WO2013153996A1 - 有機系電解質及びそれを用いた有機系電解質蓄電池 - Google Patents
有機系電解質及びそれを用いた有機系電解質蓄電池 Download PDFInfo
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- WO2013153996A1 WO2013153996A1 PCT/JP2013/060158 JP2013060158W WO2013153996A1 WO 2013153996 A1 WO2013153996 A1 WO 2013153996A1 JP 2013060158 W JP2013060158 W JP 2013060158W WO 2013153996 A1 WO2013153996 A1 WO 2013153996A1
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- organic electrolyte
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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
- H01M10/0567—Liquid materials characterised by the additives
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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
- H01M10/052—Li-accumulators
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- 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
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- 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 an organic electrolyte and an organic electrolyte storage battery using the same.
- hybrid electric vehicles HEV
- plug-in hybrid electric vehicles PHEV
- battery-driven electric vehicles BEV
- a large storage battery that can be repeatedly charged and discharged as an energy source of these electric vehicles is an essential technology.
- organic electrolyte storage batteries are more powerful than other storage batteries, including nickel-metal hydride batteries, because they have a higher operating voltage and are easy to obtain high output, and are becoming increasingly important as power sources for electric vehicles. Yes.
- an electrolytic solution in which a lithium salt is dissolved in a non-aqueous solvent such as carbonate is usually used.
- non-aqueous solvents have favorable properties in terms of battery characteristics such as high dielectric constant and high oxidation potential, and thus excellent stability during battery use.
- an organic electrolyte storage battery prepared using these electrolytes has a risk of deformation or heat generation in an overcharged state, or in some cases, ignition or rupture.
- positive electrode active materials such as lithium transition metal composite oxides used in organic electrolyte storage batteries become unstable due to the elimination of lithium ions in an overcharged state, causing a rapid exothermic reaction with the electrolyte, It is also known that lithium metal is deposited on the negative electrode and short-circuited by dendrite formation.
- the organic compounds include compounds that form a high-resistance film on the surface of the active material by oxidative polymerization in an overcharged state, compounds that repeatedly undergo redox reactions and cause self-discharge and internal short circuiting, and internal pressure operation by gas generation Compounds that actuate an electric shut-off valve are known (for example, Patent Documents 1 to 4).
- An object of this invention is to provide the compound which can be used also for the organic electrolyte storage battery of the high charge voltage of 4.7V or more.
- this invention relates to the organic type electrolyte characterized by including the compound shown by following formula (1).
- R 3 to R 16 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms including halogen. Group, halogen, unsubstituted or substituted phenyl group, or cyclohexyl group, wherein R 1 and R 2 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or (It is a straight-chain or branched alkyl group having 1 to 4 carbon atoms, including halogen. R 3 to R 16 may be bonded together to form a ring.
- the present invention also relates to an organic electrolyte storage battery using the organic electrolyte described above.
- an organic electrolyte storage battery that can be used for a high charging voltage of 4.7 V or higher can be produced.
- FIG. 1 It is a schematic cross section which shows the structure of a coin type organic electrolyte storage battery. It is a figure which shows the charge curve of Example 1, the comparative example 1, and the comparative example 2.
- FIG. 1 It is a schematic cross section which shows the structure of a coin type organic electrolyte storage battery. It is a figure which shows the charge curve of Example 1, the comparative example 1, and the comparative example 2.
- FIG. 1 It is a schematic cross section which shows the structure of a coin type organic electrolyte storage battery. It is a figure which shows the charge curve of Example 1, the comparative example 1, and the comparative example 2.
- FIG. 1 It is a schematic cross section which shows the structure of a coin type organic electrolyte storage battery. It is a figure which shows the charge curve of Example 1, the comparative example 1, and the comparative example 2.
- FIG. 1 It is a schematic cross section which shows the structure of a coin type organic electrolyte storage battery. It is a figure which shows the charge curve of Example 1, the comparativ
- the present invention is an organic electrolyte containing a compound represented by the following formula (1).
- R 3 to R 16 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms including halogen. , Halogen, unsubstituted or substituted phenyl group, or cyclohexyl group, wherein R 1 and R 2 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or halogen Or a linear or branched alkyl group having 1 to 4 carbon atoms. Note that by R 1 and R 2 are in the same direction or different directions, the ring, there is a cis- or trans-form. R 3 to R 16 may be bonded together to form a ring.
- Examples of the compound represented by the formula (1) include trans-hydrindane, cis-hydrindane, 1-fluorohydrindane, 1,4-difluorohydrindane, 1-cyclohexylhydrindane, and the like.
- the compounding ratio of the compound represented by the formula (1) is preferably 0.5% by weight or more, more preferably 1% by weight or more in the organic electrolyte.
- the upper limit is preferably 20% by weight or less, more preferably 10% by weight or less, and still more preferably 5% by weight or less.
- the compounding ratio of the compound represented by the formula (1) is less than 0.5% by weight, the effect according to the present invention cannot be obtained.
- it exceeds 20% by weight the solubility of the electrolyte salt decreases, When the viscosity increases, the performance of the storage battery may deteriorate.
- the purity of the compound represented by the formula (1) is preferably 95% or more, more preferably 98% or more, and further preferably 99% or more.
- the purity is lower than 95%, impurities that deteriorate the performance of the storage battery may be contained, which is not preferable.
- the organic electrolyte is mainly composed of an organic solvent and an electrolyte salt, and a high dielectric constant solvent and a low viscosity solvent are used as the organic solvent.
- the content of the high dielectric constant solvent in the organic solvent in the organic electrolyte is preferably 5 to 45% by volume, more preferably 10 to 40% by volume, and still more preferably 15 to 38% by volume.
- the content of the low-viscosity solvent in the organic solvent in the organic electrolyte is preferably 55 to 95% by volume, more preferably 60 to 90% by volume, and still more preferably 62 to 85% by volume.
- high dielectric constant solvent examples include ethylene carbonate, propylene carbonate, butylene carbonate, ⁇ -butyllactone, ⁇ -valerolactone, tetrahydrofuran, 1,4-dioxane, N-methyl-2-pyrrolidone, and N-methyl-2.
- low-viscosity solvent examples include dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, ethyl propyl carbonate, dipropyl carbonate, methyl butyl carbonate, dibutyl carbonate, dimethoxyethane, methyl acetate, and ethyl acetate.
- lithium hexafluorophosphate LiPF 6
- lithium tetrafluoroborate LiBF 4
- lithium hexafluoroarsenate LiAsF 6
- lithium hexafluoro antimonate LiSbF 6
- Inorganic lithium salts such as lithium perchlorate (LiClO 4 ) and lithium tetrachloroaluminate (LiAlCl 4 ), and lithium trifluoromethanesulfonate (CF 3 SO 3 Li)
- lithium bis (trifluoromethanesulfone) imide [(CF 3 SO 2 ) 2 NLi]
- lithium bis (pentafluoroethanesulfone) imide [(C 2 F 5 SO 2 ) 2 NLi]
- lithium tris (trifluoromethanesulfone) methide [(CF 3 SO 2 ) 3 CLi]
- One electrolyte salt may be used alone, or a plurality of electrolyte salts may be mixed and used.
- the electrolyte salt is usually contained in the organic electrolyte at a concentration of 0.5 to 3 mol / liter, preferably 0.8 to 2 mol / liter, more preferably 1.0 to 1.6 mol / liter. It is desirable that
- the present invention also provides an organic electrolyte storage battery using an organic electrolyte containing a compound represented by the formula (1).
- any material that can occlude and release lithium can be used as the positive electrode active material.
- lithium-containing composite oxide LiMO 2 M is one or a mixture selected from metals such as Mn, Fe, Co, Ni, etc., and a part thereof is substituted with other cations such as Mg, Al, Ti, etc.
- an olivine type material typified by LiMn 2 O 4 , LiMn 0.5 Ni 1.5 O 4 , LiFePO 4 , LiMnPO 4, or the like can also be used.
- lithium-rich materials such as Li 2 MnO 3 and Li 2 MSiO 4 (M is a metal) can also be used.
- the positive electrode preferably includes lithium and a transition metal, and particularly preferably includes a layered oxide containing cobalt, nickel, or manganese as the transition metal.
- a carbon-based negative electrode material containing artificial graphite or natural graphite is used for the negative electrode.
- a negative electrode active material a negative electrode active material into which lithium can be inserted or reacts with lithium is used.
- Such a negative electrode active material is mainly composed of graphite, but a carbon material such as amorphous carbon, or a material that forms an alloy with Li such as Li metal, Si, Sn, or Al, Si oxide, other than Si and Si Si composite oxides containing other metal elements, Sn oxides, Sn composite oxides containing other metal elements other than Sn and Sn, Li 4 Ti 5 O 12 and the like may be mixed and used.
- the separator should just be formed from the electrically insulating porous body, for example, polymer films, such as polyolefin, such as polyethylene and a polypropylene, polyester, polyethylene terephthalate, a polyimide, or a fiber nonwoven fabric.
- the material may be used alone or in combination.
- the separator may be a single layer or a multilayer (composite film).
- an electrolyte that is gelled by containing a polymer compound that swells with an organic solvent and serves as a holding body that holds the organic electrolyte may be used. This is because by including a polymer compound that swells with an organic solvent, high ionic conductivity can be obtained, excellent charge / discharge efficiency can be obtained, and battery leakage can be prevented.
- the organic electrolyte contains a polymer compound, the content of the polymer compound is preferably in the range of 0.1% by mass to 10% by mass.
- the mass ratio of the organic electrolyte to the polymer compound is preferably in the range of 50: 1 to 10: 1. By setting it within this range, higher charge / discharge efficiency can be obtained.
- polymer compound examples include ether-based polymer compounds such as polyvinyl formal, polyethylene oxide and crosslinked products containing polyethylene oxide, ester-based polymer compounds such as polymethacrylate, acrylate-based polymer compounds, and polyvinylidene fluoride,
- ether-based polymer compounds such as polyvinyl formal, polyethylene oxide and crosslinked products containing polyethylene oxide
- ester-based polymer compounds such as polymethacrylate, acrylate-based polymer compounds
- polyvinylidene fluoride examples include ether-based polymer compounds such as polyvinyl formal, polyethylene oxide and crosslinked products containing polyethylene oxide, ester-based polymer compounds such as polymethacrylate, acrylate-based polymer compounds, and polyvinylidene fluoride
- a vinylidene fluoride polymer such as a copolymer of vinylidene fluoride and hexafluoropropylene may be used.
- a high molecular compound may be used individually by
- the coin type organic electrolyte storage battery will be described with reference to FIG. 1, but the type of the organic electrolyte storage battery of the present invention is not limited to the coin type.
- the button type the pouch type, the corner type, etc.
- the present invention can also be applied to organic electrolyte storage batteries such as a mold or a cylinder having a spiral structure.
- the size of the organic electrolyte storage battery is also arbitrary, and may be large, small, or thin.
- FIG. 1 is a schematic cross-sectional view showing the structure of a coin-type organic electrolyte storage battery.
- a positive electrode 12 and a negative electrode 14 are laminated via a separator 15.
- Each of the positive electrode 12, the negative electrode 14, and the separator 15 has a disk shape, and is accommodated in a space defined by the metal exterior component 11 and the exterior component 13.
- the exterior parts 11 and 13 are filled with an organic electrolyte, and the peripheral parts of the exterior parts 11 and 13 are sealed by caulking through a seal gasket 17.
- a metal spring 18 and a spacer 19 are disposed between the exterior component 13 and the negative electrode 14.
- the positive electrode was produced as follows. Active material: 91% by weight of LiNi 1/3 Mn 1/3 Co 1/3 O 2 , conductive auxiliary agent: 6% by weight of acetylene black, binder: 3% by weight of poly (vinylidene fluoride) (hereinafter abbreviated as PVDF) % Mixture was added N-methylpyrrolidone (hereinafter abbreviated as NMP) and kneaded to prepare a slurry. The produced slurry was dropped on an aluminum current collector, formed into a film using a film applicator with a micrometer and an automatic coating machine, and dried in an oven at 110 ° C. in a nitrogen atmosphere. The produced positive electrode was punched into a circle having a diameter of 15 mm, and then pressed. The amount of the positive electrode active material was about 23 mg.
- the negative electrode was produced as follows. NMP was added to a mixture of active material: 94% by weight of artificial graphite, conductive assistant: 1% by weight of acetylene black, and binder: 5% by weight of PVDF, and kneaded to prepare a slurry. The prepared slurry was dropped on a copper current collector, formed into a film using a film applicator with a micrometer and an automatic coating machine, and dried in an oven at 110 ° C. in a nitrogen atmosphere. The produced negative electrode was punched into a circle having a diameter of 15 mm, and then pressed. The amount of the negative electrode active material was about 19 mg.
- a coin-type storage battery was prepared using a positive electrode and a negative electrode produced by the above-described method and a 25 ⁇ m-thick polypropylene separator punched into a circle and an organic electrolyte prepared as follows.
- the organic solvent ethylene carbonate (hereinafter abbreviated as EC) is used as a high dielectric constant solvent, and dimethyl carbonate (hereinafter abbreviated as DMC) is used as a low-viscosity solvent.
- EC ethylene carbonate
- DMC dimethyl carbonate
- LiPF 6 was dissolved at a rate of 1 mol / liter.
- the compounds were added as shown in Table 1 to prepare organic electrolytes. The purity of the compound is 99% or more.
- Comparative Example 1 A coin-type storage battery in which cyclohexylbenzene (purity 99% or more) was added at 5% by weight with respect to the organic electrolyte was produced and evaluated in the same manner as in Example 1.
- Table 2 shows the initial charge capacity, initial discharge capacity, and initial charge / discharge efficiency.
- Example 2 A compound to which no compound was added was prepared and evaluated in the same manner as in Example 1. Table 2 shows the initial charge capacity, initial discharge capacity, and initial charge / discharge efficiency.
- the battery to which the compound according to the formula (1) of the present invention is added has the same initial performance as the battery to which no compound is added (Comparative Example 2), and even if charged at 4.7 V, the battery is adversely affected. It was shown that it can be used without problems. It was also confirmed that the initial charge / discharge efficiency improved as the amount added increased. On the other hand, the battery to which cyclohexylbenzene was added (Comparative Example 1) did not provide any discharge capacity, and was found to be unusable at 4.7V.
- the voltage is 5.08 V or more and the battery to which cyclohexylbenzene is added (Comparative Example 1), the voltage is constant at 4.46 V, and some reaction occurs at these voltages. Is considered to have occurred.
- the battery to which no compound was added Comparative Example 2
- the voltage was not constant during the same charging time. Therefore, it was shown that the compound and cyclohexylbenzene according to the present invention have an effect of suppressing voltage increase during overcharge. From the above results, it is clear that the compound represented by the formula (1) according to the present invention is a compound that can be used for an organic storage battery having a high charge voltage of 4.7 V or higher and improves safety during overcharge. It became.
- the organic electrolyte of the present invention can be used for high charge voltage storage batteries, and contributes to the practical use of high charge voltage, that is, high energy density storage batteries by enhancing the safety of these batteries.
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Abstract
Description
本発明は、4.7V以上の高充電電圧の有機系電解質蓄電池にも使用可能な化合物を提供することを目的とする。
有機系電解質における有機溶媒中の高誘電率溶媒の含有割合は5~45容量%であることが好ましく、より好ましくは10~40容量%、さらに好ましくは15~38容量%である。
また有機系電解質における有機溶媒中の低粘度溶媒の含有割合は55~95容量%であることが好ましく、より好ましくは60~90容量%、さらに好ましくは62~85容量%である。
電解質塩は、通常、0.5~3モル/リットル、好ましくは0.8~2モル/リットル、より好ましくは1.0~1.6モル/リットルの濃度で有機系電解質中に含まれていることが望ましい。
正極としては、リチウムと遷移金属が含まれるものが好ましく、特に遷移金属として、コバルト、ニッケル、またはマンガンを含む層状酸化物が含まれることが好ましい。
負極活物質としては、リチウムが挿入可能な、もしくはリチウムと反応する負極活物質が用いられる。かかる負極活物質としては、黒鉛を主体とするが、非晶質炭素などの炭素材料、あるいはLi金属、Si、Sn、AlなどのLiと合金を形成する材料、Si酸化物、SiとSi以外の他金属元素を含むSi複合酸化物、Sn酸化物、SnとSn以外の他金属元素を含むSn複合酸化物、Li4Ti5O12などを混合して用いてもよい。
また、セパレータの両面にポリフッ化ビニリデン等の高分子化合物を塗布して用いても良い。
また、セパレータの両面にポリフッ化ビニリデン等の高分子化合物を塗布して用いる場合は、有機系電解質と高分子化合物の質量比を50:1~10:1の範囲内とすることが好ましい。この範囲内とすることにより、より高い充放電効率が得られる。
図1は、コイン型の有機系電解質蓄電池の構造を示す模式断面図である。この電池は、正極12と負極14とがセパレータ15を介して積層されたものである。正極12、負極14およびセパレータ15はいずれも円板状であり、金属製の外装部品11および外装部品13によって画成される空間内に収容されている。外装部品11,13の内部は有機系電解質が満たされており、外装部品11,13の周縁部はシールガスケット17を介してかしめられることにより密閉されている。なお、外装部品13と負極14の間には金属製のバネ18とスペーサ19が配置されている。
活物質:LiNi1/3Mn1/3Co1/3O291重量%、導電助剤:アセチレンブラック6重量%、結着材:ポリ(フッ化ビニリデン)(以下、PVDFと略す)3重量%の混合物にN-メチルピロリドン(以下、NMPと略す)を加え、混練し、スラリーを作製した。作製したスラリーをアルミニウム集電体上に滴下し、マイクロメーター付フィルムアプリケーターおよび自動塗工機を用いて製膜し、オーブン中110℃、窒素雰囲気下にて乾燥させた。作製した正極を直径15mmの円形に打ち抜いた後、プレスを行った。正極活物質量は約23mgであった。
活物質:人造黒鉛94重量%、導電助剤:アセチレンブラック1重量%、結着材:PVDF5重量%の混合物にNMPを加え、混練し、スラリーを作製した。作製したスラリーを銅集電体上に滴下し、マイクロメーター付フィルムアプリケーターおよび自動塗工機を用いて製膜し、オーブン中110℃、窒素雰囲気下にて乾燥させた。作製した負極を直径15mmの円形に打ち抜いた後、プレスを行った。負極活物質量は約19mgであった。
初期充電容量(=初期放電容量/初期充電容量×100)、初期放電容量、および初期充放電効率を表2にまとめた。
シクロヘキシルベンゼン(純度99%以上)を有機系電解質に対して5重量%となるように加えたコイン型蓄電池を実施例1と同様に作製、評価した。初期充電容量、初期放電容量、および初期充放電効率を表2にまとめた。
化合物を加えないものを実施例1と同様に作製、評価した。初期充電容量、初期放電容量、および初期充放電効率を表2にまとめた。
以上の結果より、本発明に係る式(1)で示される化合物は、4.7V以上の高充電電圧の有機系蓄電池に使用可能な、過充電時に安全性を向上させる化合物であることが明らかとなった。
Claims (13)
- 式(1)で示される化合物が、有機系電解質中に0.5~20重量%配合されていることを特徴とする請求項1に記載の有機系電解質。
- 高誘電率溶媒を5~45容量%含有する有機溶媒を含むことを特徴とする請求項1または2に記載の有機系電解質。
- 請求項1~3のいずれかに記載の有機系電解質を用いたことを特徴とする有機系電解質蓄電池。
- ポリプロピレンを含むセパレータを用いたことを特徴とする請求項4に記載の有機系電解質蓄電池。
- リチウムが挿入可能なもしくはリチウムと反応する負極活物質を用いたことを特徴とする請求項4または5に記載の有機系電解質蓄電池。
- 炭素系負極材料を用いたことを特徴とする請求項4~6のいずれかに記載の有機系電解質蓄電池。
- 負極に人造黒鉛が含まれることを特徴とする請求項4~7のいずれかに記載の有機系電解質蓄電池。
- 正極にリチウムと遷移金属が含まれることを特徴とする請求項4~8のいずれかに記載の有機系電解質蓄電池。
- 正極にコバルトを含む層状酸化物が含まれることを特徴とする請求項4~9のいずれかに記載の有機系電解質蓄電池。
- 正極にニッケルを含む層状酸化物が含まれることを特徴とする請求項4~10のいずれかに記載の有機系電解質蓄電池。
- 正極にマンガンを含む層状酸化物が含まれることを特徴とする請求項4~11のいずれかに記載の有機系電解質蓄電池。
- 最大充電電圧が4.7V以上であることを特徴とする請求項4~12のいずれかに記載の有機系電解質蓄電池。
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EP13776152.4A EP2838149A1 (en) | 2012-04-11 | 2013-04-03 | Organic electrolyte and organic electrolyte storage cell using same |
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- 2013-04-03 WO PCT/JP2013/060158 patent/WO2013153996A1/ja active Application Filing
- 2013-04-03 EP EP13776152.4A patent/EP2838149A1/en not_active Withdrawn
- 2013-04-03 US US14/391,100 patent/US20150050550A1/en not_active Abandoned
- 2013-04-03 JP JP2014510122A patent/JPWO2013153996A1/ja active Pending
- 2013-04-11 TW TW102112819A patent/TW201347269A/zh unknown
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TW201347269A (zh) | 2013-11-16 |
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