WO2001029920A1 - Shutdown and redox shuttle additives for batteries - Google Patents
Shutdown and redox shuttle additives for batteries Download PDFInfo
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- WO2001029920A1 WO2001029920A1 PCT/US2000/028975 US0028975W WO0129920A1 WO 2001029920 A1 WO2001029920 A1 WO 2001029920A1 US 0028975 W US0028975 W US 0028975W WO 0129920 A1 WO0129920 A1 WO 0129920A1
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- Prior art keywords
- cell
- battery
- additive
- substituted
- additives
- Prior art date
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- 239000000654 additive Substances 0.000 title claims abstract description 75
- 239000003792 electrolyte Substances 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 6
- 210000004027 cell Anatomy 0.000 claims description 47
- 230000000996 additive effect Effects 0.000 claims description 22
- 125000001424 substituent group Chemical group 0.000 claims description 20
- 150000001555 benzenes Chemical class 0.000 claims description 18
- 150000002367 halogens Chemical class 0.000 claims description 16
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 11
- 150000005573 methoxybenzenes Chemical class 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000002790 naphthalenes Chemical class 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 210000000352 storage cell Anatomy 0.000 claims description 6
- 150000005528 benzodioxoles Chemical class 0.000 claims description 5
- RDOXTESZEPMUJZ-UHFFFAOYSA-N methyl phenyl ether Natural products COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 5
- CRUILBNAQILVHZ-UHFFFAOYSA-N 1,2,3-trimethoxybenzene Chemical group COC1=CC=CC(OC)=C1OC CRUILBNAQILVHZ-UHFFFAOYSA-N 0.000 claims description 4
- JDCMOHAFGDQQJX-UHFFFAOYSA-N 1,2,3,4,5,6,7,8-octafluoronaphthalene Chemical compound FC1=C(F)C(F)=C(F)C2=C(F)C(F)=C(F)C(F)=C21 JDCMOHAFGDQQJX-UHFFFAOYSA-N 0.000 claims description 2
- ZRQUIRABLIQJRI-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-methoxybenzene Chemical compound COC1=C(F)C(F)=C(F)C(F)=C1F ZRQUIRABLIQJRI-UHFFFAOYSA-N 0.000 claims description 2
- SOZFIIXUNAKEJP-UHFFFAOYSA-N 1,2,3,4-tetrafluorobenzene Chemical compound FC1=CC=C(F)C(F)=C1F SOZFIIXUNAKEJP-UHFFFAOYSA-N 0.000 claims description 2
- AJKNNUJQFALRIK-UHFFFAOYSA-N 1,2,3-trifluorobenzene Chemical group FC1=CC=CC(F)=C1F AJKNNUJQFALRIK-UHFFFAOYSA-N 0.000 claims description 2
- RDOGTTNFVLSBKG-UHFFFAOYSA-N 1,2-difluoro-3-methoxybenzene Chemical compound COC1=CC=CC(F)=C1F RDOGTTNFVLSBKG-UHFFFAOYSA-N 0.000 claims description 2
- DWVNLBRNGAANPI-UHFFFAOYSA-N 1,2-dimethoxy-3-nitrobenzene Chemical compound COC1=CC=CC([N+]([O-])=O)=C1OC DWVNLBRNGAANPI-UHFFFAOYSA-N 0.000 claims description 2
- KTPHYLJFAZNALV-UHFFFAOYSA-N 2,3,4-trifluorobenzonitrile Chemical compound FC1=CC=C(C#N)C(F)=C1F KTPHYLJFAZNALV-UHFFFAOYSA-N 0.000 claims description 2
- YCSGHMDKBZNXJC-UHFFFAOYSA-N 2,3,4-trimethoxybenzonitrile Chemical compound COC1=CC=C(C#N)C(OC)=C1OC YCSGHMDKBZNXJC-UHFFFAOYSA-N 0.000 claims description 2
- LBXGBNHUNHWYRM-UHFFFAOYSA-N 2,3-dimethoxybenzonitrile Chemical compound COC1=CC=CC(C#N)=C1OC LBXGBNHUNHWYRM-UHFFFAOYSA-N 0.000 claims description 2
- 229940030010 trimethoxybenzene Drugs 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims 3
- 229920000642 polymer Polymers 0.000 claims 2
- CSPHFUKBONQAOI-UHFFFAOYSA-N 1,2-difluoro-3,4-dimethoxybenzene Chemical compound COC1=CC=C(F)C(F)=C1OC CSPHFUKBONQAOI-UHFFFAOYSA-N 0.000 claims 1
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- 239000005518 polymer electrolyte Substances 0.000 abstract description 6
- 150000001491 aromatic compounds Chemical class 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 150000005575 dimethoxybenzenes Chemical class 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- FTNJQNQLEGKTGD-UHFFFAOYSA-N 1,3-benzodioxole Chemical class C1=CC=C2OCOC2=C1 FTNJQNQLEGKTGD-UHFFFAOYSA-N 0.000 description 1
- NADHCXOXVRHBHC-UHFFFAOYSA-N 2,3-dimethoxycyclohexa-2,5-diene-1,4-dione Chemical compound COC1=C(OC)C(=O)C=CC1=O NADHCXOXVRHBHC-UHFFFAOYSA-N 0.000 description 1
- ICQWQSZIAYKVDV-UHFFFAOYSA-N 2,4,5-trimethoxypyrimidine Chemical compound COC1=CN=C(OC)N=C1OC ICQWQSZIAYKVDV-UHFFFAOYSA-N 0.000 description 1
- RJVAFLZWVUIBOU-UHFFFAOYSA-N 2,4,6-trimethoxypyrimidine Chemical compound COC1=CC(OC)=NC(OC)=N1 RJVAFLZWVUIBOU-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 206010014415 Electrolyte depletion Diseases 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- -1 difluoro- substituted dimethoxybenzenes Chemical class 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-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
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 150000005839 radical cations Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraethylene glycol dimethyl ether Natural products COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- DGQOCLATAPFASR-UHFFFAOYSA-N tetrahydroxy-1,4-benzoquinone Chemical compound OC1=C(O)C(=O)C(O)=C(O)C1=O DGQOCLATAPFASR-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—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
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
-
- 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
-
- 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 invention relates to rechargeable batteries, and more particularly to shutdown additives and redox shuttle additives for overcharge protection in rechargeable batteries.
- the redox shuttle approach to overcharge protection employs an electrolyte additive that acts as an internal current shunt when the charging potential exceeds a characteristic onset potential for the additive.
- an electrolyte additive that acts as an internal current shunt when the charging potential exceeds a characteristic onset potential for the additive.
- the ability of certain organic aromatic compound additives to extend cell life in transition metal oxide lithium solid polymer electrolyte cells under conditions of moderate to severe overcharging has been demonstrated, as illustrated in U.S. Patent 6,004,698 to Richardson et al.
- Other redox shuttle additives have been reported for both polymer electrolyte, as described by F. Tran- Van et al., Electrochim. Acta, 44, 2789 (1999), and 4 volt lithium ion cells, as shown in U.S. Patent 5,763,119 to Adachi.
- Redox shuttle additives provide an internal, automatic overcharge protection mechanism that allows charging current to pass through the cell without overcharging it.
- the ability of such additives to extend cell life in lithium and lithium ion cells under conditions of moderate to severe overcharging has been demonstrated.
- the issue of safety takes precedence over the desire for cell life extension.
- a mechanism that renders the battery harmless on overcharging is acceptable even though it ends its useful life.
- shutdown additives that achieve this goal are desired.
- shutdown additives which may also act as redox shuttle additives, for rechargeable lithium or lithium ion batteries, particularly 4 V lithium ion batteries.
- the invention is a group of shutdown additives for the electrolyte of rechargeable batteries or electrochemical storage or secondary cells, and the rechargeable batteries or electrochemical storage cells with these additives.
- the additives are low molecular weight organic aromatic compounds, and function to prevent overcharging of the cell.
- one or more of the additives When one or more of the additives is added to the electrolyte of a rechargeable cell, it will be oxidized at the positive electrode at a potential specific to the additive(s). The product of this oxidation increases the resistance of the cell by means of polymerization, precipitation, electrolyte depletion, chemical reaction, or other mechanism. This prevents further charging of the cell, thereby preventing development of unsafe conditions.
- Some of the additives also function as redox shuttle additives at less severe overcharging conditions. When one or more of them is added to the electrolyte of a rechargeable cell, it is oxidized at the positive electrode to its respective radical cation at certain potentials. The cation diffuses through the electrolyte to the negative electrode, where it is reduced to its original neutral state. This allows the additive(s) to transport an electrical charge through the cell without damage to the cell under conditions that would, in the absence of the additive(s), cause it to lose capacity or fail. Under more severe overcharging conditions, the cation transport through the electrolyte is insufficient, and the additives are oxidized at the positive electrode to shut off the cell.
- additives could find use in any rechargeable battery utilizing a non-aqueous or solid polymer electrolyte and a positive electrode which is fully charged at about 4 V vs. Li/Li + .
- These include batteries for consumer electronics, communications, power tools, electric vehicles, and load leveling.
- Fig. 1 is a cross-sectional view of a rechargeable battery or electrochemical cell.
- Fig. 2 is a graph of the onset potentials of two shutdown additives of the invention.
- Fig. 3 is a graph of the onset potentials of seven shutdown/redox shuttle additives of the invention compared to two prior art additives.
- Fig. 4 is a graph of the onset potentials of seventeen shutdown/redox shuttle additives of the invention.
- the invention applies to rechargeable batteries or electrochemical storage cells, e.g. lithium and lithium ion batteries, of the type which are well known in the art, e.g. as described in U.S. Patents 6,004,698 and 5,763,119, which are herein incorporated by reference.
- the materials of which the standard parts of the batteries or cells of the invention are made, as well as the configuration of the battery or cell, can be found in these and other references.
- Fig. 1 illustrates a battery or cell 12 that is formed within a nonreactive outer case or shell 12 with an optional insulating inner lining 14 inside case 12 that form sidewalls of battery 12.
- a negative electrode current collector 20 is positioned against one sidewall of battery 12, and a negative electrode 24, which forms the negative electrode material, is positioned next to and in contact with negative electrode current collector 20.
- negative electrode 24 and negative electrode current collector 20 may form a unitary structure, referred to as negative electrode 24.
- a positive electrode current collector 36 is positioned against an opposed sidewall of battery 12, and a positive electrode 32, which forms the positive electrode material, is positioned next to and in contact with positive electrode current collector 36.
- positive electrode 32 and positive electrode current collector 36 may form a unitary structure, referred to as positive electrode 32.
- electrolyte 28 Between negative electrode 24 and positive electrode 32 is solid polymer electrolyte 28, which is ionically conducting and also serves as an insulator or separator between the negative electrode 24 and positive electrode 32. In some batteries it may be possible that the electrolyte is liquid.
- electrolyte 28 includes the shutdown or shutdown/redox shuttle additives of the invention.
- the shutdown (SD) and shutdown/redox shuttle (SD/RS) additives of the invention have common structural features including an aromatic ring and electro- withdrawing substituents which give them high oxidation potentials and stabilize the resulting oxidized species. They fall into several structural subcategories. Some additives can be considered to be members of more than one of these subgroups.
- Category A halogenated benzenes and naphthalenes
- Category D alkyl poly ethers
- Category E substituted nitrogen-containing heterocycles
- Table I act as cell shutdown additives:
- This invention provides new additives for batteries or electrochemical storage cells, particularly for 4 volt cells inco ⁇ orating liquid or preferably polymer electrolytes.
- the prior art redox shuttle additives by Sony researchers described in U.S. Patent 5,763,119 are dimethoxybenzenes with a single halide substituent, having molecular structure "a" shown below, where X is a halogen, e.g. fluorine (SONY 1) or bromine (SONY 2).
- SONY 1 and SONY 2 onset potentials ranging from 3.93 to 4.10 V vs. Li Li + .
- the onset potentials for the two best-performing SONY additives are shown in Fig. 3, labelled SONY 1 and SONY 2. While SONY 2 is capable of providing some overcharge protection in lithium cobalt cells, a significant capacity penalty is incurred due to an inability to fully charge the cells before the onset potential is reached. Similar limitations would apply to their use in lithium manganese oxide or lithium nickel oxide cells.
- LBNL 1 - 7 in Table II Seven additives of the present invention (LBNL 1 - 7 in Table II, with molecular structures shown below) are also included in the onset potential graph of Fig. 3.
- LBNL 1 and LBNL 2 differ from additives described in U.S. Patent 5,763,119 in being difluoro- substituted dimethoxybenzenes rather than monohalo-compounds.
- LBNL 3 is also a dimethoxybenzene, but it contains no halogen, having a nitrile group in a position para to a methoxy- group.
- LBNL 4 - 7 are 4-substituted l,2-(methylenedioxy)benzenes.
- the structures of LBNL 8 - 17 are also shown below.
- the LBNL additives have redox shuttle onset potentials of about 4.25 V or higher. Lithium manganese oxide cells containing these additives can be charged to their full normal capacity at 4.2 V. These cells are protected from overcharging and maintain their original discharge capacities for at least five cycles under conditions of severe overcharging (50% greater charge capacity than normal).
- LBNL 16 LBNL 17 The onset potentials of seventeen shutdown/redox shuttle additives (LBNL 1 - 17 in Table II) are shown in Fig. 4.
- the additives of the invention fall within the general subgroups of Categories A - E, with certain exclusions, and are more specifically identified as follows.
- Category A includes halogenated benzenes without any methoxy groups (it also can include halogenated benzenes with methoxy groups, but these will be discussed under category B).
- the halogenated benzenes include benzenes with only halogen substituents, such as trifluorobenzene and tetrafluorobenzene; there are preferably at least three halogen substituents.
- Various isomers of the tri- and tetra- fluorobenzenes are included in Tables I and II (SD 6, LBNL 19, LBNL 20; SD 7, LBNL 18, LBNL 21). The structures of these compounds are as follows:
- halogenated naphthalenes such as octafluoronaphthalene (LBNL 10).
- halogenated benzenes can also include benzenes with halogens and other (non-methoxy) substituents, such as trifluorobenzonitrile (LBNL 22-24), which have the following structure where X is another substituent, e.g. nitrile:
- Category B includes substituted methoxybenzenes with no halogens. There are again preferably at least three substituents. These additives include benzenes with only methoxy groups, such as trimethoxybenzene (SD 2, LBNL 14-15), and benzenes with methoxy groups and other (non-halogen) substituents, such as dimethoxybenzonitrile (SD 10, LBNL 3, LBNL 11-12), dimethoxynitrobenzene (LBNL 8), trimethoxybenzonitrile (LBNL 9, LBNL 13), and the related compound dimethoxybenzoquinone (SD 9).
- the structures of these compounds are as follows, where X is a (non-halogen) substituent such as nitro- or nitrile group:
- Category B also includes substituted methoxybenzenes with halogens (which overlaps with Category A since they would also be halogenated benzenes).
- this group of halogenated methoxybenzene additives excludes dimethoxybenzenes with a single halogen substituent (which are shown in U.S. Patent 5,763,119).
- This group of additives does include halogenated anisoles (benzenes with a single methoxy group), such as difluoroanisole (SD 1 , LBNL 16) and pentafluoroanisole (LBNL 17), and also includes dimethoxybenzenes with at least two halogen substituents, such as the previously described difiuorodimethoxy benzenes (LBNL 1-2).
- halogenated anisoles benzenes with a single methoxy group
- LBNL 16 difluoroanisole
- LBNL 17 pentafluoroanisole
- dimethoxybenzenes with at least two halogen substituents such as the previously described difiuorodimethoxy benzenes (LBNL 1-2).
- Category C is the substituted benzodioxoles or methylenedioxybenzenes, illustrated below, where X is a substituent. These include both halogenated compounds (LBNL 5-6) and nonhalogenated compounds (LBNL 4, LBNL 7) shown above.
- Category D is alkyl polyethers, such as methoxyethyl ether (SD 3) and tri- or tetra- (ethylene glycol) dimethyl ether (SD 4-5), illustrated below. ⁇ . . ⁇
- Category E is substituted nitrogen-containing heterocycles, such as trimethoxypyrimidine (SD 8), illustrated below along with generic substituted pyrimidines (X, Y, Z can be hydrogen).
- SD 8 trimethoxypyrimidine
- X, Y, Z can be hydrogen
- the amount of additive can vary widely. The minimum is probably about 1 % by weight. The maximum can be very high. The additive could replace all of the solvent in some cases, though this might be prohibitively expensive. Typically, 1 molar solutions have been used for testing in complete cells. This is because the electrolyte is 1 molar Li salt, and is therefore depleted of Li when all of the addditve is in the oxidized form. Adjustments (increases) to the Li salt concentration would probably be made in designing a cell that would incorporate a large amount of additive.
Abstract
A group of shutdown additives are provided in the electrolyte of rechargeable batteries or electrochemical storage or secondary cells. The additives are low molecular weight organic aromatic compounds, and function to prevent overcharging of the cell. Some of the additives also function as redox shuttle additives at less server overcharging conditions. These additives can be used in any rechargeable battery utilizing a non-aqueous or solid polymer electrolyte and a positive electrode which is fully charged at about 4 V vs. Li/Li+. These include batteries for consumer electronics, communications, power tools, electric vehicles, and load leveling.
Description
Shutdown and Redox Shuttle Additives for Batteries
Related Applications
This application claims priority of Provisional Application Ser. No. 60/160,391 filed 10/18/99, which is herein incorporated by reference.
Government Rights
The United States Government has rights in this invention pursuant to Contract No. DE-AC03-76SF00098 between the United States Department of Energy and the University of California.
Background of the Invention
The invention relates to rechargeable batteries, and more particularly to shutdown additives and redox shuttle additives for overcharge protection in rechargeable batteries.
Reliable and inexpensive overcharge protection for multi-cell lithium (and other) battery stacks is a major obstacle to commercialization of these promising systems in electric vehicles and other high voltage applications. Overcharging not only can reduce rechargeable capacity and cell life, but can also create hazardous conditions. Even moderate overcharging of transition metal oxide cathodes often leads to structural and compositional changes in the oxide matrix which have significant effects on their subsequent cycling behavior.
The redox shuttle approach to overcharge protection employs an electrolyte additive that acts as an internal current shunt when the charging potential exceeds a characteristic onset potential for the additive. The ability of certain organic aromatic compound additives to extend cell life in transition metal oxide lithium solid polymer electrolyte cells under conditions of moderate to severe overcharging has been demonstrated, as illustrated in U.S. Patent 6,004,698 to Richardson et al. Other redox shuttle additives have been reported for both polymer electrolyte, as described by F. Tran-
Van et al., Electrochim. Acta, 44, 2789 (1999), and 4 volt lithium ion cells, as shown in U.S. Patent 5,763,119 to Adachi.
Overcharging of batteries can create hazardous conditions, leading to explosion, fire, and or release of toxic materials. External protection mechanisms that stop charging when a voltage, temperature, or internal pressure limit is reached are currently in use, but these are subject to failure or abuse (such as using a charger designed for a different battery). Redox shuttle additives provide an internal, automatic overcharge protection mechanism that allows charging current to pass through the cell without overcharging it. The ability of such additives to extend cell life in lithium and lithium ion cells under conditions of moderate to severe overcharging has been demonstrated. However, for many applications, the issue of safety takes precedence over the desire for cell life extension. A mechanism that renders the battery harmless on overcharging is acceptable even though it ends its useful life. Thus "shutdown" additives that achieve this goal are desired. Some of these may act as redox shuttles under moderate overcharge conditions and as shutdown additives when the overcharge conditions are more severe. Both redox shuttle and shutdown additives may be present in the same cell.
Summary of the Invention
Accordingly it is an object of the invention to provide shutdown additives for rechargeable batteries.
It is also an object of the invention to provide shutdown additives for rechargeable batteries that also act as redox shuttle additives at lower overcharge conditions.
It is another object of the invention to provide shutdown additives, which may also act as redox shuttle additives, for rechargeable lithium or lithium ion batteries, particularly 4 V lithium ion batteries.
The invention is a group of shutdown additives for the electrolyte of rechargeable batteries or electrochemical storage or secondary cells, and the rechargeable batteries or electrochemical storage cells with these additives. The additives are low molecular weight organic aromatic compounds, and function to prevent overcharging of the cell. When one or more of the additives is added to the electrolyte of a rechargeable cell, it will
be oxidized at the positive electrode at a potential specific to the additive(s). The product of this oxidation increases the resistance of the cell by means of polymerization, precipitation, electrolyte depletion, chemical reaction, or other mechanism. This prevents further charging of the cell, thereby preventing development of unsafe conditions.
Some of the additives also function as redox shuttle additives at less severe overcharging conditions. When one or more of them is added to the electrolyte of a rechargeable cell, it is oxidized at the positive electrode to its respective radical cation at certain potentials. The cation diffuses through the electrolyte to the negative electrode, where it is reduced to its original neutral state. This allows the additive(s) to transport an electrical charge through the cell without damage to the cell under conditions that would, in the absence of the additive(s), cause it to lose capacity or fail. Under more severe overcharging conditions, the cation transport through the electrolyte is insufficient, and the additives are oxidized at the positive electrode to shut off the cell.
These additives could find use in any rechargeable battery utilizing a non-aqueous or solid polymer electrolyte and a positive electrode which is fully charged at about 4 V vs. Li/Li+. These include batteries for consumer electronics, communications, power tools, electric vehicles, and load leveling.
Brief Description of the Drawings
Fig. 1 is a cross-sectional view of a rechargeable battery or electrochemical cell.
Fig. 2 is a graph of the onset potentials of two shutdown additives of the invention.
Fig. 3 is a graph of the onset potentials of seven shutdown/redox shuttle additives of the invention compared to two prior art additives.
Fig. 4 is a graph of the onset potentials of seventeen shutdown/redox shuttle additives of the invention.
Detailed Description of the Invention
The invention applies to rechargeable batteries or electrochemical storage cells, e.g. lithium and lithium ion batteries, of the type which are well known in the art, e.g. as
described in U.S. Patents 6,004,698 and 5,763,119, which are herein incorporated by reference. The materials of which the standard parts of the batteries or cells of the invention are made, as well as the configuration of the battery or cell, can be found in these and other references.
Fig. 1 illustrates a battery or cell 12 that is formed within a nonreactive outer case or shell 12 with an optional insulating inner lining 14 inside case 12 that form sidewalls of battery 12. A negative electrode current collector 20 is positioned against one sidewall of battery 12, and a negative electrode 24, which forms the negative electrode material, is positioned next to and in contact with negative electrode current collector 20. Alternatively, negative electrode 24 and negative electrode current collector 20 may form a unitary structure, referred to as negative electrode 24. Similarly, a positive electrode current collector 36 is positioned against an opposed sidewall of battery 12, and a positive electrode 32, which forms the positive electrode material, is positioned next to and in contact with positive electrode current collector 36. Alternatively, positive electrode 32 and positive electrode current collector 36 may form a unitary structure, referred to as positive electrode 32.
Between negative electrode 24 and positive electrode 32 is solid polymer electrolyte 28, which is ionically conducting and also serves as an insulator or separator between the negative electrode 24 and positive electrode 32. In some batteries it may be possible that the electrolyte is liquid. In accordance with the invention, electrolyte 28 includes the shutdown or shutdown/redox shuttle additives of the invention.
The shutdown (SD) and shutdown/redox shuttle (SD/RS) additives of the invention have common structural features including an aromatic ring and electro- withdrawing substituents which give them high oxidation potentials and stabilize the resulting oxidized species. They fall into several structural subcategories. Some additives can be considered to be members of more than one of these subgroups.
Category A: halogenated benzenes and naphthalenes
Category B: substituted methoxybenzenes
Category C: substituted benzodioxoles
Category D: alkyl poly ethers
Category E: substituted nitrogen-containing heterocycles The following compounds in Table I act as cell shutdown additives:
Table I
The onset potential graphs for the first two additives in Table I (SD 1 , SD 2) are shown in Fig. 2.
In addition, the following additives in Table II can act both as redox shuttles under moderate overcharge conditions, and as cell shutdown additives when subjected to more severe overcharging:
Table II
This invention provides new additives for batteries or electrochemical storage cells, particularly for 4 volt cells incoφorating liquid or preferably polymer electrolytes. The prior art redox shuttle additives by Sony researchers described in U.S. Patent 5,763,119 are dimethoxybenzenes with a single halide substituent, having molecular structure "a" shown below, where X is a halogen, e.g. fluorine (SONY 1) or bromine (SONY 2).
a SONY 1 SONY 2
They have onset potentials ranging from 3.93 to 4.10 V vs. Li Li+. The onset potentials for the two best-performing SONY additives are shown in Fig. 3, labelled SONY 1 and SONY 2. While SONY 2 is capable of providing some overcharge protection in lithium cobalt cells, a significant capacity penalty is incurred due to an
inability to fully charge the cells before the onset potential is reached. Similar limitations would apply to their use in lithium manganese oxide or lithium nickel oxide cells.
Seven additives of the present invention (LBNL 1 - 7 in Table II, with molecular structures shown below) are also included in the onset potential graph of Fig. 3. LBNL 1 and LBNL 2 differ from additives described in U.S. Patent 5,763,119 in being difluoro- substituted dimethoxybenzenes rather than monohalo-compounds. LBNL 3 is also a dimethoxybenzene, but it contains no halogen, having a nitrile group in a position para to a methoxy- group. LBNL 4 - 7 are 4-substituted l,2-(methylenedioxy)benzenes. The structures of LBNL 8 - 17 are also shown below. The LBNL additives have redox shuttle onset potentials of about 4.25 V or higher. Lithium manganese oxide cells containing these additives can be charged to their full normal capacity at 4.2 V. These cells are protected from overcharging and maintain their original discharge capacities for at least five cycles under conditions of severe overcharging (50% greater charge capacity than normal).
LBNL 1 LBNL 2
LBNL 4 LBNL 5 LBNL 6 LBNL 7
LBNL 12 LBNL 13
LBNL 14 LBNL 15
LBNL 16 LBNL 17
The onset potentials of seventeen shutdown/redox shuttle additives (LBNL 1 - 17 in Table II) are shown in Fig. 4.
The additives of the invention fall within the general subgroups of Categories A - E, with certain exclusions, and are more specifically identified as follows.
Category A includes halogenated benzenes without any methoxy groups (it also can include halogenated benzenes with methoxy groups, but these will be discussed under category B). The halogenated benzenes include benzenes with only halogen substituents, such as trifluorobenzene and tetrafluorobenzene; there are preferably at least three halogen substituents. Various isomers of the tri- and tetra- fluorobenzenes are included in Tables I and II (SD 6, LBNL 19, LBNL 20; SD 7, LBNL 18, LBNL 21). The structures of these compounds are as follows:
Also included in Category A are halogenated naphthalenes, such as octafluoronaphthalene (LBNL 10).
The halogenated benzenes can also include benzenes with halogens and other (non-methoxy) substituents, such as trifluorobenzonitrile (LBNL 22-24), which have the following structure where X is another substituent, e.g. nitrile:
X
Category B includes substituted methoxybenzenes with no halogens. There are again preferably at least three substituents. These additives include benzenes with only methoxy groups, such as trimethoxybenzene (SD 2, LBNL 14-15), and benzenes with methoxy groups and other (non-halogen) substituents, such as dimethoxybenzonitrile (SD 10, LBNL 3, LBNL 11-12), dimethoxynitrobenzene (LBNL 8), trimethoxybenzonitrile (LBNL 9, LBNL 13), and the related compound dimethoxybenzoquinone (SD 9). The structures of these compounds are as follows, where X is a (non-halogen) substituent such as nitro- or nitrile group:
X X
o
OCH'
OCH-
O
2,6-dimethoxy-l ,4-benzoquinone
Category B also includes substituted methoxybenzenes with halogens (which overlaps with Category A since they would also be halogenated benzenes). However, this group of halogenated methoxybenzene additives excludes dimethoxybenzenes with a
single halogen substituent (which are shown in U.S. Patent 5,763,119). This group of additives does include halogenated anisoles (benzenes with a single methoxy group), such as difluoroanisole (SD 1 , LBNL 16) and pentafluoroanisole (LBNL 17), and also includes dimethoxybenzenes with at least two halogen substituents, such as the previously described difiuorodimethoxy benzenes (LBNL 1-2). The structure of a halogenated anisole is as follows:
OCH-
Category C is the substituted benzodioxoles or methylenedioxybenzenes, illustrated below, where X is a substituent. These include both halogenated compounds (LBNL 5-6) and nonhalogenated compounds (LBNL 4, LBNL 7) shown above.
Category D is alkyl polyethers, such as methoxyethyl ether (SD 3) and tri- or tetra- (ethylene glycol) dimethyl ether (SD 4-5), illustrated below.
Ό. . Ό
2-methoxyethyl ether
Λ .0^ ^o.
tri(ethylene glycol) dimethyel ether o^ X ΛX ^o.
tetra(ethylene glycol) dimethyel ether
Category E is substituted nitrogen-containing heterocycles, such as trimethoxypyrimidine (SD 8), illustrated below along with generic substituted pyrimidines (X, Y, Z can be hydrogen).
2,4,6-trimethoxypyrimidine
The amount of additive can vary widely. The minimum is probably about 1 % by weight. The maximum can be very high. The additive could replace all of the solvent in some cases, though this might be prohibitively expensive. Typically, 1 molar solutions have been used for testing in complete cells. This is because the electrolyte is 1 molar Li salt, and is therefore depleted of Li when all of the addditve is in the oxidized form. Adjustments (increases) to the Li salt concentration would probably be made in designing a cell that would incorporate a large amount of additive.
Changes and modifications in the specifically described embodiments can be carried out without departing from the scope of the invention which is intended to be limited only by the scope of the appended claims.
Claims
1. A battery or electrochemical storage cell, comprising a positive electrode, a negative electrode, an electrolyte between the positive and negative electrodes, and a shutdown additive in the electrolyte, wherein the shutdown additive is selected from:
A. halogenated benzenes, without additional substituents, and with additional substituents but excluding methoxy substituents, and halogenated naphthalenes,
B. substituted methoxybenzenes, without additional substituents, and with additional substituents, including halogens, but excluding monohalodimethoxybenzenes,
C. substituted benzodioxoles,
D. alkyl polyethers,
E. substituted nitrogen containing heterocycles.
2. The battery or cell of Claim 1 wherein the additive is a halogenated benzene without additional substituents, a halogenated benzene with additional substituents but excluding methoxy substituents, or a halogenated naphthalene.
3. The battery or cell of Claim 2 wherein the additive is selected from trifluorobenzene, tetrafluorobenzene, trifluorobenzonitrile, and octafluoronaphthalene.
4. The battery or cell of Claim 1 wherein the additive is a substituted methoxybenzene without additional substituents, a substituted methoxybenzene with additional substituents excluding halogens, or a substituted methoxybenzene with additional halogen substituents but excluding monohalodimethoxybenzenes.
5. The battery or cell of Claim 4 wherein the additive is selected from trimethoxybenzene, dimethoxybenzonitrile, trimethoxybenzonitrile, dimethoxynitrobenzene, difluoroanisole, pentafluoroanisole, and difluorodimethoxybenzene.
6. The battery or cell of Claim 1 wherein the additive is a substituted benzodioxple.
7. The battery or cell of Claim 1 wherein the additive is an alkyl polyether.
8. The battery or cell of Claim 1 wherein the additive is a substituted nitrogen containing heterocycle.
9. The battery or cell of Claim 1 wherein the electrolyte is a solid polymer.
10. The battery or cell of claim 1 wherein the battery or cell is a lithium battery or cell.
11. The battery or cell of Claim 10 wherein the battery or cell is a 4 V lithium battery or cell.
12. A method of preventing overcharging of a battery or electrochemical storage cell, comprising providing a shutdown additive in the electrolyte of the battery or cell, wherein the shutdown additive is selected from: A. halogenated benzenes, without additional substituents, and with additional substituents but excluding methoxy substituents, and halogenated naphthalenes, B. substituted methoxybenzenes, without additional substituents, and with additional substituents, including halogens, but excluding monohalodimethoxybenzenes, C. substituted benzodioxoles, D. alkyl polyethers, E. substituted nitrogen containing heterocycles.
13. An electrolyte with additive composition for a battery or electrochemical storage cell, comprising an electrolyte and a shutdown additive in the electrolyte, wherein the shutdown additive is selected from: A. halogenated benzenes, without additional substituents, and with additional substituents but excluding methoxy substituents, and halogenated naphthalenes, B. substituted methoxybenzenes, without additional substituents, and with additional substituents, including halogens, but excluding monohalodimethoxybenzenes, C. substituted benzodioxoles, D. alkyl polyethers, E. substituted nitrogen containing heterocycles.
14. The composition of Claim 13 wherein the electrolyte is a solid polymer.
15. The composition of Claim 13 wherein the shutdown additive is selected from the additives listed in Tables I and II.
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