US20020160273A1 - New organic borate compounds and the nonaqueous electrolytes and lithium secondary batteries using the compounds - Google Patents

New organic borate compounds and the nonaqueous electrolytes and lithium secondary batteries using the compounds Download PDF

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US20020160273A1
US20020160273A1 US09/957,455 US95745501A US2002160273A1 US 20020160273 A1 US20020160273 A1 US 20020160273A1 US 95745501 A US95745501 A US 95745501A US 2002160273 A1 US2002160273 A1 US 2002160273A1
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lithium
battery
nonaqueous electrolyte
solvent
lithium secondary
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Juichi Arai
Hideaki Katayama
Mitsuru Kobayashi
Hiroyuki Yamaguchi
Hideki Takahashi
Masaru Kato
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Kanto Chemical Co Inc
Hitachi Ltd
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Kanto Chemical Co Inc
Hitachi Ltd
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Assigned to KANTO KAGAKU KABUSHIKI KAISHA, HITACHI, LTD. reassignment KANTO KAGAKU KABUSHIKI KAISHA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KATO, MASARU, TAKAHASHI, HIDEKI, YAMAGUCHI, HIROYUKI, KATAYAMA, HIDEAKI, KOBAYASHI, MITSURU, ARAI, JUICHI
Publication of US20020160273A1 publication Critical patent/US20020160273A1/en
Priority to US10/641,085 priority Critical patent/US6824928B2/en
Priority to US10/972,404 priority patent/US7022878B2/en
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    • 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
    • H01M10/0568—Liquid materials characterised by the solutes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L50/00—Electric propulsion with power supplied within the vehicle
    • B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
    • B60L50/51—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells characterised by AC-motors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L58/00—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles
    • B60L58/10—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling batteries
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/022—Boron compounds without C-boron linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/04—Esters of boric acids
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
    • 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
    • H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L2240/00—Control parameters of input or output; Target parameters
    • B60L2240/10—Vehicle control parameters
    • B60L2240/36—Temperature of vehicle components or parts
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0034—Fluorinated solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a new organic borate compound, a nonaqueous electrolyte using the compound, and a lithium secondary battery and an electric appliance both using the electrolyte; the invention relating especially to a new organic borate compound high in oxidation resistance, a nonaqueous electrolyte improved in oxidation resistance by use of the compound, a lithium secondary battery and an electric appliance, both improved in cycle life by use of the electrolyte, and various applications of the electric appliance.
  • Lithium secondary batteries each made up of positive and negative electrodes capable of occluding and releasing lithium, a nonaqueous electrolyte, and other components, are high in energy density per weight and volume and in voltage. They are, therefore hoped to be used as portable compact power supplies or as power supplies for electric automobiles. Since lithium secondary batteries have a high driving voltage of 3 V or more, they use a nonaqueous electrolyte wide in withstand voltage range. Compared with aqueous electrolytes, nonaqueous electrolytes have the drawbacks that they are low in electroconductivity and that a large portion of organic solvents suitable for an nonaqueous electrolyte are high in flammability (or low in flashing point).
  • organic lithium salt is proposed as lithium salt excellent in dissociation characteristics over the lithium hexafluorophosphate (LiPF 6 ) or lithium tetrafluoroborate (LiBF 4 ) that is now mainly used.
  • LiPF 6 lithium hexafluorophosphate
  • LiBF 4 lithium tetrafluoroborate
  • Hei 05-326018 is known as a promising material having high solubility against a nonaqueous electrolytic solvent in comparison to an inorganic electrolyte. It is indicated, however, that the lithium bis-(trifluoromethanesulfonyl)imide (LiN [SO 2 CF 3 ] 2 ) has the drawback that it corrodes the aluminum used as the positive-electrode current collector for a secondary battery.
  • organic lithium salt having boron to form its central ion and disalicylate to form its ligands and organic lithium salt having boron to form its central ion and a benzenediolate derivative to form its ligands, are disclosed in Japanese Application Patent Laid-Open Publication No. Hei 07-65843.
  • these compounds have a benzene ring and are thus low in solubility, they cannot satisfy the electroconductivity or oxidation resistance required.
  • the present invention is intended to supply: an organic borate compound from which a nonaqueous electrolyte high in electroconductivity can be created, and whose characteristics do not deteriorate even in a nonaqueous electrolyte having a noncombustible fluorinated solvent mixture; a lithium secondary battery using the organic borate compound; a nonaqueous electrolyte enabling the characteristics of an electrochemical capacitor to be improved; a long-life lithium secondary battery and an electric appliance, both using the nonaqueous electrolyte, and; various applications of the electric appliance.
  • Electroconductivity is determined by the number of lithium ions and the mobility level thereof. Also, solubility is considered to exist within the radius of the ions surrounded by the solvent. For these reasons, the present inventors have considered it possible to suppress local coagulation of the solvent by increasing the anion of lithium salt dimensionally and delocalizing the electric charge of the ions, and to obtain highly dissociative and highly soluble lithium salt by introducing into the anion a functional group which can improve the affinity between the anion and the solvent and increase the electron withdrawing ability of the central element in the anion. Consequently, the inventors have energetically studied such a compound to complete the present invention.
  • the present invention relates to an organic borate compound characterized in that it is represented by general formula (1)
  • X denotes lithium or quaternary ammonium or quaternary phosphonium and R 1 , R 2 , R 3 , and R 4 each denote an independent halogen-atom displacement alkyl group whose carbon number ranges from 1 to 4.
  • the organic borate represented by general formula (1) above is a new compound excellent in solubility against a nonaqueous solvent, and the electrolytes using this compound are high in electroconductivity. More specifically, a halogen displacement acyloxy group having an excellent electron withdrawing ability and enabling an electric charge to be delocalized in a carbonyl group has been introduced into boron, the central element of the anion. Also, the ion radius of the anion has been increased and the electric charge of the ions has been delocalized. Consequently, it has been possible to improve solubility. For this reason, a nonflammable fluorinated solvent small in dipole moment and low in dielectric constant can also be applied to an electrolyte having such a supporting electrolytic property. Unlike imide-based organic salt, the compound described above does not corrode the current collector of aluminum, because the central ion of the compound is surrounded by ligands.
  • the organic borate compound in an embodiment of the present invention has the chemical structure represented as general formula 1, wherein X denotes lithium or quaternary ammonium quaternary phosphonium and R 1 , R 2 , R 3 , and R 4 each denote an independent halogen-atom displacement alkyl group whose carbon number ranges from 1 to 4.
  • R 1 , R 2 , R 3 , and R 4 are each a trifluoromethyl group or a pentafluoroethyl group.
  • a nonaqueous electrolyte that is very high in solubility against ring carbonate such as ethylene carbonate or propylene carbonate, against chain carbonate such as dimethyl carbonate or ethyl methyl carbonate, or against ether such as dimethoxyethane, and using each such solvent independently or in mixed form, can be obtained from the organic borate compound formed according to the present invention.
  • a nonaqueous electrolyte high in electroconductivity can be obtained from either a compound using the fluorinated alkyl groups represented as R 1 , R 2 , R 3 , and R 4 in general formula (1), or a compound using partially fluorinated alkyl groups, since these compounds have a solubility of at least 1.8 mol.dm ⁇ 3 , even for a solution in which, in addition to the above-mentioned nonaqueous solvents, a nonflammable fluorinated solvent low in dielectric constant such as nonafluorobutyl methyl ether (tradename: HFE7100), is contained in the range from 5 to 90 volume percent. Furthermore, in addition to being wide in operating electric potential range because of its oxidation decomposition potential being high (about 5 V) against a lithium metal, the electrolyte obtained by dissolving such organic lithium borate does not corrode aluminum.
  • Examples of a compound which can be embodied using the organic borate pertaining to the present invention include: lithium tetrakis (trifluoroacetate) borate, lithium tetrakis (difluoroacetate) borate, lithium tetrakis (fluoroacetate) borate, lithium tetrakis (chlorodifluoroacetate) borate, lithium tetrakis (trichloroacetate) borate, lithium tetrakis (dichloroacetate) borate, lithium tetrakis (pentafluoropropanoate) borate, lithium tetrakis (3-chlorotetrafluoropropanoate) borate, lithium tetrakis (heptafluorobutanoate) borate, lithium tetrakis (2,2-bis-trifluoromethylbutanoate) borate, tetraethyl ammonium tetrakis (trifluoroa
  • Organic lithium borate based on the present invention can be synthesized using such a process as represented by, for example, the following formula:
  • organic lithium borate based on the present invention can be easily synthesized by generating reactions between boric acid, 3-quivalent acid anhydride, and lithium carbonate.
  • the aforementioned process is one example of synthesizing the organic lithium borate pertaining to the present invention, and the synthesizing process is not limited to the aforementioned process.
  • organic borate ammonium salt or organic borate phosphonium salt can be obtained by using carboxylic acid quaternary ammonium salt or carboxylic acid quaternary phosphonium salt, instead of lithiumcarbonate.
  • a chain carbonate such as dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, dipropyl carbonate, or methylpropyl carbonate
  • a ring carbonate such as ethylene carbonate, propylene carbonate, butylene carbonate, triphloropropylene carbonate, or chloroethylene carbonate, vinylene carbonate, or dimethylvinylene carbonate
  • ring ester such as ⁇ -butyrolactone or valerolactone
  • chain ether such as 1,3-dioxysolan or tetrahydrofuran
  • tetrahaloacetate borate based on the invention can be used as an additive, with LiPF 6 , LiBF 4 , LiN (SO 2 CF 2 CF 3 ) 2 , LiN (SO 2 CF 3 ) 2 or the like, as the main supporting salt.
  • the positive electrode of the lithium secondary battery can use a lithium composite oxide containing a transition element capable of occluding and releasing lithium, such as cobalt, nickel, or manganese.
  • the negative electrode can use a lithium metal capable of occluding and releasing lithium, graphite, an amorphous carbon material, silica, an oxide of tin, or a complex consisting of these substances and carbon.
  • the separator of the lithium secondary battery can use polyethylene, polypropylene, or a microstructured porous film laminate consisting of these substances.
  • problems associated with the prior organic lithium salts namely, the corrosion of aluminum and the insufficiency in oxidation suppression potential, can be solved by using the above-mentioned organic lithium borate as a supporting electrolyte.
  • oxidation resistance improves, the high-temperature storage characteristics of lithium secondary batteries can be improved.
  • organic lithium borates based on the present invention can be dissolved to concentrations of at least 0.8 mol/dm ⁇ 3 in solvent mixtures heavily laden with a fluorinated solvent, in particular, it is possible to obtain nonaqueous electrolytes that offer a maximum electroconductivity value at a low concentration of 0.4 mol/dm ⁇ 3 .
  • lithium secondary batteries from consumer product-use ones to large-capacity ones intended for electric power storage and for electric automobile use can be essentially made nonflammable and thus the appropriate lithium secondary battery significantly improved in safety and high in reliability can be supplied according to a particular application.
  • improvement in the safety of conventional lithium secondary batteries and reduction in the weight and size thereof are anticipated.
  • FIG. 1 is an infrared absorption spectral diagram showing an embodiment of the present invention.
  • FIG. 2 is an infrared absorption spectral diagram showing another embodiment of the present invention.
  • FIG. 3 is an infrared absorption spectral diagram showing yet another embodiment of the present invention.
  • FIG. 4 is an infrared absorption spectral diagram showing a further embodiment of the present invention.
  • FIG. 5 is a cathode polarization curve.
  • FIG. 6 is a cross-sectional view of a cylindrical battery, an embodiment of the present invention.
  • FIG. 7 is a block diagram showing the driving system of the electric automobile pertaining to the present invention.
  • FIG. 8 is a protection circuit diagram relating to the present invention.
  • FIG. 9 is a block diagram showing the control system of the electric automobile pertaining to the present invention.
  • FIG. 10 is a block diagram showing the electric power storage system of the electric automobile pertaining to the present invention.
  • Lithium bis-salicylate borate has been dissolved, as comparative example 1, in a substance (solvent A) that was created by mixing propylene carbonate (PC) and dimethyl carbonate (DMC) at a volume ratio of 1:2 as the solvent
  • solvent A propylene carbonate
  • DMC dimethyl carbonate
  • the lithium bis-salicylate borate has been dissolved only to a concentration of 0.1 mol/dm ⁇ 3 (hereinafter, mol/dm ⁇ 3 is expressed as M).
  • the electroconductivity of the nonaqueous electrolyte at this concentration has been 0.43 mS/cm when evaluated with the CM-60S conductivity meter (manufactured by Toh-A D.K.K.) that uses the CGT-511B cell.
  • lithium salt LB1 has been dissolved in solvent A. Consequently, LB1 has been dissolved to a concentration exceeding 1.2 M, and a maximum electroconductivity of 7.8 mS/cm has been obtained with 0.8 M. These results indicate that the use of lithium salt LB1 based on the present invention improves solubility and electroconductivity by factors of at least 12 and up to 18, respectively.
  • lithium salt LB2 has been dissolved insolvent A containing a 1:2PC/DMC mixture. Consequently, LB2 has been dissolved to a concentration exceeding 1.2 M, and a maximum electroconductivity of 5.8 mS/cm has been obtained with 0.6 M.
  • lithium salt LB3 has been dissolved in solvent A containing a 1:2 PC/DMC mixture. Consequently, LB3 has also been dissolved to a concentration exceeding 1.2 M, and a maximum electroconductivity of 4.3 mS/cm has been obtained with 0.5 M.
  • lithium salt LB4 has been dissolved in solvent A containing a 1:2 PC/DMC mixture. Consequently, LB4 has been dissolved to a concentration exceeding 0.1 M, and an electroconductivity of 0.02 mS/cm has been obtained.
  • lithium salt LB5 has been dissolved in solvent A containing a 1:2PC/DMC mixture. Consequently, LB5 has been dissolved to a concentration exceeding 1.2 M, and a maximum electroconductivity of 6.2 mS/cm has been obtained with 0.8 M.
  • Lithium bis-salicylate borate and lithium bis-benzenediolate have been dissolved, as comparative examples 2 and 3, respectively, by use of, as the noncombustible solvent , a substance (solvent B) that was created by mixing nonafluorobutyl methyl ether (tradename: HFE7100) and dimethyl carbonate (DMC) at the volume ratio of 80 versus 20 (HFE7100 versus DMC) where solvent B loses its flammability.
  • solvent B nonafluorobutyl methyl ether
  • DMC dimethyl carbonate
  • LB1, LB2, and LB5 have been dissolved, as embodiments 12, 13, and 14, respectively, in solvent B.
  • LB1 has been dissolved to a concentration exceeding 1.2 M, and a maximum electroconductivity of 1.55 mS/cm has been obtained with a concentration of 0.8 M. That is to say, the use of LB1 has enabled electroconductivity to be improved by 2.2 times that of the comparative example 4 in which LiN (SO 2 CF 3 ) 2 was used.
  • LB2 has also been dissolved to a concentration exceeding 1.2 M, and a maximum electroconductivity of 1.7 mS/cm has been obtained with a concentration of 0.6 M.
  • LB2 has enabled electroconductivity to be improved by 2.4 times that of the comparative example 5 in which LiN (SO 2 CF 3 ) 2 was used.
  • LB5 has also been dissolved to a concentration exceeding 1.2 M, and a maximum electroconductivity of 1.8 mS/cm has been obtained with a concentration of 0.6 M. That is to say, the use of LB5 has enabled electroconductivity to be improved by 2.6 times that of the comparative example 5 in which LiN (SO 2 CF 3 ) 2 was used.
  • the organic lithium borate compounds pertaining to the present invention have high solubility against solvent mixtures heavily laden with a fluorinated solvent small in dipole moment and low in dielectric constant, and offer high electroconductivities at low concentrations in comparison to prior, well-known organic lithium borates. This means that the use of the organic lithium borate compounds pertaining to the present invention enables costs to be reduced by saving lithium salt consumption, and electrolytes of better characteristics to be obtained.
  • a nonaqueous electrolyte containing LiN (SO 2 CF 3 ) 2 dissolved to a concentration of 0.7 M in solvent A has been prepared as comparative example 6.
  • a nonaqueous electrolyte containing LB1 dissolved to 0.7 M in solvent A a nonaqueous electrolyte containing LB2 dissolved to 0.7 M in solvent A
  • a nonaqueous electrolyte containing LB3 dissolved to 0.7 M in solvent A a nonaqueous electrolyte containing LB3 dissolved to 0.7 M in solvent A
  • a nonaquous electrolyte containing LB5 dissolved to 0.7M in solvent A have been prepared as embodiments 15, 16, and 17, respectively.
  • the anticorrosion performance of aluminum against anions has been evaluated using the above-mentioned electrolytes in order to perform the evaluations mentioned below. That is to say, a cell using aluminum as its working electrode and a lithium metal as its counter electrode and reference electrode, has been fabricated and evaluations have been performed on the current values obtained 10 minutes after the aluminum was maintained at a potential of 4.0 V (vs. the lithium metal).
  • the use of the organic lithium borates pertaining to the present invention reduces, even at a high potential of 4 V, the anodic oxidation of aluminum to 1/1800 in embodiment 15 and 1/3600 in embodiments 16,17 and 18, respectively, in comparison to the LiN (SO 2 CF 3 ) 2 in comparative example 6.
  • This means that the use of the organic lithium borate compounds pertaining to the present invention enables the provision of highly soluble and highly electroconductive electrolytes suppressed in terms of aluminum current collector corrosion.
  • PC a highly acid-resistant solvent
  • the oxidation currents against the potential values have been measured at a potential sweep rate of 10 mV/sec by application of an electrochemical cell using platinum as its working electrode and lithium as its counter electrode and reference electrode. Measurement results are shown in FIG. 5.
  • LiN (SO 2 CF 3 ) 2 in comparative example 7 significant changes in oxidation current from 5.8 V onward have been observed.
  • no significant changes in oxidation current have been observed until 6.7 V, 6.5 V, 6.4 V, and 6.8 V were reached in the cases of LB1 in embodiment 19, LB2 in embodiment 20, LB3 in embodiment 21, and LB5 in embodiment 22, respectively.
  • oxidation resistance has improved at 0.9 V in LB1, 0.7 V in LB2, 0.6 V in LB3, and 1.0 V in LB5.
  • the acetate displacement-type lithium salt of the present invention that uses boron as the central element of its anion is highly in solubility and in electroconductivity and does not corrode aluminum. It has also been found that the aforementioned lithium salt features a high oxidation potential and thus that the salt is a suitable material as the supporting electrolyte for a lithium battery high in capacity and in operating voltage.
  • a nonaqueous electrolyte containing tetraethyl ammonium tetrafluoroborate ((CH 3 CH 2 ) 4 NFB 4 ) dissolved to a concentration of 1 M in PC has been prepared as example 8 for comparison.
  • a nonaqueous electrolyte containing-tetrakis (trifluoroacetate) borate ((CH 3 CH 2 ) 4 NB(OCO-CF 3 ) 4 ) dissolved to 1 M in PC has been prepared as embodiment 23.
  • the corresponding potential windows have been evaluated at a sweep rate of 10 mV/sec by application of cyclic volumetry with an electrochemical cell using platinum as its working electrode and lithium as its counter electrode and reference electrode.
  • potential values from 1.0 to 5.5 V have been obtained in comparative example 8, whereas those of embodiment 23 have been from 1 to 6 V and the potential window has therefore increased by 0.5 V at the oxidation side.
  • a cylindrical lithium secondary battery of the structure shown in FIG. 6 has been fabricated using the method described below.
  • Artificial graphite and PVDF have been used as a negative-electrode activation substance and a binding agent, respectively, then these substances have been mixed at a rate of 91:9 in terms of weight, and this mixture has been dissolved in N-methylpyrrolidone (hereinafter referred to as NMP), which is one type of solvent, and kneaded to obtain a negative-electrode paste material.
  • NMP N-methylpyrrolidone
  • both sides of a copper foil used as a negative-electrode current collector 1 have been coated with the paste material, and then after the copper foil was dried, heated, pressurized, and vacuum-dried in that order, a negative electrode layer 2 has been formed on both sides of negative-electrode current collector 1 to obtain a negative electrode.
  • Cobalt acid lithium, graphite carbon, and PVDF have been used as a positive-electrode activation substance, a negative-electrode activation substance, and a binding agent, respectively, then these substances have been mixed at a rate of 85:7:8 in terms of weight, and this mixture has been dissolved in NMP, which is one type of solvent, and kneaded to obtain a positive-electrode paste material.
  • both sides of a copper foil used as positive-electrode current collector 3 have been coated with the paste material, and then after the copper foil was dried, heated, pressurized, and vacuum-dried in that order, a positive electrode layer 4 has been formed on both sides of positive-electrode current collector 3 to obtain a positive electrode.
  • a negative electrode lead 5 and a positive electrode lead 6 both made of a nickel foil, were connected to uncoated portions of the negative electrode and positive electrode by electric welding, these electrodes have been placed among separators 7 and the outermost separator has been fixed by winding a tape around it to form an electrode group.
  • negative electrode lead 5 from this electrode group was routed through the bottom of a can and then inserted into an stainless-steel-made outer packaging can 10 via a polypropylene-made insulator 8 for electrical insulation, outer packaging can 10 and the other end of negative electrode lead 5 have been connected at the bottom of the can by electric welding to form a negative electrode circuit.
  • positive electrode lead 6 has been connected to a positive electrode cap 12 via a positive-electrode insulator 9 by electric welding.
  • An electrolyte has been prepared by dissolving 1M-concentration LiN (SO 2 CF 3 ) 2 to 1 M (mol/dm ⁇ 3 ) in a solvent which was created by mixing ethylene carbonate (EC) and dimethyl carbonate (DMC) at a volume ratio of 1:2 (hereinafter, the composition of the electrolyte is shown as 1M-Lin(SO 2 CF 3 ) 2 EC/DMC (1/2 in volume ratio)).
  • a cylindrical lithium secondary battery (cobalt-based battery) similar to that which was used in comparative example 1, has been fabricated by mechanically staking a positive electrode cap 12 equipped with a gasket 11 , and negative-electrode outer packaging can 10 .
  • the battery has been removed from the test cell, then allowed to stand at room temperature for one day, and undergone temporary discharge to 3 V at a fixed current of 1 A, followed by fixed-voltage recharging at a fixed current of 1 A and under a stopping current condition of 20 mA.
  • the discharge capacity obtained when the battery was discharged to 3 V at a fixed current of 1 A has been evaluated as an index of the battery storage characteristics (hereinafter, this index is referred to as the recovery capacity).
  • the recovery capacity of this battery in comparative example 9 was 1,020 mAh. Accordingly, a value of 67% has been obtained as the maintenance ratio of the capacity with respect to the initial capacity of 1,510 mAh.
  • a battery has been fabricated as embodiment 24 by use of 1M-LB1 EC/DMC (1/2 in volume ratio) as its nonaqueous electrolyte.
  • the initial capacity of this battery was 1,610 mAh.
  • the battery After high-temperature storage, the battery has attained a recovery capacity of 1,420 mAh, which was an increase of 400 mAh in comparison to the recovery capacity of the battery in comparative example 9.
  • the capacity maintenance ratio of the battery was 87%, which was 20% greater than in comparative example 9.
  • a battery has been fabricated as embodiment 25 by use of 1M-LB2 EC/DMC (1/2 in volume ratio) as its nonaqueous electrolyte.
  • the initial capacity of this battery was 1,590 mAh.
  • the battery After high-temperature storage, the battery has attained a recovery capacity of 1,380 mAh, which was an increase of 360 mAh in comparison to the recovery capacity of the battery in comparative example 9.
  • the capacity maintenance ratio of the battery was 86%, which was 19% greater than in comparative example 9.
  • a battery has been fabricated as embodiment 26 by use of 1M-LB5 EC/DMC (1/2 in volume ratio) as its nonaqueous electrolyte.
  • the initial capacity of this battery was 1,620 mAh.
  • the battery After high-temperature storage, the battery has attained a recovery capacity of 1,390 mAh, which was an increase of 370 mAh in comparison to the recovery capacity of the battery in comparative example 9.
  • the battery has attained a capacity maintenance ratio of 85%, which was 18% greater than in comparative example 9.
  • a battery has been fabricated as comparative example 10 by use of 1M-LiPF 6 EC/DMC (1/2 in volume ratio) as its electrolyte.
  • the initial capacity of this battery was 1,650 mAh.
  • the recovery capacity and capacity maintenance ratio of the battery were 1,390 mAh and 85%, respectively.
  • An electrolyte for use in embodiment 27 has been prepared by dissolving 2-weight % LB1 in 1M-LiPF 6 EC/DMC (1/2 in volume ratio), and a battery has been fabricated as embodiment 27 by use of the above-mentioned electrolyte.
  • the initial capacity of this battery was 1,640 mAh.
  • the battery After high-temperature storage, the battery has attained a recovery capacity of 1,430 mAh, which was an increase of 40 mAh in comparison to the recovery capacity of the battery in comparative example 10. Also, the battery has attained a capacity maintenance ratio of 87%, which was 2% greater than in comparative example 10.
  • An electrolyte for use in embodiment 28 has been prepared by dissolving 2-weight % LB2 in 1M-LiPF 6 EC/DMC (1/2 in volume ratio), and a battery has been fabricated as embodiment 28 by use of the above-mentioned electrolyte.
  • the initial capacity of this battery was 1,630 mAh.
  • the battery After high-temperature storage, the battery has attained a recovery capacity of 1,410 mAh, which was an increase of 20 mAh in comparison to the recovery capacity of the battery in comparative example 10. Also, the battery has attained a capacity maintenance ratio of 86%, which was 1% greater than in comparative example 10.
  • An electrolyte for use in embodiment 29 has been prepared by dissolving 2-weight % LB5 in 1M-LiPF 6 EC/DMC (1/2 in volume ratio), and a battery has been fabricated as embodiment 29 by use of the above-mentioned electrolyte.
  • the initial capacity of this battery was 1,660 mAh.
  • the battery After high-temperature storage, the battery has attained a recovery capacity of 1,450 mAh, which was an increase of 60 mAh in comparison to the recovery capacity of the battery in comparative example 10. Also, the battery has attained a capacity maintenance ratio of 87%, which was 2% greater than in comparative example 10.
  • An electrolyte for use in embodiment 30 has been prepared by dissolving 2-weight % LB1 and 2-weight % vinylene carbonate in 1M-LiPF 6 EC/DMC (1/2 in volume ratio), and a battery has been fabricated as embodiment 30 by use of the above-mentioned electrolyte.
  • the initial capacity of this battery was 1,640 mAh.
  • the battery After high-temperature storage, the battery has attained a recovery capacity of 1,460 mAh, which was an increase of 70 mAh in comparison to the recovery capacity of the battery in comparative example 10. Also, the battery has attained a capacity maintenance ratio of 89%, which was 4% greater than in comparative example 10.
  • a battery has been fabricated as comparative example 11 by use of 1M-LiN (SO 2 CF 3 ) 2 HFE7100/DMC (8/2 in volume ratio) as its electrolyte.
  • the initial capacity of this battery was 1,570 mAh.
  • the recovery capacity and capacity maintenance ratio of the battery were 1,110 mAh and 70%, respectively.
  • a battery has been fabricated as embodiment 31 by use of 1M-LB1 HFE7100/DMC (8/2 in volume ratio) as its nonaqueous electrolyte.
  • the initial capacity of this battery was 1,610 mAh.
  • the recovery capacity and capacity maintenance ratio of the battery were 1,330 mAh and 82%, respectively, which were increases of 220 mAh and 12% in recovery capacity and capacity maintenance ratio, respectively, in comparison to the battery in comparative example 11.
  • a battery has been fabricated as embodiment 32 by use of 1M-LB2 HFE7100/DMC (8/2 in volume ratio) as its nonaqueous electrolyte.
  • the initial capacity of this battery was 1,620 mAh.
  • the recovery capacity and capacity maintenance ratio of the battery were 1,350 mAh and 83%, respectively, which were increases of 240 mAh and 13% in recovery capacity and capacity maintenance ratio, respectively, in comparison to the battery in comparative example 11.
  • a battery has been fabricated as embodiment 33 by use of 1M-LB5 HFE7100/DMC (8/2 in volume ratio) as its nonaqueous electrolyte.
  • the initial capacity of this battery was 1,630 mAh.
  • the recovery capacity and capacity maintenance ratio of the battery were 1,350 mAh and 82%, respectively, which were increases of 240 mAh and 12% in recovery capacity and capacity maintenance ratio, respectively, in comparison to the battery in comparative example 11.
  • the use of the organic lithium borate pertaining to the present invention greatly improves reliability with respect to high-temperature storage under a charged status. This is considered to be due to the fact that the improvement of oxidation resistance suppresses the acceleration of the anion with the decomposition temperature at high potential.
  • FIG. 7 is a view showing the driving system configuration of an electric automobile which uses either of the lithium secondary batteries described in embodiments 24 to 33.
  • the electric automobile in FIG. 7 is constructed so that when the key switch is turned and the accelerator pedal is stepped, the torque or rotational speed of the motor inside will be controlled according to the particular stepping angle of the accelerator pedal.
  • a regenerative brake equivalent to an engine brake will be applied, and when the brake pedal is stepped, the regenerative brake force will further increase.
  • Forward or reverse running of the vehicle is selected according to the particular status of the shift lever signal, and the transmission gear ratio is always kept constant.
  • the vehicle employs an IGBT vector control inverter scheme using an induction motor, and a supply voltage of 336 V is determined from the IGBT withstand voltage.
  • the maximum output and maximum torque of the vehicle are set to 45 kW and 176 N.m, respectively, from its power performance (acceleration and climbing performance) as an automobile, and its rated output is set to 30 kW from the maximum speed specifications.
  • the main control items include fail-safe control as well as forward and reverse running of the vehicle and regenerative control.
  • the engine in this embodiment employs water cooling, as with a general engine.
  • the coolant circulation channel is provided in the aluminum frame shrouding the motor body, and thus the optimum configuration based on temperature rise simulation results is achieved.
  • the coolant after flowing in from the coolant inlet in the internal channel of the frame and absorbing the heat released from the motor body, is discharged and then cooled by a radiator provided in the coolant circulation channel.
  • Such water-cooled structure has been adopted to improve cooling performance by about three times that of air cooling.
  • the inverter uses IGBT as its power device, and gives forth a maximum calorific value of several kilowatts during maximum output. Heat is also released from surge-absorbing resistors, filter capacitors, and more, and these components need to be controlled below a predetermined maximum allowable temperature in order to provide efficient cooling. It is particularly important to cool IGBT, and a method available to cool IGBT is either air cooling, water cooling, oil cooling, or others. In this embodiment, forced water cooling has been adopted because of its ease of handling and its high efficiency.
  • the protection circuit shown in FIG. 8 is formed in each lithium secondary battery used as the power supply in embodiments 31 to 33. This protection circuit protects the battery from overcharge and overdischarge.
  • the protection circuit as shown in FIG. 8, includes a balance-compensating circuit which adjusts the cell voltages of each battery, and is provided in each battery. This balance-compensating circuit is controlled by a microcomputer. Since conventional lithium secondary batteries use a flammable electrolyte, a thermistor is provided in each battery to detect and monitor temperature and pressure.
  • nonflammable electrolytes not having a flashing point are used that do not require special temperature or pressure monitoring, since the electrolytes have the nature that even if a flame is brought into contact with the electrolyte, the flame will not ignite the battery fluid. Thereby, the number of safety devices required can be reduced by providing the protection circuit. As shown in FIG. 7, when overdischarge is detected, the power circuit will be automatically opened and closed.
  • this embodiment shows an example in which an induction motor is used, this embodiment can likewise be applied to an electric automobile that uses, as shown in FIG. 9, a permanent magnet-type synchronous motor and a DC shunt motor.
  • INV stands for Inverter.
  • IM is short for Induction Motor
  • E Encoder
  • SM Synchronous Motor
  • PS Position Sensor
  • PWM Pulse Width Modulation
  • DCM DC Motor
  • CH for Chopper
  • N* for speed command
  • T* torque command.
  • each line in the figure denotes a control motor type, a system configuration, and major control parameters.
  • FIG. 10 is a block diagram showing a nighttime electric power storage system which uses a multitude of lithium secondary batteries described in either embodiment 30, 31, or 32.
  • This example of an electric power storage system applies to a total battery capacity of 2,000 kW ⁇ 4 h, a cell capacity of 1,000 Wh, series connection of 360 batteries, and parallel connection of 24 battery banks.
  • embodiment 35 also requires battery protection from overcharge and overdischarge and the protection circuit shown in FIG. 8 includes monitoring and balance-compensating circuits. In this embodiment, the batteries are protected similarly to embodiment 34.
  • this embodiment is also valid for a home-use air-conditioning system, an electric water heater, and the like.

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US20090036599A1 (en) * 2006-03-24 2009-02-05 Nippon Chemical Industrial Co., Ltd. Powdery three-dimensionally crosslinked clathrate particle, process of producing same, dispersion, and resin composition
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