or polyethylene (PE)) as polymer.
In the scope of another extra or substituting preferred implementation, described phosphatic material comprises or phosphatic powder.
Substantially, described battery packages and/or battery firebreak device can comprise described at least one phosphatic compound or phosphatic material in a different manner.
For example, described battery packages and/or battery firebreak device can be filled with described at least one phosphatic compound or phosphatic material at least partly, or contain the structure that comprises described at least one phosphate-containing compound or phosphate-containing material.Wherein, this structure can be loose or be connected with described battery packages and/or battery firebreak device.Equally, described at least one phosphatic compound or phosphatic material can be integrated at least one material of described battery packages and/or battery firebreak device.Wherein, described phosphatic material itself can be heat-labile at least partly.
In the scope of a substituting or extra preferred implementation, described battery packages and/or battery firebreak device have heat-labile film.Described at least one phosphatic compound or phosphatic material can be at least partly and heat-labile membrane bounds.Thermally labile film can be for example fusing when the temperature surpassing particularly higher than conventional operating temperature range, cracking, decomposition, evaporation or otherwise destroyed at least partly.This heat-labile film can be particularly when surpassing certain temperature (for example 130 ℃ or 140 ℃ or 150 ℃ or 160 ℃ or 170 ℃ or 180 ℃) melt at least partly or be thermoplastic and/or cracking at least partly.Wherein said heat-labile film can comprise or by least one thermoplastic polymer, at least one polyolefin particularly, and for example polypropylene (PP) and/or polyethylene (PE) form.Substituting or extraly, described heat-labile film can contain specified breakpoint or the specified knick point of the material thickness with minimizing, for example, with the form of perforation or cutting.
In the scope of another preferred implementation, described battery packages and/or battery firebreak device have matrix, particularly pack matrix.In principle, this matrix, particularly pack matrix and can be formed by one or more materials.For example, described matrix, particularly pack matrix and can refer to metallic object or refer to laminated material and/or the composite material being formed by multiple material.Described matrix, particularly pack matrix and can be at least partly with described at least one phosphatic compound or phosphatic material, fill, or contain the structure that comprises described at least one phosphate-containing compound or phosphate-containing material.Wherein, this structure can be loose or with described matrix, particularly pack matrix and be connected.Equally, described at least one phosphatic compound or phosphatic material can be integrated into described matrix, particularly pack at least one material of matrix.In the situation of battery packages, can arrange matrix, particularly pack matrix, it is designed at least one primary cell of protection and avoids externalities.
In the scope of another execution mode, described matrix, the inner side of particularly packing matrix cover with phosphatic material.For example, wherein said matrix, the inner side of particularly packing matrix can use the layer being formed by phosphatic material to apply.Wherein, this layer can comprise or for example, be formed by polymer-phosphate composite material (polymer-ferric phosphate composite material).Wherein, this layer (particularly polymer-phosphate composite material) can be with netted form or form with the form of netted formation.Like this, described battery packages and/or battery firebreak device can be equipped with described at least one phosphatic compound in simple especially mode.
In the scope of another execution mode, described phosphatic material arrangements (for example parcel) at described heat-labile film and described matrix, particularly pack between the inner side of matrix.For example, wherein said heat-labile film and described matrix, particularly pack matrix and can form a kind of double wall.By this way, described battery packages and/or battery firebreak device can be advantageously for example equipped with a large amount of described at least one phosphatic compounds with the form of phosphate-containing powder, particularly do not have therein to stop in the situation of accessibility of described at least one primary cell.
In the scope of another execution mode, described matrix, particularly pack matrix and comprise aluminium.Advantageously, aluminium light weight and can carry out rigidity and flexibly operation.
Described matrix, particularly pack matrix can by aluminium for example with aluminium (duricrust) housing or for example bag-shaped aluminium foil form and form.
Similarly, described matrix, particularly pack matrix and can comprise at least one aluminium lamination.For example, wherein said matrix, particularly pack matrix and can be formed by laminated material, this laminated material by two or more particularly the layer of film-form forms, at least one in these layers layer is aluminium lamination.Wherein, described matrix, particularly pack matrix also can with (duricrust) housing or for example bag-shaped metal forming (particularly laminating foil) form and form.
Described matrix, particularly pack matrix can be for example with the form of for example prismatic or columniform duricrust housing and form.
In the scope of an execution mode, described battery packages and/or battery firebreak device are prismatic or columniform battery duricrust housings for example.
But, described matrix, particularly pack matrix and also can form with the form of for example bag-shaped film.
In the scope of an execution mode, wherein said battery packages and/or battery firebreak device are the flexible blister-packs (bag type package) that is used in particular for pocket type (Pouch) battery.
For example, described battery packages and/or battery firebreak device can be packing (particularly housing) and/or the firebreak devices for one or more batteries, battery module and/or the battery pack of automobile batteries or automobile batteries.
About other technical characterstic and the advantage of battery packages of the present invention, here can be clearly referring to the elaboration relevant to battery of the present invention and referring to accompanying drawing and accompanying drawing explanation.
Another theme of the present invention is battery, automobile batteries for example, and this power brick is containing for example, according to battery packages of the present invention and/or battery firebreak device and particularly at least one primary cell that contains organic bath, lithium battery.Wherein, described at least one primary cell can be particularly by described battery packages and/or battery firebreak device or described at least one phosphatic compound or phosphatic material at least in part, optionally fully wrap.
In this case, described battery can comprise a plurality of according to battery packages of the present invention and/or battery firebreak device.For example, described battery can have at least one packing that is designed for single battery and/or fireproof battery packages of the present invention and/or battery firebreak device and/or at least one and is designed for the packing of the single battery group being formed by a plurality of batteries and/or fireproof battery packages of the present invention and/or battery firebreak device and/or at least one and is designed for packing and/or fireproof battery packages of the present invention and/or the battery firebreak device of two or more battery pack.
Substantially, described power brick is containing bag-type battery and for example cylindric or prismatic batteries with duricrust housing.Described battery also can comprise duricrust housing and one or more bag-type battery.
For example, a plurality of primary cells can for example be packed with the form of flexible blister-pack respectively individually in the first embodiment of battery packages of the present invention, the primary cell that wherein two or more packings are crossed again together in the second embodiment of the identical or different type of battery packages of the present invention for example with the form of flexible film's packing or pack with the form of duricrust housing.Optionally, the battery pack that two or more packings are crossed can be again particularly packed with the form of duricrust housing in the 3rd embodiment of the identical or different type of battery packages of the present invention.
In the scope of an execution mode, the mass ratio of electrolyte (particularly liquid electrolyte) and described at least one phosphate-containing compound 2:1 to 1:2, particularly 1:1 to 1:2, for example at 1:1 to 1:1.5 or 1:1.1, for example, in the scope of about 1:1.
Organic bath can refer to particularly organically liquid electrolyte especially.
For example, described organic bath can comprise at least one organic solvent or at least one organic carbonate.Described at least one organic carbonate for example can be selected from ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), carbonic acid two ethyls (DEC) or their mixture.
In addition, described organic bath can comprise the conducting salt of at least one conducting salt, particularly alkali metal containing, for example, contain the conducting salt of lithium.For example, described electrolyte can comprise at least one conducting salt, and this conducting salt is selected from lithium hexafluoro phosphate (LiPF
6), two (oxalate closes) lithium borate (LiBoB), lithium perchlorate (LiClO
4), LiBF4 (LiBF
4) and their mixture.For example, described electrolyte can comprise lithium hexafluoro phosphate (LiPF
6) as conducting salt.
The negative electrode of described at least one battery for example can comprise at least one metal oxide, and this metal oxide is selected from iron lithium phosphate (LiFePO especially
4), lithium and cobalt oxides (LiCoO
2), lithium nickel oxide (LiNiO
2), lithium nickel cobalt manganese oxide (NCM, Li(Ni, Co, Mn) O
2, for example Ni:Co:Mn ratio is 1:1:1 or other Ni:Co:Mn ratio, for example 5:3:2), lithium manganese oxide (LiMnO
4), Li-Ti oxide (Li
4ti
5o
12) and their mixture.
Because can advantageously stop very as soon as possible thermal runaway by described at least one phosphatic compound, when organic bath decomposes and before particularly reaching the critical temperature of cathodic metal oxide for example, stop, in this critical temperature otherwise extraly the decomposition reaction of metal oxide cathode materials may occur and discharge oxygen, this can cause forming of the flammable mixture that become to be grouped into organic bath by oxygen and therefore cause and catch fire, described battery packages and/or battery firebreak device for example can improve, at the cathode material that uses decomposition temperature for example lower than the unstable metal oxide of 200 ℃ (lithium and cobalt oxides LiCoO
2and/or lithium nickel oxide LiNiO
2) time fail safe.
For example using decomposition temperature for example, higher than the situation of the stable cathode material (so-called NCM and/or iron lithium phosphate based on Ni-Co-Mn) of 200 ℃, by battery packages of the present invention and/or battery firebreak device, the oxygen by cathode material can be discharged and even delay or postpone till far to surpass the temperature of 200 ℃ and reduce quantitatively this oxygen to discharge, and therefore can further improve the fail safe of battery.
Therefore, the negative electrode of described at least one battery advantageously comprises lithium nickel cobalt manganese oxide (NCM, Li(NiCoMn) O
2, for example wherein Ni:Co:Mn ratio is 1:1:1 or other Ni:Co:Mn ratio, for example 5:3:2) and/or iron lithium phosphate (LiFePO
4).
Described heat-labile film particularly can be arranged between described at least one battery and described at least one phosphatic compound or phosphatic material.Described heat-labile film particularly can be separated from one another by described at least one battery and described at least one phosphate-containing compound or phosphatic material.For example, described heat-labile film can at least in part, optionally fully wrap up described at least one battery.Substituting or extraly, described polymer-phosphate composite material can be at least in part, optional described at least one battery of parcel fully.
Described at least one battery can refer to lithium ion battery especially.
About other technical characterstic and the advantage of battery of the present invention, here can be clearly referring to the elaboration relevant to battery packages of the present invention and referring to accompanying drawing and accompanying drawing explanation.
Drawings and Examples
Other advantage of theme of the present invention and favourable embodiment will be illustrated and be set forth in the following description by drawings and Examples.Wherein it is noted that the only descriptive feature of tool of described drawings and Examples, and can not think and limit by any way the present invention.Wherein shown:
Fig. 1 is equipped with the schematic cross-section of battery of the first execution mode of battery packages of the present invention; With
Fig. 2 is equipped with the schematic cross-section of battery of the second execution mode of battery packages of the present invention,
Fig. 3 has 200mg FePO
4200mg LiPF
6the rate of heat addition of EC/DMC or 200mg EC/DMC changes (Verlaeufe);
Fig. 4 does not have FePO
41M LiPF
6the pressure of EC/DMC or EC/DMC changes;
Fig. 5 has 200mg FePO
4or do not there is FePO
4200mg LiPF
6the rate of heat addition of EC/DMC changes;
Fig. 6 has 200mg FePO
4or do not there is FePO
4200mg LiPF
6eC/DMC and there is 200mg NCM/LiCoO
2200mg LiPF
6the rate of heat addition of EC/DMC changes;
Fig. 7 a, 7b have 200mg FePO
4and there is the charged LiFePO of 200mg maximum 80% or 50%
4200mg LiPF
6the rate of heat addition of EC/DMC changes or pressure changes; With
Fig. 8 has 200mg FePO
4do not there is FePO
4200mg LiPF
6the pressure of EC/DMC-time changes;
The scope of the first execution mode showing at Fig. 1, battery packages 10 has packing matrix 12, and the inner side of this matrix covers with phosphatic material 11.Wherein, phosphatic material for example can comprise or ferric phosphate and/or iron lithium phosphate.Wherein, packing matrix 12 be by aluminium, formed and be hard substantially.Therefore,, in the scope of this execution mode, battery packages 10 also can be called battery duricrust housing.
Fig. 1 shown, battery packages 10 also has heat-labile film 13 except packing matrix 12, plastic film for example, for example fusing or the cracking when surpassing certain temperature of this film.Therefore, this thermally labile film 13 can for example be formed by least one thermoplastic polymer, particularly polypropylene and/or polyethylene.
Fig. 1 shows, wherein said for example with the phosphatic material 11 of powder type partly with thermally labile film 13 adjacency, and be wherein particularly wrapped in the chamber forming between heat-labile film 13 and the inner side of packing matrix 12.
Fig. 1 has shown, has arranged a large amount of primary cell 1 in battery packages 10, and this primary cell contains organic bath.Wherein, this primary cell 1 particularly has organic bath, and this electrolyte comprises for example at least one organic carbonate (for example ethylene carbonate, propylene carbonate, dimethyl carbonate and/or carbonic acid two ethyls) and at least one conducting salt (lithium hexafluoro phosphate).Described primary cell 1 can refer to lithium ion battery especially.
The scope of the execution mode showing at Fig. 1, when the temperature in battery packages 10 surpasses certain temperature, 13 fusing or the crackings of described thermally labile film, thus described phosphatic material 11 covers or wetting this battery stoped the decomposition of organic bath.
The difference of the second execution mode of the battery packages of the present invention 10 showing in Fig. 2 and the first execution mode showing in Fig. 1 is on the one hand substantially, phosphatic for example thin layer 11 coating for the inner side of packing matrix.For example, phosphatic layer 11 can for example, for example be formed with the form of netted formation by polymer-phosphate composite material (polymer-ferric phosphate composite material).Wherein, described polymer-phosphate composite material 11 particularly can comprise at least one thermoplastic polymer as polymer 11, for example polypropylene and/or polyethylene.
The type of action of the second execution mode wherein, showing in Fig. 2 based on Fig. 1 in the similar principle of the first execution mode that shows.For example, as long as the temperature in battery packages 10 surpasses certain temperature (scope of 130-150 ℃), at least one polymer of polymer-phosphate composite material (for example polypropylene (PP) and/or polyethylene (PE)) melts and discharges described at least one phosphatic compound 11, and the electrolyte that then this phosphatic compound can suppress to start decomposes and therefore stop liberated heat.In this situation, the particle of described at least one phosphate-containing compound can keep being connected or gently flowing down (abreiseln) with the inwall of packing matrix 12 at least in part.
On the other hand, the second execution mode of the battery packages of the present invention 10 showing in Fig. 2 is substantially with the difference of the first execution mode showing in Fig. 1, packing matrix 12 is flexible aluminium foil or the flexible laminated material being formed by the layer of two kinds or more of particularly film-forms, and wherein at least one layer of this laminated material is aluminium lamination.In the scope of this execution mode, battery packages 10 or this battery also can be called bag-type battery packing or bag-type battery.
In Fig. 2, also show, in battery packages, be furnished with a large amount of stacking primary cells 1 each other, these primary cells there is respectively negative electrode 2, anode 4 and be arranged in the middle of spacer 3, negative electrode 2 cathode current conductor (Ableiter) 5 of next-door neighbour's aluminum and anode 4 next-door neighbour anode current conductor 6 made of copper in addition wherein.For the reason of clearness (Uebersichtlichkeit), three such batteries 1 in Fig. 2, have only been shown.But the layer order of setting forth still can be in multiple times repeatedly, thereby make the number n of stacking battery 1 so each other can be greater than 3.
The negative electrode 2 of the primary cell 1 showing in Fig. 1 and 2 can comprise at least one metal oxide, for example iron lithium phosphate, lithium and cobalt oxides, lithium nickel oxide and/or lithium nickel cobalt manganese oxide especially.
Embodiment
By adiabatic calorimeter (English: accelerated rate calorimetry) study ferric phosphate and there is the impact of the iron lithium phosphate of different lithium contents on organic bath.
That as organic bath, use is conducting salt lithium hexafluoro phosphate (LiPF
6) solution at ethylene carbonate (EC) and dimethyl carbonate (DEC) with the 1M in the solvent mixture of the ratio (w/w) of 1:1.
What as adiabatic calorimeter, use is the so-called calorimeter with heating-wait for-search (heat-wait-search) work pattern, wherein first sample is heated to predetermined temperature, this system can autobalance (equilibrieren) in standby mode process until reach desirable temperature.Wherein, in seek mode, can find targetedly heat release, as long as wherein reach or surpass set detection limit value, outside heating region can be followed the tracks of exothermic temperature and raises and make exothermic reaction visible under adiabatic condition.As long as there is not exothermic phenomenon in seek mode, this system heating is to next temperature rank (heating mode).As detection limit value, select the rate of heat addition of 0.02 ℃/min.Temperature interval is 5K.Measurement is carried out in the temperature range of 50-350 ℃ under the atmosphere of protective gas.
Except temperature and rate of heat addition variation, also described respectively pressure variation.
Fig. 3 has shown, the rate of heat addition of the mixture 20 being formed by ethylene carbonate-dimethyl carbonate solvent mixture of the lithium hexafluoro phosphate of the ferric phosphate of 200mg and the 1M of 200mg changes, and is changed by the rate of heat addition of the mixture 21 not forming containing ethylene carbonate-dimethyl carbonate solvent mixture of lithium hexafluoro phosphate of the ferric phosphate of 200mg and 200mg; Fig. 3 has shown that maximum heating speed is in both cases lower than 1 ℃/min.Yet it has shown visibly different initial temperature (heat release is surveyed and started).The measurement of the ethylene carbonate-dimethyl carbonate solvent mixture 20 that contains lithium hexafluoro phosphate is approximately 190 ℃ of beginnings, and containing the initial temperature of ethylene carbonate-dimethyl carbonate solvent mixture 21 of lithium hexafluoro phosphate, is not approximately 250 ℃.
Fig. 4 has shown that ethylene carbonate-dimethyl carbonate solvent mixture 20', the 21' of corresponding not phosphoric acid iron are along with the pressure variation of temperature.In addition, described to approach desirable gas curve 22 in Fig. 4, this curve has only been considered the expansion of argon gas (protective gas) in reaction system.Fig. 4 shown, not ethylene carbonate-dimethyl carbonate solvent mixture 20', the 21' of the phosphoric acid iron behavior ideal-like gas when being up to approximately 80 ℃.Fig. 4 shows, for ethylene carbonate-dimethyl carbonate solvent mixture 20', the 21' of phosphoric acid iron be not compared to the ethylene carbonate-dimethyl carbonate solvent mixture 20, the 21(20:190 ℃ that contain accordingly ferric phosphate showing in Fig. 3 respectively, 21:250 ℃) significantly lower temperature (20':155 ℃, 21':180 ℃) can have been observed and decompose and therefore pressure rising.Than not containing ethylene carbonate-dimethyl carbonate solvent mixture 21, the 21' of lithium hexafluoro phosphate, the ethylene carbonate-dimethyl carbonate solvent mixture 20 that contains lithium hexafluoro phosphate, the rate of heat addition that 20' occurs at lower temperature or pressure raise and may the reversible endothermic decomposition based on lithium hexafluoro phosphate react (LiPF
6(s) → LiF (s)+PF
5(g), H > 0) and the solvent polymeric reaction that causes thus.
Fig. 5 has shown that containing ferric phosphate contains again ethylene carbonate-dimethyl carbonate solvent mixture 20 of lithium hexafluoro phosphate and not phosphoric acid iron and comparison that the rate of heat addition of ethylene carbonate-dimethyl carbonate solvent mixture 20' of containing lithium hexafluoro phosphate changes.Fig. 5 has shown, phosphoric acid iron and the maximum heating speed of ethylene carbonate-dimethyl carbonate solvent mixture 20' of containing lithium hexafluoro phosphate is that approximately 30 ℃/min and initial temperature are approximately 180 ℃ not, contains in contrast ethylene carbonate-dimethyl carbonate solvent mixture 20 that lithium hexafluoro phosphate contains again lithium hexafluoro phosphate and only has the maximum heating speed lower than 1 ℃.Therefore, by adding ferric phosphate can advantageously significantly suppress electrolytical decomposition.In addition, by ferric phosphate, also advantageously reducing adiabatic temperature improves and initial temperature is passed to higher temperature.
Fig. 6 shown, replace 200mg ferric phosphate 20 and by 200mg by nickel, cobalt and manganese oxide (NCM) and lithium and cobalt oxides (LiCoO
2) blend 23 that forms adds ethylene carbonate-dimethyl carbonate solvent mixture that 200mg contains lithium hexafluoro phosphate to and but can not reach inhibitory action, but even from approximately 130 ℃ and therefore even obviously before ethylene carbonate-dimethyl carbonate solvent mixture 20' of phosphoric acid iron not, just can observe thermal runaway.
In order to study phosphate gegenion to inhibiting impact, studied in addition the iron lithium phosphate with different lithium contents.It is prepared as follows: the lithium ion battery with iron lithium phosphate negative electrode and rated capacity 2Ah is applied to specific electriferous state (20a:80%, 20b:50%) by CC-CV electric charge (constant charge-constant voltage).In this situation, along with higher electriferous state, lithium content reduces, and wherein when 100% electriferous state, has the ferric phosphate that goes lithiumation.Produced iron lithium phosphate is removed, repeatedly used dimethyl carbonate (DMC) to rinse and is dried in a vacuum under the atmosphere of protective gas from battery.
Fig. 7 a, 7b shown, the rate of heat addition of the 50% charged iron lithium phosphate of the 80% charged iron lithium phosphate of the mixture of ethylene carbonate-dimethyl carbonate solvent mixture 20 that 200mg ferric phosphate (=100% charged or go completely the iron lithium phosphate of lithiumation) and 200mg contain lithium hexafluoro phosphate, 200mg and the mixture of ethylene carbonate-dimethyl carbonate solvent mixture 20a that 200mg contains lithium hexafluoro phosphate and 200mg and the mixture of ethylene carbonate-dimethyl carbonate solvent mixture 20b that 200mg contains lithium hexafluoro phosphate changes or pressure changes.Fig. 7 a, 7b have shown that all rates of heat addition change in addition lower than 1 ℃/min, and this shows that the electriferous state of lithium content, iron lithium phosphate and the gegenion of phosphate radical itself almost do not have or not impact suppressing electrolyte decomposition.
Fig. 8 shown contain ferric phosphate contain again ethylene carbonate-dimethyl carbonate solvent mixture 20 of lithium hexafluoro phosphate and not phosphoric acid iron and ethylene carbonate-dimethyl carbonate solvent mixture 20' of containing lithium hexafluoro phosphate along with the discharging pressure of time changes.This figure has obviously shown exothermic process delaying in time.
Claims (15)
1. battery packages (10) and/or the battery firebreak device of the primary cell that contains organic bath at least one (1), it comprises at least one phosphatic compound (11).
2. according to the battery packages of claim 1 and/or battery firebreak device, wherein said at least one phosphatic compound is metal phosphate, and it is selected from ferric phosphate, lithium phosphate, iron lithium phosphate, manganese phosphate, cobalt phosphate and/or manganese phosphate and mixture especially.
3. according to the battery packages of claim 1 or 2 and/or battery firebreak device, wherein said battery packages and/or battery firebreak device (10) have phosphatic material (11), and this material comprises described at least one phosphatic compound (11),
Wherein this phosphatic material (11) is polymer-phosphate composite material or phosphatic powder.
4. according to the battery packages of one of claims 1 to 3 and/or battery firebreak device, wherein said battery packages and/or battery firebreak device (10) have heat-labile film (13).
5. according to the battery packages of claim 3 or 4 and/or battery firebreak device, wherein said phosphatic material (11) at least partly with heat-labile film (13) in abutting connection with and/or itself be heat-labile at least partly.
6. according to the battery packages of one of claim 3 to 5 and/or battery firebreak device, wherein said thermally labile film (13) and/or described polymer-phosphate composite material (11) comprise at least one thermoplastic polymer, particularly polypropylene and/or polyethylene.
7. according to the battery packages of one of claim 1 to 6 and/or battery firebreak device, wherein said battery packages and/or battery firebreak device (10) have matrix (12), particularly pack matrix, wherein this matrix (12), the inner side of particularly packing matrix cover with described phosphatic material (11).
8. according to the battery packages of claim 7 and/or battery firebreak device, wherein said phosphatic material (11) is arranged, is particularly wrapped in described heat-labile film (13) and described matrix (12), is particularly packed between the inner side of matrix.
9. according to the battery packages of claim 7 or 8 and/or battery firebreak device, wherein said matrix (12), particularly pack matrix and comprise aluminium.
10. according to the battery packages of one of claim 1 to 9 and/or battery firebreak device, wherein said battery packages and/or battery firebreak device (10) are especially for the battery duricrust housing of bag-type battery or the battery thin film of toughness packing.
11. batteries, it comprises
-according to the battery packages of one of claim 1 to 10 (10) and/or battery firebreak device, and
-at least one primary cell that contains organic bath (10), particularly lithium battery.
12. according to the battery of claim 11, and wherein the mass ratio of electrolyte and described at least one phosphatic compound arrives the scope of 1:2 at 2:1.
13. according to the battery of claim 11 or 12, and wherein said organic bath comprises
At least one organic carbonate and/or
At least one is containing the conducting salt of lithium, and this conducting salt is selected from lithium hexafluoro phosphate, two (oxalate closes) lithium borate, lithium perchlorate, LiBF4 and their mixture especially.
14. according to claim 11 to one of 13 battery, and the negative electrode (2) of wherein said at least one battery (1) comprises at least one metal oxide, particularly lithium nickel cobalt manganese oxide and/or iron lithium phosphate.
15. according to claim 11 to one of 14 battery, and wherein said at least one battery (1) is lithium ion battery.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE201210212956 DE102012212956A1 (en) | 2012-07-24 | 2012-07-24 | Battery packaging and battery fire-inhibition device e.g. battery hard shell housing used for e.g. battery for motor car and mobile telephone, have galvanic cell comprising phosphate-containing compound(s) and organic electrolyte |
| DE102012212956.1 | 2012-07-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103579697A true CN103579697A (en) | 2014-02-12 |
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ID=49999122
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310310357.5A Pending CN103579697A (en) | 2012-07-24 | 2013-07-23 | Battery package and/or battery fireproof device |
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| CN (1) | CN103579697A (en) |
| DE (1) | DE102012212956A1 (en) |
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| CN104218202A (en) * | 2014-07-30 | 2014-12-17 | 浙江超威创元实业有限公司 | Lithium battery having fire-proof and explosion-proof device and electrical vehicle equipped with same |
| CN104218193A (en) * | 2014-07-30 | 2014-12-17 | 浙江超威创元实业有限公司 | Lithium battery having fire-proof and explosion-proof device and electrical vehicle equipped with same |
| CN104218194A (en) * | 2014-07-30 | 2014-12-17 | 浙江超威创元实业有限公司 | Lithium battery having fire-proof and explosion-proof device and electrical vehicle equipped with same |
| CN104218201A (en) * | 2014-07-30 | 2014-12-17 | 浙江超威创元实业有限公司 | Lithium battery having fire-proof and explosion-proof device and electrical vehicle equipped with same |
| CN104241565A (en) * | 2014-07-30 | 2014-12-24 | 浙江超威创元实业有限公司 | Lithium battery provided with fire-proof and explosion-proof device and electric car adopting battery |
| US10319970B2 (en) | 2014-07-30 | 2019-06-11 | Zhejiang Chilwee Chuangyuan Industry Company Ltd. | Lithium-ion battery and electric vehicle utilizing the same |
| US10892454B2 (en) | 2017-01-09 | 2021-01-12 | Industrial Technology Research Institute | Battery module with thermal dissipation and thermal runaway prevention |
| US10665909B2 (en) | 2017-07-17 | 2020-05-26 | International Business Machines Corporation | Battery thermal run-away and combustion prevention system |
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