WO2004093224A1 - Solution d'electrolyte non aqueux et batterie a electrolyte non aqueux utilisant une telle solution - Google Patents

Solution d'electrolyte non aqueux et batterie a electrolyte non aqueux utilisant une telle solution Download PDF

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Publication number
WO2004093224A1
WO2004093224A1 PCT/JP2004/004961 JP2004004961W WO2004093224A1 WO 2004093224 A1 WO2004093224 A1 WO 2004093224A1 JP 2004004961 W JP2004004961 W JP 2004004961W WO 2004093224 A1 WO2004093224 A1 WO 2004093224A1
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Prior art keywords
aqueous electrolyte
group
battery
electrolyte
positive electrode
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PCT/JP2004/004961
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English (en)
Japanese (ja)
Inventor
Masashi Otsuki
Yasuo Horikawa
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Bridgestone Corporation
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Priority to JP2005505366A priority Critical patent/JPWO2004093224A1/ja
Publication of WO2004093224A1 publication Critical patent/WO2004093224A1/fr

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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a non-aqueous electrolyte and a non-aqueous electrolyte battery provided with the same, and more particularly to a non-aqueous electrolyte having excellent permeability to an electrode and / or a separator.
  • the electrolyte material penetrates poorly into the battery material such as the separator and the battery electrode material, and particularly the electrolyte material penetrates poorly into the separator. After packing the members, the electrolytic solution was injected into the battery can while evacuating the battery can. Therefore, the conventional non-aqueous electrolyte battery had a complicated manufacturing process and low productivity. On the other hand, if the nonaqueous electrolyte is injected without evacuation of the battery can, it is necessary to leave the battery until the nonaqueous electrolyte penetrates into the battery electrode material, etc. Usually required a standing period of about two weeks.
  • the conventional non-aqueous electrolyte has a problem that the internal resistance is large because of poor permeability to the battery electrode material and the separator.
  • the internal resistance of the battery is R
  • the current value that can be taken out of the battery is I
  • the value of the voltage drop is E
  • the voltage drops according to E IR according to Ohm's law.
  • Lithium-ion secondary batteries published by Masayuki Yoshio and Akiya Ozawa, Nikkan Kogyo Shimbun Inc., have been devised in order to reduce the internal resistance of batteries by adding a conductive agent to the electrode material, Control is introduced.
  • battery components such as separators
  • an object of the present invention is to provide a non-aqueous electrolyte capable of solving the above-mentioned problems of the prior art, having excellent permeability to a battery electrode material and / or a separator, and capable of reducing the internal resistance of a battery. It is in.
  • Another object of the present invention is to provide a non-aqueous electrolyte battery having a low internal resistance, comprising the non-aqueous electrolyte.
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, have found that the power of adding a specific compound to a conventional non-aqueous electrolyte mainly comprises a non-aqueous electrolyte formed from the compound.
  • the present inventors have found that the internal resistance of a nonaqueous electrolyte battery can be reduced by improving the permeability of the electrolyte to the battery electrode material and / or the separator, and have completed the present invention.
  • the first nonaqueous electrolytic solution of the present invention has a time of 0.5 seconds after the nonaqueous electrolytic solution is dropped on the electrode until the contact angle of the nonaqueous electrolytic solution to the electrode becomes 2 ° or less. Less than or equal to.
  • the electrode is a positive electrode
  • an active material of the positive electrode is a lithium-containing composite oxide.
  • the active material of the positive electrode that is L i C O_ ⁇ 2, L i M n 2 ⁇ 4 and L i N I_ ⁇ least one lithium-containing composite oxide selected from the group consisting of 2 More preferred. ⁇
  • the electrode is a positive electrode, it is either the active material of the positive electrode is M n 0 2 and fluorinated graphite.
  • the electrode is a negative electrode
  • the active material of the negative electrode is graphite
  • the non-aqueous electrolyte contains a compound having at least one of phosphorus and nitrogen in a molecule.
  • a compound having phosphorus and nitrogen in the molecule is preferable, and a compound having phosphorus-nitrogen double bond is more preferable.
  • the non-aqueous electrolyte further contains ester carbonate.
  • a first non-aqueous electrolyte battery of the present invention includes the above-mentioned first non-aqueous electrolyte of the present invention, a positive electrode, and a negative electrode.
  • the time until the contact angle of the non-aqueous electrolyte with the separator becomes 25 ° or less is 2 seconds or less. It is characterized.
  • the separator is a porous polymer membrane, and the separator is made of polypropylene (PP), polyethylene (PE), and polyethylene'polypropylene copolymer (P EZ PP). It consists of either.
  • the non-aqueous electrolyte contains a compound having at least one of phosphorus and nitrogen in a molecule.
  • a compound having phosphorus and nitrogen in a molecule is preferable, and a compound having a phosphorus-nitrogen double bond is more preferable.
  • the non-aqueous electrolyte further contains ester carbonate.
  • a second non-aqueous electrolyte battery of the present invention includes the second non-aqueous electrolyte of the present invention, a positive electrode, a negative electrode, and a separator.
  • the non-aqueous electrolyte which is excellent in the permeability to a battery electrode material and / or a separator and which can reduce the internal resistance of a battery can be provided.
  • the non-aqueous electrolyte is provided and the internal resistance is low, a non-aqueous electrolyte battery having excellent pulse discharge characteristics ⁇ large current discharge and charging characteristics can be provided.
  • FIG. 1 is a schematic diagram of a non-aqueous electrolyte dropped on an electrode.
  • FIG. 2 is a schematic diagram of the non-aqueous electrolyte dropped on the separator.
  • FIG. 3 is a graph showing the change over time of the contact angle of the electrolyte of Example 1 with respect to the positive electrode.
  • FIG. 4 is a graph showing the change over time of the contact angle of the electrolyte of Comparative Example 1 with respect to the positive electrode.
  • FIG. 5 is a graph showing the remaining discharge capacity of the batteries of Example 1 and Comparative Example 1.
  • FIG. 6 is a graph showing the change over time of the contact angle of the electrolytic solution of Example 65 with the separator.
  • FIG. 7 is a graph showing the change over time of the contact angle of the electrolytic solution of Comparative Example 9 with the separator.
  • the time until the contact angle ⁇ i of the nonaqueous electrolyte 1 with respect to the electrode 2 becomes 2 ° or less after dropping the nonaqueous electrolyte 1 on the electrode 2 is 0. It is characterized by being less than 5 seconds.
  • the conventional non-aqueous electrolyte had a time of 0.5 seconds or more until the contact angle of the non-aqueous electrolyte with the electrode became 2 ° or less after dropping on the electrode, so the permeability to the electrode was poor.
  • the non-aqueous electrolyte battery provided with the first non-aqueous electrolyte of the present invention has significantly improved pulse discharge characteristics ⁇ large current discharge and charging characteristics as compared with the conventional non-aqueous electrolyte batteries. It is suitable as a large secondary battery for electric vehicles and fuel cell vehicles and a small primary battery for tire internal pressure alarm devices.
  • the first nonaqueous electrolyte of the present invention preferably has a viscosity at 25 ° C of 10 mPa's (10 cP) or less.
  • the non-aqueous electrolyte whose viscosity at 25 ° C exceeds K) mPa's (lOcP) is dropped on the electrode and the time required for the contact angle of the non-aqueous electrolyte to the electrode to become 2 ° or less is 0. It tends to be 5 seconds or longer, and the effect of reducing the internal resistance of the battery is insufficient.
  • the first nonaqueous electrolyte of the present invention more preferably has a viscosity at 25 ° C. of 5 mPa's (5 cP) or less.
  • the first nonaqueous electrolytic solution of the present invention is not particularly limited as long as it satisfies the above-mentioned properties relating to the permeability to the electrode, but includes at least a supporting salt, and contains at least phosphorus and nitrogen in the molecule. It is preferable to include a compound containing one of them. Further, the non-aqueous electrolytic solution may contain a non-protonic organic solvent such as a carbonate ester as necessary.
  • the second nonaqueous electrolytic solution of the present invention was added dropwise nonaqueous electrolyte 1 separator 3 on the contact angle theta 2 of the non-aqueous electrolyte 1 against separator one 3 the time until the 25 ° or less 2 Seconds or less.
  • the conventional non-aqueous electrolyte had a time of 5 seconds or longer until the contact angle of the non-aqueous electrolyte with the separator became 25 ° or less after dropping on the separator, so the permeability to the separator was poor and the internal Although the increase in resistance was caused, the second electrolytic solution of the present invention Since the permeability to the separator is extremely good, the internal resistance of the battery can be kept low. Therefore, the non-aqueous electrolyte battery provided with the second non-aqueous electrolyte of the present invention has significantly improved pulse discharge characteristics ⁇ large current discharge and charging characteristics as compared with the conventional non-aqueous electrolyte battery, and in particular, It is suitable as a large secondary battery for electric vehicles and fuel cell vehicles.
  • the second non-aqueous electrolyte of the present invention preferably has a viscosity at 25 ° C. of 10 mPa ′ S (10 cP) or less.
  • the non-aqueous electrolyte whose viscosity at 25 ° C exceeds lOmPa's (lOcP) is dropped on the separator and the time until the contact angle of the non-aqueous electrolyte with the separator becomes 25 ° or less is 2 seconds. And the effect of reducing the internal resistance of the battery is insufficient.
  • the second nonaqueous electrolytic solution of the present invention more preferably has a viscosity at 25 ° C of 5 mPa's (5 cP) or less.
  • the second nonaqueous electrolytic solution of the present invention is not particularly limited as long as it satisfies the above-mentioned properties relating to permeability to the separator, but includes at least a supporting salt, and contains at least phosphorus and nitrogen in the molecule. It is preferable to include a compound containing one of them.
  • the non-aqueous electrolyte may contain an aprotic organic solvent such as a carbonate ester, if necessary.
  • Examples of the compound having phosphorus in the molecule that can be suitably used in the first and second nonaqueous electrolytes of the present invention include an esterinol phosphate compound, a polyphosphate ester compound, and a condensed phosphate ester compound. .
  • Compounds having nitrogen in the molecule that can be suitably used in the first and second nonaqueous electrolytes of the present invention include cyclic nitrogen-containing compounds such as triazine compounds, guanidine compounds, and pyrrolidine compounds. Is mentioned.
  • phosphazene compounds As the compound having phosphorus and nitrogen in the molecule which can be suitably used in the first and second non-aqueous electrolytes of the present invention, phosphazene compounds, isomers of phosphazene compounds, phosphazene compounds, and A compound having phosphorus in the molecule And the compound exemplified as the compound having nitrogen in the molecule.
  • these compounds having phosphorus and nitrogen in the molecule are naturally examples of the compound having phosphorus in the molecule and the compound having nitrogen in the molecule.
  • compounds having phosphorus and nitrogen in the molecule are preferable from the viewpoint of cycle characteristics.
  • a compound having a phosphorus-nitrogen double bond such as a phosphazene compound is particularly preferable from the viewpoint of improving thermal stability and high-temperature storage characteristics. .
  • phosphazene compound examples include a chain phosphazene compound represented by the following formula (I) and a cyclic phosphazene compound represented by the following formula (II).
  • R 1 R 2 and R 3 each independently represent a monovalent substituent or a halogen element
  • X 1 represents carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, antimony, bismuth , oxygen, sulfur, selenium, tellurium
  • Polo - represents a substituent containing at least one element selected from the group consisting ⁇ beam
  • Upsilon Upsilon 2 and Upsilon 3 are each independently a divalent linking group, 2 Represents a valence element or a single bond.
  • R 4 represents a monovalent substituent or a halogen element.
  • N represents 3 to 15.
  • the phosphazene compounds represented by the formula (I) or (II) those which are liquid at 25 ° C. (room temperature) are preferable.
  • the occupancy of the liquid phosphazene compound at 25 ° C. is preferably 300 mPa's (300 cP) or less, more preferably 20 mPa's (20 cP) or less, and particularly preferably 5 mPa ⁇ s (5 cP) or less.
  • the viscosity is measured using a viscometer (R type) Viscometer M odel RE 5 0 0 - using SL, Toki Sangyo Co., Ltd.), lrpm, 2rptn, 3rpm, 5rpra, 7rpm, 10rpra, 20rpm, and 5 to 120 seconds Dzu' measured at each rotational speed of Orpm, The rotational speed when the indicated value became 50 to 60% was used as the analysis condition, and the viscosity at that time was measured. If the viscosity at 25 ° C exceeds 3 ⁇ 400 mPa's (300 cP), the supporting salt becomes difficult to dissolve, the wettability to the positive electrode material, negative electrode material, separator, etc.
  • RR 2 and R 3 are not particularly limited as long as they are monovalent substituents or halogen elements.
  • the monovalent substituent include an alkoxy group, an alkyl group, a hydroxyl group, an acyl group, an aryl group, and the like. Among them, an alkoxy group is preferable because the viscosity of the electrolytic solution can be reduced.
  • preferred examples of the halogen element include fluorine, chlorine, and bromine.
  • ⁇ ⁇ ⁇ 3 may be all the same kind of the substituent, may some of them in different kinds of substituents.
  • examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like, and an alkoxy-substituted alkoxy group such as a methoxyethoxy group and a methoxyethoxyethoxy group.
  • R 1 ! ⁇ 3 is preferably a methoxy group, an ethoxy group, a methoxy ethoxy group, or a methoxy ethoxy ethoxy group, and all are methoxy groups from the viewpoint of low viscosity and high dielectric constant. Or an ethoxy group is particularly preferred.
  • alkynole group examples include a methynole group, an ethylenole group, a propyl group, a butyl group, a pentyl group and the like.
  • acyl group examples include a formyl group, an acetyl group, a propioyl group, a butyryl group, an isoptyryl group, and a valeryl group.
  • aryl group include a fuel group, a trinole group, and a naphthyl group.
  • the hydrogen element in these monovalent substituents is preferably substituted with a halogen element.
  • halogen element fluorine, chlorine, and bromine are preferable.
  • fluorine is particularly preferred, followed by chlorine.
  • the effect of improving the cycle characteristics of the secondary battery tends to be greater than that in the case where the hydrogen element is replaced by chlorine.
  • X 1 represents at least one element selected from the group consisting of carbon, silicon, nitrogen, phosphorus, oxygen, and sulfur from the viewpoint of harmfulness and environmental considerations. Substituents containing species are preferred. Among these substituents, a substituent having a structure represented by the following formula ( ⁇ ), (IV) or (V) is more preferable.
  • R 5 to R 9 independently represent a monovalent substituent or a halogen element.
  • Y 5 to Y 9 independently represent a divalent linking group, a divalent element, or a single bond; and ⁇ represents a divalent group or a divalent element.
  • R 5 to R 9 are the same monovalent substituents or halogen elements as described for R ⁇ R 3 in the formula (I). Preferred examples are given. Further, these may be of the same type within the same substituent, or may be of different types. R 5 and R 6 in the formula (III), and R 8 and R 9 in the formula (V) may be bonded to each other to form a ring.
  • Equation (111), (IV), in (V), Y 5 as the group represented by to Y 9, similar divalent linking group as described in the Yi ⁇ Y 3 that put the formula (I) Or a divalent element.
  • a group containing sulfur, Z, or selenium is particularly preferable because the risk of ignition and ignition of the electrolytic solution is reduced. These may be of the same type within the same substituent, or some may be of different types.
  • Z represents, for example, CH 2 , CHR (R represents an alkyl group, an alkoxyl group, a fuel group, etc .; the same applies hereinafter), an NR group, oxygen, sulfur, selenium, Boron, aluminum, scandium, gallium, yttrium, indium, lanthanum, thallium, carbon, silicon, titanium, tin, germanium, zirconium, lead, phosphorus, vanadium, arsenic, jap, antimony, tantalum, bismuth, chromium, molybdenum, tenorenole , polonium, tungsten, iron, cobalt, and a divalent group containing at least one element selected from the group consisting of nickel.
  • a divalent group containing at least one element selected from the group consisting of sulfur and selenium is preferable .
  • Z may be a divalent element such as oxygen, sulfur, and selenium.
  • a phosphorus-containing substituent represented by the formula (III) is particularly preferable, since the risk of ignition and ignition can be particularly effectively reduced. Further, when the substituent is a substituent containing sulfur as represented by the formula (IV), it is particularly preferable in terms of reducing the interface resistance of the electrolytic solution.
  • R 4 is not particularly limited as long as it is a monovalent substituent or a halogen element.
  • the monovalent substituent include an alkoxy group, an alkyl group, a carboxyl group, an acyl group, an aryl group, and the like. Among them, an alkoxy group is preferable because the viscosity of the electrolytic solution can be reduced.
  • the halogen element for example, fluorine, chlorine, bromine and the like are preferably mentioned.
  • the alkoxy group include a methoxy group, an ethoxy group, a methoxetoxy group, a propoxy group, a phenoxy group and the like.
  • a methoxy group, an ethoxy group Groups, n-propoxy groups and phenoxy groups are particularly preferred, and when used in non-aqueous electrolyte secondary batteries, methoxy groups, ethoxy groups, methoxyethoxy groups and phenoxy groups are particularly preferred.
  • the hydrogen element in these monovalent substituents is preferably substituted with a halogen element.
  • the halogen element include fluorine, chlorine, and bromine. Is, for example, a trifluoro mouth ethoxy group.
  • n 3 to 13.
  • the phosphazene compound represented by the formula (VI) is a low-viscosity liquid at room temperature (25 ° C.) and has a freezing point depressing action. Therefore, by adding the phosphazene compound to the electrolytic solution, it is possible to impart excellent low-temperature characteristics to the electrolytic solution, and a low viscosity of the electrolytic solution is achieved, and a low internal resistance and high! / ⁇ It is possible to provide a non-aqueous electrolyte battery having conductivity. Therefore, it is possible to provide a non-aqueous electrolyte battery that exhibits excellent discharge characteristics over a long period of time even when used under low-temperature conditions, particularly in regions and periods when the temperature is low.
  • n is preferably from 3 to 5, more preferably from 3 to 4, because it can impart excellent low-temperature properties to the electrolytic solution and can reduce the viscosity of the electrolytic solution. It is good.
  • the value of n is small, the boiling point is low, and the ignition prevention characteristics at the time of flame contact can be improved.
  • the value of n increases, so that it can be used stably even at high temperatures. It is also possible to select and use multiple phosphazenes in a timely manner to obtain the desired performance using the above properties.
  • n in the formula (VI) By appropriately selecting the value of n in the formula (VI), it becomes possible to prepare an electrolyte having more favorable viscosity, solubility suitable for mixing, low-temperature characteristics, and the like.
  • These phosphazene compounds may be used alone or in a combination of two or more.
  • the viscosity of the phosphazene compound represented by the formula (VI) is not particularly limited as long as it is 20 mPa's (20 cP) or less, but from the viewpoint of improving conductivity and improving low-temperature characteristics, it is 10 mPa's (10 cP). ) Or less, more preferably 5 mPa's (5 cP) or less.
  • phosphazene compounds of the formula (II) a phosphazene compound represented by the following formula (VII) is preferable from the viewpoint of improving the deterioration resistance and safety of the electrolytic solution.
  • R 1G each independently represents a monovalent substituent or fluorine, at least one of all R 1D is a monovalent substituent containing fluorine or fluorine, and n is 3 to 8 Represents However, not all R 10 is fluorine.
  • the electrolyte can be provided with excellent self-extinguishing properties or flame retardancy to improve the safety of the electrolyte.
  • All R 1 .
  • at least one of them contains a phosphazene compound which is a monovalent substituent containing fluorine, it is possible to impart more excellent safety to the electrolytic solution.
  • a phosphazene compound represented by the formula (VII) and at least one of all R 1Q is fluorine is contained, more excellent safety can be provided.
  • a phosphazene compound represented by the formula (VII) in which at least one of all R 10 is a monovalent substituent containing fluorine or fluorine is more difficult to burn the electrolytic solution. This can provide more excellent safety to the electrolytic solution.
  • Examples of the monovalent substituent in the formula (VII) include an alkoxy group, an alkyl group, an acyl group, an aryl group, a carboxyl group, and the like.
  • the alkoxy group is particularly excellent in improving the safety of the electrolytic solution. It is suitable.
  • Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, a butoxy group, and an alkoxy-substituted alkoxy group such as a methoxyethoxy group.
  • a methoxy group, an ethoxy group, and an n-propoxy group are particularly preferable in terms of excellent improvement. Further, a methoxy group is preferable from the viewpoint of reducing the viscosity of the electrolytic solution.
  • n is preferably from 3 to 5, more preferably from 3 to 4, from the viewpoint that excellent safety can be imparted to the electrolytic solution.
  • the monovalent substituent is preferably substituted with fluorine.
  • R 1Q in the formula (VII) is not fluorine, at least one monovalent substituent contains fluorine.
  • the content of the fluorine in the phosphazene compound is preferably from 3 to 70% by weight, and more preferably from 7 to 45% by weight. When the content is within the above range, “excellent safety” can be particularly suitably imparted to the electrolytic solution.
  • the molecular structure of the phosphazene compound represented by the formula (VII) may contain a halogen element such as chlorine and bromine in addition to the above-mentioned fluorine. Most preferably, fluorine is followed by chlorine. Those containing fluorine tend to have a greater effect of improving the cycle characteristics of the secondary battery than those containing chlorine.
  • the viscosity of the phosphazene compound represented by the formula (VII) is not particularly limited as long as it is 20 mPa's (20 cP) or less, but from the viewpoint of improving conductivity and improving low-temperature characteristics, the viscosity is preferably 10 raPa-s (lOcP ) Or less, and more preferably 5 raPa-s (5 cP) or less.
  • the phosphazene compound is a solid at 25 ° C. (room temperature)
  • a phosphazene compound represented by the following formula (VI 11) is also preferable.
  • R 11 each independently represents a monovalent substituent or a halogen element; n represents 3 to 6.
  • the phosphazene compound represented by the formula (VIII) is solid at room temperature (25 ° C.), when it is added to an electroconductive solution, it is dissolved in the electrolytic solution and the viscosity of the electrolytic solution increases. However, if the addition amount is a predetermined amount, a nonaqueous electrolyte battery having a low rate of increase in the viscosity of the electrolyte, a low internal resistance, and a high conductivity is obtained. In addition, since the phosphazene compound represented by the formula (VIII) dissolves in the electrolyte, the electrolyte has excellent long-term stability.
  • R 11 is not particularly limited as long as it is a monovalent substituent or a halogen element.
  • the monovalent substituent include an alkoxy group, an alkyl group and a carboxy group.
  • aryl groups, aryl groups and aryl groups are examples of the monovalent substituent.
  • the halogen element for example, a halogen element such as fluorine, chlorine, bromine, and iodine is preferably exemplified.
  • an alkoxy group is particularly preferred, since it can suppress an increase in the viscosity of the electrolytic solution.
  • the alkoxy group is preferably a methoxy group, an ethoxy group, a methoxetoxy group, a propoxy group (isopropoxy group, n-propoxy group), a phenoxy group, a trifluoroethoxy group or the like, which suppresses an increase in the viscosity of the electrolytic solution.
  • a methoxy group, an ethoxy group, a propoxy group (isopropoxy group, n-propoxy group), a phenoxy group, a trifluoroethoxy group, and the like are more preferable.
  • the monovalent substituent preferably contains the halogen element described above.
  • n is particularly preferably 3 or 4 from the viewpoint that the increase in the viscosity of the electrolytic solution can be suppressed.
  • the phosphazene compound represented by (VIII) for example, the formula (VI II) to your stomach structure a R 11 turtles butoxy group and n is 3, R 11 turtles preparative In formula (VIII) A structure wherein at least one of an xy group and a phenoxy group and n is 4, a structure wherein R 11 is an ethoxy group and n is 4 in the formula (VIII), and a structure wherein R 11 is isopropoxy in the formula (VII I) A structure in which n is 3 or 4; a structure in which R 11 is an n-propoxy group in the formula (VI ⁇ ) and n is 4; and a compound in which R 11 is a trifluoroethoxy group in the formula (VI II) And n is 3 or 4, and in the formula (VI 11), R 11 is a phenoxy group and n is 3 or 4, particularly in that it can suppress an increase in the viscosity of the electrolyte. preferable.
  • the isomer of the phosphazene compound include a compound represented by the following formula (IX).
  • the compound of the formula (IX) is an isomer of a phosphazene compound represented by the following formula (X). 0 R 14
  • R 12 , R 13 and R ′′ each independently represent a monovalent substituent or a halogen element
  • X 2 represents carbon, silicon, germanium, tin, nitrogen
  • Li down represents arsenic, antimony, bismuth, oxygen, sulfur, selenium, a substituent containing at least one element selected from the group consisting of tellurium ⁇ Pi polonium
  • Y 12 and Y 13 are each independently Represents a divalent linking group, a divalent element or a single bond.
  • R 12 , R 13 and R 14 in the formula (IX) are not particularly limited as long as they are monovalent substituents or halogen elements, and are the same as those described for Ri R 3 in the above formula (I). Both a valent substituent and a halogen element are preferably exemplified.
  • Te formula (IX) smell, the divalent linking group or a bivalent element represented by Y 12 and Y 13, similar to that described in ⁇ ⁇ ⁇ 3 that put the formula (I) A divalent linking group, a divalent element, and the like are all preferably exemplified.
  • the substituent represented by X 2 any of the same substituents as those described for X 1 in the formula (I) are preferably exemplified.
  • the isomer of the phosphazene compound represented by the formula (IX) and the formula (X), when added to the electrolyte, allows the electrolyte to exhibit extremely excellent low-temperature characteristics. Can be improved in deterioration resistance and safety.
  • the isomer represented by the formula (IX) is an isomer of the phosphazene compound represented by the formula (X).
  • the degree of vacuum and / or It can be produced by adjusting the temperature, and the content (% by volume) of the isomer can be measured by the following measuring method.
  • the peak area of the sample is determined by Geno Permeation Chromatography (GPC) or High Performance Liquid Chromatography, and the peak area is compared with the previously determined area per mole of the isomer. It can be measured by obtaining the molar ratio and converting the volume taking into account the specific gravity.
  • GPC Geno Permeation Chromatography
  • High Performance Liquid Chromatography High Performance Liquid Chromatography
  • the phosphoric acid ester examples include alkynolephosphates such as trifuninolephosphate, tripaw / rephosphate, tris (fluorenetinole) phosphate, tris (trifluoroneopentinole) phosphate, alkoxyphosphate and alkoxyphosphate. These derivatives may be mentioned.
  • a supporting salt serving as a lithium ion ion source is preferable.
  • the supporting salt is not particularly limited, for example, L i C 10 4, L i BF 4, L i PF 6, L i CF 3 S_ ⁇ 3, ⁇ Pi, L i A s F 6, L i Lithium salts such as C 4 F 9 S ⁇ 3 , Li (CF 3 S ⁇ 2 ) 2 N, and Li (C 2 F 5 S 0 2 ) 2 N are preferred. These may be used alone or in combination of two or more.
  • the concentration of the supporting salt in the electrolyte is preferably from 0.2 to 1.5 mol / L (M), more preferably from 0.5 to 1 mol / L (M). If the concentration of the supporting salt is less than 0.2 mol / L (M), sufficient conductivity of the electrolyte cannot be secured, which may impair the charge / discharge characteristics of the battery. ), The viscosity of the electrolyte increases, and sufficient mobility of lithium ions cannot be secured.Therefore, sufficient conductivity of the electrolyte cannot be secured as described above, and the discharge and charge characteristics of the battery are hindered. May occur.
  • the first and second non-aqueous electrolytes of the present invention in addition to the above-described compound containing at least one of phosphorus and nitrogen in the molecule and the supporting salt, also have a viscosity of the electrolyte without reacting with the negative electrode. From the viewpoint of keeping the content low, it is preferable to contain an aprotic organic solvent.
  • aprotic organic solvent specifically, dimethyl carbonate (DMC), ethynolecarbonate (DEC), dipheninolecarbonate, ethynolemethinolecarbonate (EMC), ethylene carbonate (EC), Propylene carbonate (PC),
  • DMC dimethyl carbonate
  • DEC ethynolecarbonate
  • EMC ethynolemethinolecarbonate
  • EC ethylene carbonate
  • PC Propylene carbonate
  • carbonates such as y-butyrolactone (GBL) and ⁇ -valerolatatotone
  • ethers such as 1,2-dimethoxetane (DME) and tetrahydrofuran (THF).
  • DME 1,2-dimethoxetane
  • THF tetrahydrofuran
  • Cyclic carbonates are preferred in that they have a high relative dielectric constant and are excellent in the solubility of the supporting salt, while chain-like carbonates have a low viscosity, so that the viscosity of the electrolytic solution is reduced. It is suitable. These may be used alone or in combination of two or more.
  • the content of the compound containing at least one of phosphorus and nitrogen in the molecule at night is preferably 0.1 vol% or more, More preferably, it is at least volume%. Further, from the viewpoint of improving the safety of the electrolyte, the content is preferably 3% by volume or more, more preferably 5% by volume or more. On the other hand, the content of the compound containing at least one of phosphorus and nitrogen in the molecule in the second nonaqueous electrolyte of the present invention is preferably 0.1% by volume or more from the viewpoint of improving the permeability of the electrolyte to the separator. It is preferably at least 0.5% by volume. Further, from the viewpoint of improving the safety of the electrolyte, the content is preferably 3% by volume or more, more preferably 5% by volume or more.
  • a first non-aqueous electrolyte battery of the present invention includes the above-described first non-aqueous electrolyte of the present invention, a positive electrode, and a negative electrode. If necessary, a non-aqueous electrolyte battery such as a separator is provided. Equipped with components commonly used in the technical field.
  • a second non-aqueous electrolyte battery of the present invention includes the above-described second non-aqueous electrolyte of the present invention, a positive electrode, a negative electrode, and a separator. It has members commonly used in the technical field.
  • the positive electrode active materials of the first and second nonaqueous electrolyte batteries of the present invention are partially different between the primary battery and the secondary battery.
  • fluorinated graphite is used as the positive electrode active material of the nonaqueous electrolyte primary battery.
  • Mn0 2 even electrochemical synthesis may be chemical synthesis
  • V 2 0 5 Mo_ ⁇ 3, Ag. C R_ ⁇ 4, CuO, Cu S, F e S 2, S_ ⁇ . ⁇ , S ⁇ C 1 2 , Ti S 2
  • MnO 2 and fluorinated graphite are preferred among them because of their high capacity, high safety, and high discharge potential and excellent electrolyte wettability. These materials may be used alone or in combination of two or more.
  • V 2 0 5, V 6 0 13, Mn0 2, Mn 0 metal oxides such as 3, L i C O_ ⁇ 2, L i N i 0 2, L i Mn 2 ⁇ 4, L i F e 0 2 and L i F e P0 4 such as a lithium-containing composite Sani ⁇ of, T i S 2, Mo S metal sulfides such as 2, Poria diphosphate etc.
  • the lithium-containing composite oxide may be a composite oxide containing two or three transition metals selected from the group consisting of Fe, Mn, Co, and Ni.
  • L i C O_ ⁇ 2 L i N i 0 2
  • L i Mn 2 ⁇ 4 is particularly preferred. These materials may be used alone or in combination of two or more.
  • the negative electrode active materials of the first and second nonaqueous electrolyte batteries of the present invention are partially different between the primary battery and the secondary battery.
  • the negative electrode active material of the nonaqueous electrolyte primary battery is lithium metal itself.
  • a lithium alloy examples of the metal that forms an alloy with lithium include Sn, Pb, Al, Au, Pt, In, Zn, Cd, Ag, and Mg. Among them, A1, Zn, and Mg are preferable from the viewpoint of large reserves and toxicity. These materials may be used alone or in combination of two or more.
  • negative electrode active materials for nonaqueous electrolyte secondary batteries include lithium metal itself, alloys of lithium with Al, In, Pb or Zn, and carbon materials such as black holes doped with lithium.
  • carbon materials such as graphite are preferable, and graphite is particularly preferable, in view of higher safety and excellent wettability of the electrolytic solution.
  • examples of graphite include natural graphite, artificial graphite, mesophase carbon microbeads (MCM B), and the like, and broadly graphitizable carbon and non-graphitizable carbon. These materials The materials may be used alone or in combination of two or more.
  • the positive electrode and the negative electrode can be mixed with a conductive agent and a binder as needed.
  • the conductive agent include acetylene black and the like.
  • the binder polyvinylidene fluoride (PVDF) is used. , Polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), carboxymethyl cellulose (CMC), and the like. These additives can be used in the same mixing ratio as in the past.
  • the mass ratio of the positive electrode active material: the binder: the conductive agent is 8: 1. : 0.2 to 8: 1: 1.
  • the mass ratio of active material: binder: conductive agent is preferably 94: 3: 3:
  • the shapes of the positive electrode and the negative electrode are not particularly limited, and may be appropriately selected from known shapes as electrodes. For example, a sheet shape, a column shape, a plate shape, a spiral shape and the like can be mentioned.
  • the separator used in the second nonaqueous electrolyte battery of the present invention is disposed between the positive and negative electrodes, and prevents a short circuit of current due to contact between both electrodes.
  • a material of the separator a material capable of reliably preventing contact between the two electrodes and capable of passing or containing an electrolyte, for example, polypropylene (PP), polyethylene (PE), polyethylene-polypropylene copolymer Suitable examples include nonwoven fabrics made of synthetic resins such as (PE / PP), polytetrafluoroethylene, cellulosic, polybutylene terephthalate, and polyethylene terephthalate, and porous polymer films.
  • porous polymer membranes made of polyolefin such as polypropylene, polyethylene and polyethylene-polypropylene copolymer having a thickness of about 20 to 50 zm are particularly preferred.
  • the separator 1 can be used for the first nonaqueous electrolyte battery of the present invention.
  • first and second nonaqueous electrolyte batteries of the present invention known members usually used for nonaqueous electrolyte batteries can be suitably used.
  • first and second nonaqueous electrolyte batteries of the present invention There are no particular restrictions on the form of the first and second nonaqueous electrolyte batteries of the present invention described above.
  • Various known forms, such as a cylindrical battery having a monolithic structure, are preferably exemplified.
  • a nonaqueous electrolyte battery can be manufactured by preparing a sheet-shaped positive electrode and a negative electrode, and sandwiching a separator between the positive electrode and the negative electrode.
  • a nonaqueous electrolyte battery is manufactured by forming a sheet-shaped positive electrode, sandwiching a current collector, and stacking and winding a sheet-shaped negative electrode. Can be made.
  • L IMN 2 0 4 (positive electrode active material) 94 parts by mass of acetylene black (conductive agent) and 3 parts by mass of polyvinylidene fluoride (binder) and 3 parts by mass of an organic solvent (acetic Echiru 50/50 mass% mixed solvent with ethanol), apply the kneaded material to a 25 ⁇ thick aluminum foil (current collector) with a doctor blade, and dry with hot air (100 to 120 ° C) Thus, a positive electrode sheet having a thickness of 80 im was produced.
  • the safety of the above electrolyte was evaluated based on the combustion behavior of a flame ignited in an atmospheric environment by a method arranging the UL (Underwriting Laboratory) standard UL 94 HB method. At that time, ignitability, flammability, carbide formation, and the phenomenon during secondary ignition were also observed. Specifically, based on UL test standards, a non-combustible quartz fiber was impregnated with 1.OmL of the above electrolytic solution to prepare a 127 mm x 12.7 mm test piece.
  • the case where the test flame does not ignite the test piece is “non-flammable”, the case where the ignited flame does not reach the 25 hidden line and the ignition of the falling object is not recognized. If the flame is ⁇ flame retardant '', the ignited flame extinguishes in the 25-100 mm line and no ignition is found on the falling object, ⁇ self-extinguishing '', if the ignited flame exceeds the lOOnm line The combination was evaluated as “flammability”. Table 1 shows the results.
  • a lithium metal foil with a thickness of 150 / zm is overlaid on the above-mentioned positive electrode sheet via a separator (microporous film: made of polypropylene) with a thickness of 25 ⁇ ⁇ , and rolled up. Produced.
  • the length of the positive electrode of the cylindrical electrode was about 260 mm.
  • the electrolytic solution was injected into the cylindrical electrode and sealed to prepare an AA lithium battery (a non-aqueous electrolytic solution secondary battery).
  • FIG. 4 shows the change over time of the contact angle of the electrolyte of Comparative Example 1 with respect to the positive electrode.
  • L i C o 0 2 instead of L i M n 2 ⁇ 4 as a cathode active material, in Example 4 and Comparative Example 3, L i N i 0 2 was used to prepare a positive electrode, and the permeability to the positive electrode was tested.
  • Table 1 You. In Table 1, DMC indicates dimethyl carbonate, and Li BETI indicates Li (C 2 F 5 S ⁇ 2 ) 2 N.
  • the cyclic phosphazene B is a compound of the formula (II) in which n is 3, one of six R 4 is an ethoxy group, and five are fluorine (viscosity at 25 ° C .: 1.2 mPa-s (l .2cP)) is a compound of the formula (II) wherein n is 4, one of eight R 4 is an ethoxy group, and seven are fluorine (viscosity at 25 ° C .: 1 lmPa's (L IcP)); cyclic phosphazene D is represented by the formula (II), wherein n is 3 and one of the six R 4 is a methoxyethoxyethoxyethoxy group (CH 3 OC 2 H 4 OC in 2 H 4 OC 2 H 4 ⁇ I), compound 5 is a fluorine: a (viscosity at 25 ° C .5mPa's (4.5cP) ).
  • X 1 is a substituent represented by the formula (III) in the formula (I) and 1 , Y 2 R 2 , Y 3 R 3 , Y 5 R 5 and Y 6 R 6 Among them, three are an ethoxy group, two are fluorine, and Z is 0 (oxygen) (viscosity at 25 ° C: 4.7 mPa's (4.7 cP));
  • the chain phosphazene F is a compound represented by the following formula (XI) (viscosity at 25 ° C .: 4.9 mPa-s (4.9 cP));
  • the chain phosphazene G is a compound represented by the following formula (XII) (viscosity at 25 ° C: 2.8 mPa-s (2.8 cP));
  • the chain phosphazene H is a compound represented by the following formula (XIII) (viscosity at 25 ° C: 3.9 mPa-s (3.9 cP)).
  • the phosphate ester X is a compound represented by the following formula (XIV) (viscosity at 25 ° C .: 2.5 mPa's (2.5 cP)).
  • phosphazane Y is a compound represented by the following formula (XV) (viscosity at 25 ° C .: 5.0 mPa-s (5.0 cP)).
  • 0C 2 H 5 0C 2 H 5 triazine Z is a compound represented by the following formula (XVI) (viscosity at 25 ° C .: 2. ImPa-s (2.lcP)).
  • Example 3 A non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the above-mentioned electrolyte, and the 2 C capacity was measured. Table 1 shows the results.
  • Example 3 and Comparative Example 2 the L IMN 2 ⁇ Yore , examples L i CO0 2 instead of 4 4 and Comparative Example 3 as the positive electrode active material, using L i N i 0 2 .
  • Example 1 the residual capacity of the batteries produced in Example 1 and Comparative Example 1 was measured when the batteries were discharged at a rate of 0.125C, 0.2C, 0.5C, 1.0C, 2.0C, and 3.0C.
  • Fig. 5 shows the results.
  • the battery of Example 1 has a higher remaining capacity at each discharge rate than the battery of Comparative Example 1.
  • the battery of Example 1 has a higher capacity remaining ratio when subjected to a high rate discharge than the battery of Comparative Example 1, and is excellent in large current discharge characteristics. ⁇ Permeability of electrolyte to negative electrode of secondary battery>
  • Graphite [GD A-K 2 manufactured by Mitsui Mining & Smelting Co., Ltd.] (carbon material) 94 parts by mass, 3 parts by mass of acetylene black (conductive agent) and 3 parts by mass of polyvinylidene fluoride (binder) The mixture is kneaded with an organic solvent (50/50 mass% mixed solvent of ethyl acetate and ethanol), and the kneaded product is coated on a 25 ⁇ thick aluminum foil (current collector) with a doctor blade. Then, hot-air drying (100 to 120 ° C) was performed to produce a 150-zm-thick negative electrode sheet. 5 ⁇ L of the same electrolytic solution as in Example 1 was dropped on the negative electrode sheet, and the contact angle between the droplet of the electrolytic solution and the negative electrode sheet was measured in the same manner as in Example 1. Table 2 shows the results.
  • a 25 im-thick separator (microporous film: made of polypropylene) was interposed on the same positive electrode sheet as in Example 1, and the negative electrode sheets prepared as described above were stacked and rolled up to produce a cylindrical electrode. .
  • the length of the positive electrode of the cylindrical electrode was about 260 mm.
  • the electrolytic solution was injected into the cylindrical electrode and sealed, and an AA lithium battery (non-aqueous electrolyte secondary battery) was prepared, and the 2C capacity was measured. Table 2 shows the results.
  • Examples 23 to 49 and Comparative Examples 6 to 7 An electrolytic solution having the formulation shown in Table 2 was prepared, the permeability of the electrolytic solution to the negative electrode was evaluated in the same manner as in Example 22, and the safety of the electrolytic solution was evaluated in the same manner as in Example 1.
  • a negative electrode was prepared using mesophase carbon microbeads (MCMB) [Nikki Carbon two-stroke beads] instead of graphite as the carbon material, and the permeability to the negative electrode was also tested.
  • MCMB mesophase carbon microbeads
  • MCMB mesophase carbon microbeads
  • a non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 22 using the electrolyte, and the 2 C capacity was measured. Table 2 shows the results.
  • Mn 2 positive electrode active material
  • acetylene black conductive agent
  • polyvinylidene fluoride binder
  • PC propylene carbonate
  • DME dimethoxyethane E Tan
  • n 3
  • a cyclic phosphazene compound in which one of six R 4 is a phenoxy group (PhO_), and five are fluorine, viscosity at 25 ° 0: 1.71111′′5 ( 1.70?)) 10% by volume was added, and Li BF 4 (supporting salt) was dissolved at a concentration of 0.75 mol / L (M) to prepare an electrolytic solution.
  • An electrolytic solution having the formulation shown in Table 3 was prepared, the permeability of the electrolytic solution to the positive electrode was evaluated in the same manner as in Example 51, and the safety of the electrolytic solution was evaluated in the same manner as in Example 1. Also, a non-aqueous electrolyte primary battery was prepared in the same manner as in Example 51 using the electrolyte, and the number of pulse discharges was measured. Table 3 shows the results.
  • Non-toning supporting salt Additive Discharge Active material Penetration time Evaluation Safety Organic solvent (M) (% by mass) Number of times
  • Example 50 Less than 0.1 second
  • Example 51 Mn0 2 Less than 0.1 second
  • Example 52 Mn0 2 Less than 0.1 second
  • Example 53 Mn0 2 Less than 0.1 second
  • Example 54 Mn0 2 Less than 0.1 second
  • Example 56 Mn0 2 Less than 0.1 second
  • Example 60 Mn0 2 Less than 0.1 second
  • a non-aqueous secondary battery was manufactured as follows. First, L i CO0 2 against [Nippon Chemical Industrial Co., Ltd.] (positive electrode active material) 100 parts by weight of acetylene black (conductive agent) 10 parts by weight, Teflon (R) Vine After adding 10 parts by mass of a binder (binder) and kneading with an organic solvent (50/50% by mass mixed solvent of ethyl acetate and ethanol), roll-rolled to form a thin layer with a thickness of 100 ⁇ and a width of 40 mm. A positive electrode sheet was produced.
  • L i CO0 2 against [Nippon Chemical Industrial Co., Ltd.] positive electrode active material 100 parts by weight of acetylene black (conductive agent) 10 parts by weight, Teflon (R) Vine After adding 10 parts by mass of a binder (binder) and kneading with an organic solvent (50/50% by mass mixed solvent of ethyl acetate and ethanol), roll
  • a negative electrode sheet made of graphite with a thickness of 150 ⁇ was used as the negative electrode.
  • the separator was sandwiched between one positive electrode sheet and one negative electrode sheet and rolled up to produce a cylindrical electrode.
  • the length of the positive electrode of the cylindrical electrode was about 260.
  • the above-mentioned electrolytic solution was injected into the cylindrical electrode and sealed, to prepare an AA lithium battery (non-aqueous electrolyte secondary battery), and the internal resistance (DC resistance of the battery) was measured according to a conventional method. It was measured. As a result, the internal resistance of the battery was 0.10 ⁇ .
  • FIG. 7 shows the change over time of the contact angle of the electrolytic solution of Comparative Example 9 with the separator.
  • a polypropylene separator (porous polymer membrane, thickness 25 / ra, Celgard) was used instead of a polyethylene separator.
  • polyethylene # polypropylene copolymer separator (porous polymer membrane, thickness 25 / zm, Celgard # 35 04) was used. Table 4 shows the results.
  • a non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 65 using the electrolyte and the separator shown in Table 4, and the internal resistance was measured. Table 4 shows the results.
  • Example 70 PP Kaman (Q) Self-extinguishing 0.07
  • Example 72 PP wood

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Abstract

La présente invention a trait à une solution d'électrolyte non aqueux présentant une excellente perméabilité à travers un matériau d'électrode et/ou un séparateur et permettant la réduction de la résistance interne d'une batterie. Un mode d'une telle solution d'électrolyte non aqueux est caractérisé en ce qu'un angle de contact (υ1) formé par la solution d'électrolyte non aqueux (1) avec une électrode (2) se transforme en un angle égal ou inférieure à 2° dans moins de 0,5 seconde après la chute de la solution d'électrolyte non aqueux (1) sur l'électrode (2). Un autre mode d'une telle solution d'électrolyte non aqueux est caractérisé en ce qu'un angle de contact (υ2) formé par la solution d'électrolyte non aqueux (1) avec un séparateur (3) se transforme en un angle égal ou inférieur à 25° en moins de 2 seconds après la chute de la solution d'électrolyte non aqueux (1) sur le séparateur (3).
PCT/JP2004/004961 2003-04-11 2004-04-06 Solution d'electrolyte non aqueux et batterie a electrolyte non aqueux utilisant une telle solution WO2004093224A1 (fr)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
JP2013168241A (ja) * 2012-02-14 2013-08-29 Sumitomo Chemical Co Ltd ナトリウム二次電池用負極材、ナトリウム二次電池用電極及びナトリウム二次電池
WO2019054418A1 (fr) * 2017-09-12 2019-03-21 セントラル硝子株式会社 Additif d'électrolyte non aqueux, électrolyte non aqueux, et batterie à électrolyte non aqueux

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JP2001102088A (ja) * 1999-07-29 2001-04-13 Bridgestone Corp 非水電解液電池
JP2001217006A (ja) * 1999-11-25 2001-08-10 Bridgestone Corp 非水電解液二次電池
WO2002021630A1 (fr) * 2000-09-07 2002-03-14 Bridgestone Corporation Additif pour batterie secondaire à électrolyte non aqueux
WO2002021628A1 (fr) * 2000-09-07 2002-03-14 Bridgestone Corporation Additif pour electrolyte liquide non aqueux, element secondaire a electrolyte liquide non aqueux et condensateur a double couche electrique et a electrolyte liquide non aqueux
WO2002021629A1 (fr) * 2000-09-07 2002-03-14 Bridgestone Corporation Additif pour electrolyte liquide non aqueux, cellule secondaire d'electrolyte liquide non aqueux et condensateur electrique d'electrolyte liquide non aqueux a double couche

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Publication number Priority date Publication date Assignee Title
JP2001102088A (ja) * 1999-07-29 2001-04-13 Bridgestone Corp 非水電解液電池
JP2001217006A (ja) * 1999-11-25 2001-08-10 Bridgestone Corp 非水電解液二次電池
WO2002021630A1 (fr) * 2000-09-07 2002-03-14 Bridgestone Corporation Additif pour batterie secondaire à électrolyte non aqueux
WO2002021628A1 (fr) * 2000-09-07 2002-03-14 Bridgestone Corporation Additif pour electrolyte liquide non aqueux, element secondaire a electrolyte liquide non aqueux et condensateur a double couche electrique et a electrolyte liquide non aqueux
WO2002021629A1 (fr) * 2000-09-07 2002-03-14 Bridgestone Corporation Additif pour electrolyte liquide non aqueux, cellule secondaire d'electrolyte liquide non aqueux et condensateur electrique d'electrolyte liquide non aqueux a double couche

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013168241A (ja) * 2012-02-14 2013-08-29 Sumitomo Chemical Co Ltd ナトリウム二次電池用負極材、ナトリウム二次電池用電極及びナトリウム二次電池
WO2019054418A1 (fr) * 2017-09-12 2019-03-21 セントラル硝子株式会社 Additif d'électrolyte non aqueux, électrolyte non aqueux, et batterie à électrolyte non aqueux
JP2019053984A (ja) * 2017-09-12 2019-04-04 セントラル硝子株式会社 非水電解液用添加剤、非水電解液、及び非水電解液電池
JP7223221B2 (ja) 2017-09-12 2023-02-16 セントラル硝子株式会社 非水電解液用添加剤、非水電解液、及び非水電解液電池
US11757130B2 (en) 2017-09-12 2023-09-12 Central Glass Co., Ltd. Additive for non-aqueous electrolyte solution, non-aqueous electrolyte solution, and non-aqueous electrolyte solution battery

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