WO2014112420A1 - 二次電池用活物質、二次電池用電極、二次電池、電池パック、電動車両、電力貯蔵システム、電動工具および電子機器 - Google Patents

二次電池用活物質、二次電池用電極、二次電池、電池パック、電動車両、電力貯蔵システム、電動工具および電子機器 Download PDF

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WO2014112420A1
WO2014112420A1 PCT/JP2014/050188 JP2014050188W WO2014112420A1 WO 2014112420 A1 WO2014112420 A1 WO 2014112420A1 JP 2014050188 W JP2014050188 W JP 2014050188W WO 2014112420 A1 WO2014112420 A1 WO 2014112420A1
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secondary battery
group
active material
positive electrode
hydrocarbon group
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English (en)
French (fr)
Japanese (ja)
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雅輝 三沢
小谷　徹
寿朗 西
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Sony Corp
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Sony Corp
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Priority to KR1020157018109A priority Critical patent/KR102099491B1/ko
Priority to EP14740333.1A priority patent/EP2947712B1/en
Priority to US14/760,403 priority patent/US9899670B2/en
Priority to CN201480004602.2A priority patent/CN104919630B/zh
Publication of WO2014112420A1 publication Critical patent/WO2014112420A1/ja
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • 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 technology relates to an active material for a secondary battery capable of occluding and releasing an electrode reactant, a secondary battery electrode and a secondary battery using the active material for the secondary battery, and a battery pack using the secondary battery.
  • the present invention relates to an electric vehicle, an electric power storage system, an electric tool, and an electronic device.
  • Electronic devices such as mobile phones and personal digital assistants (PDAs) are widely used, and further downsizing, weight reduction, and long life of the electronic devices are demanded. Accordingly, as a power source, development of a battery, in particular, a secondary battery that is small and lightweight and capable of obtaining a high energy density is in progress.
  • secondary batteries are not limited to the electronic devices described above, but are also being considered for various other uses. Examples include battery packs that are detachably mounted on electronic devices, electric vehicles such as electric cars, power storage systems such as household power servers, and electric tools such as electric drills. It is done.
  • Secondary batteries that use various charge / discharge principles have been proposed to obtain battery capacity.
  • secondary batteries that use the storage and release of electrode reactants, and secondary batteries that use precipitation and dissolution of electrode reactants. Secondary batteries are attracting attention. This is because higher energy density can be obtained than lead batteries and nickel cadmium batteries.
  • the secondary battery includes an electrolyte solution together with a positive electrode and a negative electrode, and the positive electrode includes an active material (positive electrode active material) that can occlude and release an electrode reactant.
  • an oxide lithium composite oxide
  • the positive electrode active material an oxide (lithium composite oxide) containing lithium (Li) and one or more transition metal elements as constituent elements is generally widely used.
  • a metal oxide such as magnesium oxide (MgO) is formed on the surface of the positive electrode containing a lithium-transition metal composite oxide (Li x Ni 1-y Co y O z ).
  • the film of the thing is formed (for example, refer patent document 1).
  • the positive electrode active material LiA 1-xy B x C y O 2 : A is Co, B is Ni, C is Mn, etc.
  • a metal oxide such as magnesium (Mg) oxide see, for example, Patent Document 2.
  • Lithium-nickel-manganese-M composite oxide Li x Ni y Mn 1-yz M z O 2 : M is Fe, etc.
  • lithium in order to improve capacity, charge / discharge cycle durability and safety - and mixing the cobalt composite oxide (Li x CoO 2) (e.g., see Patent Document 3.).
  • LiFSI lithium bisfluorosulfonylimide
  • a non-solvated polymer and a polar aprotic compound such as sulfamide are used as a binder (see, for example, Patent Document 6).
  • LiTFSI lithium bistrifluoromethanesulfonylimide
  • a mixture of a positive electrode active material (manganese oxide) and a conductive agent is heat-treated in an organic solvent containing imidazole and LiFSI (see, for example, Patent Document 10).
  • the electrode is immersed in a pretreatment electrolytic solution in which a lithium salt (LiTFSI) is dissolved in an organic solvent containing a nitrile compound. A voltage is applied (see, for example, Patent Document 11).
  • LiTFSI is contained in the electrolyte (see, for example, Patent Documents 12 and 13).
  • Japanese Patent No. 3172388 Japanese Patent No. 3691279 JP 2002-1003007 A JP 2004-165151 A JP 2010-129449 A Special table 2007-522616 JP 10-289733 A JP 2002-352864 A Special table 2011-513924 gazette JP 2010-225498 A JP 2010-245017 A JP 2011-150958 A JP 2006-294375 A
  • an active material for a secondary battery an electrode for a secondary battery, a secondary battery, a battery pack, an electric vehicle, an electric power storage system, an electric tool, and an electronic device that can obtain excellent battery characteristics.
  • the active material for a secondary battery according to an embodiment of the present technology is capable of occluding and releasing electrode reactants, and has a peak due to SO 2 ⁇ obtained by negative ion analysis using time-of-flight secondary ion mass spectrometry.
  • the ratio IS / IF between the intensity IS and the intensity IF of the peak due to LiF 2 ⁇ is 0.04 or more.
  • An electrode for a secondary battery according to an embodiment of the present technology includes an active material capable of occluding and releasing an electrode reactant, and the active material is the same as the active material for a secondary battery according to an embodiment of the present technology described above. It has a configuration.
  • a secondary battery according to an embodiment of the present technology includes an electrolyte solution together with a positive electrode and a negative electrode, and the positive electrode has the same configuration as the electrode for a secondary battery according to an embodiment of the present technology described above.
  • a battery pack, an electric vehicle, an electric power storage system, an electric power tool, or an electronic device according to an embodiment of the present technology includes a secondary battery, and the secondary battery is similar to the secondary battery according to the embodiment of the present technology described above. It has a configuration.
  • FIG. 5 is a sectional view taken along line VV of the spirally wound electrode body shown in FIG. It is a block diagram showing the structure of the application example (battery pack) of a secondary battery.
  • Active material for secondary battery Application example of active material for secondary battery 2-1. Secondary battery electrode and secondary battery (cylindrical lithium ion secondary battery) 2-2. Secondary battery electrode and secondary battery (laminate film type lithium ion secondary battery) 2-3. Secondary battery electrode and secondary battery (lithium metal secondary battery) 3. Applications of secondary batteries 3-1. Battery pack 3-2. Electric vehicle 3-3. Power storage system 3-4. Electric tool
  • Secondary battery active material An active material for a secondary battery according to an embodiment of the present technology (hereinafter also simply referred to as “active material”) is used for an electrode of a secondary battery.
  • the secondary battery is, for example, a lithium secondary battery, and the active material described here may be used as, for example, a positive electrode active material or a negative electrode active material.
  • the active material can occlude and release the electrode reactant.
  • This electrode reactant is a substance that can move between electrodes during the electrode reaction, such as lithium in a lithium secondary battery.
  • time-of-flight secondary ion mass spectrometry when a negative ion analysis is performed on an active material using time-of-flight secondary ion mass spectrometry, the peak intensity ratio resulting from the two specific negative ions obtained by the negative ion analysis satisfies a specific condition. ing.
  • This time-of-flight secondary ion mass spectrometry is a so-called TOF-SIMS (Time-of-flight secondary ion mass spectrometry).
  • the peak due to SO 2 ⁇ is a peak mainly caused by a sulfonyl group (> SO 2 ) or the like existing on the surface of the active material and in the vicinity thereof, and the higher the intensity IS of the peak, the more the active material The decomposition reaction of the electrolyte solution used for the secondary battery is suppressed.
  • the surface layer part having a sulfonyl group covers the main part (center part) responsible for occlusion and release of the electrode reactant, so even if the center part is activated during the electrode reaction, the main part is chemically It is because it is protected by. Thereby, since the chemical stability of the active material is improved, the electrolytic solution is hardly decomposed even when the electrode reaction is repeated.
  • the composition (ion species and their ratio) in the vicinity of the surface of a sample (here, active material) is measured. Therefore, the fact that a peak due to SO 2 ⁇ is detected by negative ion analysis of the active material indicates that a sulfonyl group that generates SO 2 ⁇ exists near the surface of the active material. .
  • the peak due to LiF 2 ⁇ is a peak mainly caused by other materials (for example, electrolyte salt and decomposition products thereof) used in the secondary battery together with the active material.
  • LiF lithium fluoride
  • the strength ratio IS / IF is 0.04 or more because the balance between the above two peak strengths IS and IF is optimized, so that the decomposition reaction of the electrolytic solution is suppressed and the electrical resistance of the active material is increased. This is because suppression is compatible. Specifically, if the intensity ratio IS / IF is too small (IS / IF ⁇ 0.04), the amount of coverage of the central portion by the surface layer portion having a sulfonyl group is insufficient, or fluorine that causes generation of inert substances The abundance of is excessive.
  • the function of suppressing the decomposition of the electrolytic solution is not exhibited, or the electrical resistance of the active material is remarkably increased.
  • the intensity ratio IS / IF is within an appropriate range (IS / IF ⁇ 0.04), the covering amount of the central portion by the surface layer portion having a sulfonyl group is ensured, and the amount of fluorine present is It can be reduced. For this reason, it is difficult for the decomposition reaction of the electrolytic solution to occur, and the electric resistance of the active material is hardly increased.
  • composition of active material This active material may have any configuration as long as it can absorb and release the electrode reactive material and the intensity ratio IS / IF satisfies the above-described conditions.
  • FIG. 1 shows a cross-sectional configuration of the active material 100.
  • the active material 100 includes, for example, a central portion 101 that can occlude and release an electrode reactive material and a covering portion 102 provided in the central portion 101.
  • the central portion 101 is a main portion (inner portion) existing inside the active material 100, and includes one or more electrode materials capable of occluding and releasing the electrode reactant.
  • the type of electrode material is not particularly limited as long as the electrode active material can be occluded and released.
  • This electrode material is preferably a compound containing lithium (Li) as a constituent element (lithium-containing compound). This is because a high energy density can be obtained.
  • the lithium-containing compound may be, for example, a lithium composite oxide, a lithium phosphate compound and a lithium sulfide, or an intercalation compound containing lithium.
  • the lithium composite oxide is an oxide containing lithium and one or more transition metal elements as constituent elements
  • the lithium phosphate compound is lithium and one or more transition metal elements.
  • the lithium-containing compound is preferably a lithium composite oxide and a lithium phosphate compound. This is because a higher energy density can be obtained stably.
  • the lithium composite oxide is, for example, a compound having an average composition represented by any of the following formulas (11) to (13), and has a so-called layered rock salt type crystal structure.
  • M1 is at least one of the group consisting of elements of Group 2 to Group 15 (excluding Ni and Mn) in the long-period periodic table, and X is Group 16 and Group 17 in the long-period periodic table.
  • A1, b1, c1, d1 and e1 are 0 ⁇ a1 ⁇ 1.5, 0 ⁇ b1 ⁇ 1, 0 ⁇ c1 ⁇ 1, ⁇ 0.1 ⁇ d1 ⁇ 0.2 and 0 ⁇ e1 ⁇ 0.2, where the composition (molar ratio) of Li varies depending on the charge / discharge state, and the value of a1 is the value of the complete discharge state .)
  • M2 is at least one member selected from the group consisting of V, Cu, Zr, Zn, Mg, Al, Ga, Y, and Fe.
  • A2, b2, and c2 are 0.9 ⁇ a2 ⁇ 1.1, 0 ⁇ b2 ⁇ 0.3 and ⁇ 0.1 ⁇ c2 ⁇ 0.1 are satisfied, and the composition (molar ratio) of Li varies depending on the charge / discharge state, and the value of a2 is the value of the complete discharge state. .
  • M3 is at least one member selected from the group consisting of V, Cu, Zr, Zn, Mg, Al, Ga, Y and Fe.
  • A3, b3, c3, d3 and e3 are 0.9 ⁇ a3 ⁇ . 1.1, 0 ⁇ b3 ⁇ 1, 0 ⁇ c3 ⁇ 1, 0 ⁇ d3 ⁇ 0.5, ⁇ 0.1 ⁇ e3 ⁇ 0.1 and 0 ⁇ 1-b3-c3-d3 are satisfied.
  • the composition (molar ratio) of A3 varies depending on the charge / discharge state, and the value of a3 is the value of the complete discharge state.
  • lithium composite oxide having a layered rock salt type crystal structure examples include lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), nickel cobalt manganese composite lithium oxide (LiCoNiO 2 ), and the like.
  • the compound of may be sufficient.
  • lithium complex oxide contains cobalt (Co) as a transition metal element. This is because a high discharge voltage can be obtained.
  • the lithium composite oxide is a compound having an average composition represented by the following formula (14), for example, and has a so-called spinel crystal structure.
  • M4 is at least one of the group consisting of Co, Ni, Mg, Al, B, Ti, V, Cr, Fe, Cu, Zn, Mo, Sn, Ca, Sr and W.
  • a4, b4 , C4 and d4 satisfy 0.9 ⁇ a4 ⁇ 1.1, 0 ⁇ b4 ⁇ 0.6, 3.7 ⁇ c4 ⁇ 4.1, and 0 ⁇ d4 ⁇ 0.1.
  • the value of a4 is the value of the complete discharge state.
  • lithium composite oxide having a spinel crystal structure examples include lithium manganate (LiMn 2 O 4 ), and other compounds may be used.
  • the lithium phosphate compound is, for example, a compound having an average composition represented by any of the following formulas (15) and (16), and has a so-called olivine type crystal structure.
  • Li a5 M5 b5 PO 4 (15) (M5 is at least one of the group consisting of Group 2 to Group 15 elements in the long-period periodic table. A5 and b5 satisfy 0 ⁇ a5 ⁇ 2 and 0.5 ⁇ b5 ⁇ 2. )
  • Li a6 M6PO 4 (16)
  • M6 is at least one selected from the group consisting of Co, Mn, Fe, Ni, Mg, Al, B, Ti, V, Nb, Cu, Zn, Mo, Ca, Sr, W, and Zr.
  • lithium phosphate compound having an olivine-type crystal structure examples include lithium iron phosphate (LiFePO 4 ), and other compounds may be used.
  • lithium composite oxides and lithium phosphate compounds lithium composite oxides having a layered rock salt type crystal structure are preferable. This is because a high energy density can be obtained.
  • the electrode material may be any one kind or two or more kinds of oxides, disulfides, chalcogenides, conductive polymers, and the like.
  • oxide include titanium oxide, vanadium oxide, and manganese dioxide.
  • disulfide include titanium disulfide and molybdenum sulfide.
  • chalcogenide is niobium selenide.
  • conductive polymer include sulfur, polyaniline, and polythiophene.
  • the central portion 101 (for example, the above-described lithium-containing compound) has, for example, one or more elements (hereinafter referred to as “coating elements”) having different types from the transition metal element constituting the lithium-containing compound on the surface. .) May be included. This is because the electrochemical stability of the active material 100 is improved.
  • the type of the covering element is not particularly limited, but among them, it is preferable that the element is a different type of element from the transition metal element (so-called main transition metal element) contained in the lithium-containing compound.
  • This main transition metal element is one type of transition metal element having the largest content ratio (molar ratio) among the transition metal elements contained in the lithium-containing compound.
  • the lithium-containing compound is LiCo 0.98 Al 0.01 Mg 0.01 O 2
  • the main transition metal element is Co.
  • a covering element will be any 1 type or 2 types or more of elements other than Co.
  • Specific examples of the covering element include nickel (Ni), manganese (Mn), and phosphorus (P).
  • the covering portion 102 is provided on at least a part of the surface of the central portion 101.
  • coated part 102 may be provided in the whole surface of the center part 101, and may be provided in a part of the surface. In the latter case, the covering portions 102 may exist at a plurality of locations on the surface of the central portion 101.
  • Covering portion 102 is, for example, compounds having sulfonyl group (> SO 2) (hereinafter, referred to as. "Sulfonyl compound”) contains one, or two or more. This is because the presence of the sulfonyl group on the surface of the central portion 101 protects the central portion 101 chemically as described above, thereby improving the chemical stability of the active material 100.
  • This sulfonyl compound may have only one sulfonyl group, or may have two or more.
  • the sulfonyl compound may be any compound as long as it has one or more sulfonyl groups as described above.
  • the sulfonyl compound includes, for example, any one type or two or more types from the group consisting of compounds represented by the following formulas (1) to (4).
  • R1 to R4 are each a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, or a group in which two or more of them are bonded. Yes, any two or more of R1 to R4 may be bonded to each other.
  • R5 and R6 are each a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, or a group in which two or more of them are bonded. And R5 and R6 may be bonded to each other, and M is a metal element.
  • R7 to R12 are each a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, or a group in which two or more of them are bonded. Yes, any two or more of R7 to R12 may be bonded to each other.
  • R13 to R16 are each a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, or a group in which two or more of them are bonded. Yes, any two or more of R13 to R16 may be bonded to each other.
  • the compound represented by the formula (1) is a chain compound having one sulfonyl group.
  • the compound represented by the formula (2) is a chain compound having two sulfonyl groups.
  • the compound represented by formula (3) is a cyclic compound having one sulfonyl group, and does not have an unsaturated bond (carbon-carbon double bond) in the ring.
  • the compound represented by Formula (4) is a cyclic compound having one sulfonyl group, and has an unsaturated bond (carbon-carbon double bond) in the ring.
  • each of formula (1) and formula (2) have a nitrogen bond (> N-) together with a sulfonyl group.
  • the sulfur atom (S) and nitrogen bond (nitrogen atom (N)) in the sulfonyl group may or may not be bonded to each other.
  • it is preferable that the sulfur atom and the nitrogen bond are bonded to each other. This is because a higher effect can be obtained.
  • Each type of R1 to R4 in the formula (1) is a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, or two types thereof.
  • the above is not particularly limited as long as it is any of the bonded groups. This is because if the sulfonyl compound has the chemical structure shown in Formula (1), the above-described advantages can be obtained without depending on the types of R1 to R4.
  • R1 to R4 may be the same type or different from each other, and any two or more of R1 to R4 may be the same type. Also, any two or more of R1 to R4 are bonded to each other, and a ring may be formed by the bonded groups.
  • the hydrocarbon group is a general term for monovalent groups composed of carbon (C) and hydrogen (H), and may be linear or branched having one or more side chains.
  • the hydrocarbon group may be an unsaturated hydrocarbon group having a carbon-carbon multiple bond (carbon-carbon double bond or carbon-carbon triple bond), or a saturated hydrocarbon group having no carbon-carbon multiple bond.
  • hydrocarbon group examples include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a cycloalkyl group, and the number of carbon atoms thereof is not particularly limited. This is because the above-described advantages can be obtained without depending on the number of carbon atoms.
  • the alkyl group has 1 to 12 carbon atoms
  • the alkenyl group and the alkynyl group have 2 to 12 carbon atoms
  • the aryl group has 6 to 18 carbon atoms
  • the cycloalkyl group has 3 to 18 carbon atoms.
  • the carbon number of the alkyl group, alkenyl group, and alkynyl group is more preferably 6 or less, and still more preferably 4 or less. This is because excellent solubility and compatibility are ensured.
  • the alkyl group includes a methyl group (—CH 3 ), an ethyl group (—C 2 H 5 ), a propyl group (—C 3 H 7 ), and the like.
  • Examples of the alkenyl group include a vinyl group (—CH ⁇ CH 2 ) and an allyl group (—CH 2 —CH ⁇ CH 2 ).
  • the alkynyl group includes an ethynyl group (—C ⁇ CH) and the like.
  • the aryl group includes a phenyl group and a naphthyl group.
  • the cycloalkyl group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like.
  • the halogen group is, for example, a fluorine group, a chlorine group, a bromine group, or an iodine group, and among them, a fluorine group is preferable. This is because a higher effect can be obtained.
  • the halogenated hydrocarbon group is a group in which at least a part of the above-described hydrocarbon groups is substituted (halogenated) with a halogen group.
  • the type of this halogen group is as described above.
  • the halogenated hydrocarbon group includes, for example, a trifluoromethyl group (—CF 3 ) and a pentafluoroethyl group (—C 2 F 5 ).
  • the oxygen-containing hydrocarbon group is a general term for monovalent groups composed of oxygen (O) together with carbon and hydrogen. It is the same as that of the above-mentioned hydrocarbon group that it may be linear or branched, and may or may not have a carbon-carbon multiple bond.
  • the oxygen-containing hydrocarbon group examples include an alkoxy group, and the number of carbon atoms is not particularly limited. This is because the above-described advantages can be obtained without depending on the number of carbon atoms.
  • the alkoxy group preferably has 1 to 18 carbon atoms, more preferably 6 or less, and still more preferably 4 or less. This is because excellent solubility and compatibility are ensured.
  • the alkoxy group includes a methoxy group (—OCH 3 ), an ethoxy group (—OC 2 H 5 ), a propoxy group (—OC 3 H 7 ), and the like.
  • the halogenated oxygen-containing hydrocarbon group is a group in which at least a part of the oxygen-containing hydrocarbon groups described above is substituted (halogenated) with a halogen group.
  • the type of this halogen group is as described above.
  • the halogenated oxygen-containing hydrocarbon group includes a trifluoromethoxy group (—OCF 3 ) and a pentafluoroethoxy group (—OC 2 F 5 ).
  • the group in which two or more of them are bonded is any two of the above-described hydrogen group, hydrocarbon group, oxygen-containing hydrocarbon group, halogen group, halogenated hydrocarbon group, and halogenated oxygen-containing hydrocarbon group. It is a group bonded so that more than one kind is monovalent as a whole.
  • the type of the group to which two or more types are bonded is not particularly limited.
  • a group in which an aryl group and an alkyl group are bonded (benzyl group), a cycloalkyl group and an alkyl group are bonded.
  • each of R1 to R4 may be a group other than the series of groups described above. More specifically, R1 to R4 may be, for example, derivatives of the above-described series of groups. This derivative is obtained by introducing one or more substituents into a series of groups, and the type of the substituents may be arbitrary.
  • the type of M in the formula (2) is not particularly limited as long as it is a metal element, but among these, an alkali metal element is preferable. This is because a higher effect can be obtained.
  • the alkali metal element include lithium (Li), sodium (Na), and potassium (K). Among them, lithium is preferable.
  • Specific examples of the compound represented by the formula (1) include any one kind or two kinds or more of the group consisting of compounds represented by the following formulas (1-1) to (1-13). is there.
  • Specific examples of the compound represented by the formula (2) include any one or more of the group consisting of the compounds represented by the following formulas (2-1) to (2-11). is there.
  • Specific examples of the compound represented by the formula (3) include any one or more of the group consisting of compounds represented by the following formulas (3-1) to (3-11). is there.
  • Specific examples of the compound represented by the formula (4) include one or more of the group consisting of compounds represented by the following formulas (4-1) to (4-11). is there.
  • the sulfonyl compound may be other compounds than the above as long as it has a chemical structure represented by any one of formulas (1) to (4). Further, the sulfonyl compound may be a compound having a structure other than the chemical structure shown in each of formulas (1) to (4) as long as it has one or more sulfonyl groups.
  • the coating amount of the central portion 101 by the covering portion 102 is not particularly limited, but is preferably 0.1% by weight to 5% by weight, for example, 0.2% by weight to 3% by weight with respect to the central portion 101. % Is more preferable. This is because the covering function of the covering portion 102 is exhibited without hindering the occlusion / release of the electrode reactant in the central portion 101. Specifically, when the coating amount is less than 0.1% by weight, the central portion 101 is not sufficiently covered by the covering portion 102, and thus the chemical stability of the active material 100 is difficult to improve. On the other hand, when the coating amount is more than 5% by weight, the central portion 101 is difficult to occlude and release the electrode reactant, and the energy density is likely to decrease.
  • the peak intensity ratio due to two negative ions obtained by the negative ion analysis of the active material using TOF-SIMS satisfies other conditions.
  • the intensity ratio IN / IF of the two peaks is preferably 0.03 or more. Details regarding the procedure for obtaining the intensity ratio IN / IF and the apparatus used are the same as those for the intensity ratio IS / IF described above.
  • the peak caused by SNO 2 - is a peak mainly caused by a sulfonyl group and a nitrogen bond existing on the surface of the active material and in the vicinity thereof.
  • the peak intensity IN increases, the decomposition reaction of the electrolytic solution is suppressed, and the generation of gas due to the decomposition reaction of the electrolytic solution is suppressed. This is because even if a decomposition product of the electrolytic solution is generated, the decomposition product is difficult to gasify. Thereby, since the generation amount of gas is suppressed, even if the electrode reaction is repeated, the secondary battery using the active material is less likely to swell.
  • the intensity ratio IN / IF is 0.03 or more because the balance between the intensity IN and IF of the two peaks described above is optimized, so that the suppression of gas generation and the increase in electrical resistance of the active material are suppressed. This is because they are compatible. Specifically, if the intensity ratio IN / IF is too small (IN / IF ⁇ 0.03), it becomes a source of a component (SNO 2 ⁇ that exhibits a function of suppressing gas generation at and near the surface of the active material. The amount of functional groups) is insufficient. Thereby, when the intensity ratio IS / IF satisfies the above-described conditions, the decomposition reaction of the electrolytic solution can be suppressed, but it is difficult to suppress gas generation.
  • the intensity ratio IN / IF is within an appropriate range (IN / IF ⁇ 0.03), the amount of the component that exhibits the function of suppressing gas generation is secured.
  • the strength ratio IS / IF satisfies the above-described conditions, not only the decomposition reaction of the electrolytic solution is suppressed, but also gas is hardly generated and the electric resistance of the active material is hardly increased.
  • the active material in this case may have any configuration as long as the electrode reactant can be occluded and released and the intensity ratios IS / IF and IN / IF satisfy the above-described conditions.
  • the covering portion 102 when the intensity ratio IN / IF satisfies the above-described condition includes one or more of compounds having a nitrogen bond together with a sulfonyl group (hereinafter referred to as “nitrogen-containing sulfonyl compound”). Preferably it is. This is because the presence of the sulfonyl group and the nitrogen bond on the surface of the central portion 101 and the vicinity thereof improves the chemical stability of the active material 100 and suppresses gas generation as described above.
  • the nitrogen-containing sulfonyl compound may be any compound as long as it has a nitrogen bond with the sulfonyl group as described above.
  • the nitrogen-containing sulfonyl compound includes, for example, any one type or two or more types from the group consisting of the compounds represented by Formula (1) and Formula (2).
  • Specific examples of the nitrogen-containing sulfonyl compound include any one selected from the group consisting of the compounds represented by formulas (1-1) to (1-13) and formulas (2-1) to (2-11). There are two types or more.
  • the nitrogen-containing sulfonyl compound may be a compound other than the above as long as it has a chemical structure represented by either formula (1) or formula (2). Further, the nitrogen-containing sulfonyl compound may be a compound having a structure other than the chemical structure shown in each of the formulas (1) and (2) as long as it has a nitrogen bond together with the sulfonyl group.
  • the average particle diameter (median diameter) of the active material is not particularly limited, but is preferably 2 ⁇ m to 50 ⁇ m. This is because a decrease in energy density is suppressed and the possibility of occurrence of a short circuit is reduced.
  • the average particle size is smaller than 2 ⁇ m, the surface area of the active material becomes too large, so when the active material layer containing the active material is formed, the addition amount of a conductive agent and a binder is increased. It is necessary to let Thereby, since the amount of the active material per unit mass is reduced, the energy density is easily lowered. Further, when the active material layer needs to be compression-molded, the active material layer is easily peeled off from the current collector or the like at the time of compression molding. On the other hand, when the average particle size is larger than 50 ⁇ m, the active material easily penetrates the separator and the like, and thus the possibility of occurrence of a short circuit increases.
  • This active material is manufactured, for example, by the following procedure.
  • the active material 100 including the center portion 101 and the covering portion 102 illustrated in FIG. 1 is manufactured will be described.
  • a central portion 101 made of an electrode material capable of occluding and releasing an electrode reactant is prepared.
  • the central portion 101 may have a covering element on the surface of the central portion 101 such as a lithium-containing compound.
  • the covering raw material When providing the covering element on the surface of the central portion 101, for example, after preparing a compound (coating raw material) containing the covering element as a constituent element, the covering raw material is pulverized and mixed together with the central portion 101, The coating element in the coating raw material is deposited on the surface of the central portion 101.
  • This pulverization and mixing method is, for example, any one type or two or more types such as a ball mill, a jet mill, a pulverizer, and a fine pulverizer.
  • a liquid such as water may be added to the mixture of the central portion 101 and the coating raw material.
  • a mechanochemical treatment such as mechanofusion, or a vapor phase growth method such as a sputtering method or a chemical vapor deposition (CVD) method may be used.
  • a wet method such as a method of mixing the central portion 101 and the coating raw material in a solvent such as water or ethanol, a neutralization titration method, or a sol-gel method using a metal alkoxide as a raw material may be used.
  • the number of times of this deposition process is not particularly limited, and may be one time or two or more times.
  • different types of coating elements may be used in each deposition process.
  • a baking treatment may be performed in an oxidizing atmosphere (in air or pure oxygen).
  • the firing temperature is not particularly limited, but is, for example, 300 ° C. to 1000 ° C.
  • the particle size may be adjusted by performing a light pulverization treatment or classification operation.
  • a covering portion 102 is formed on the surface of the central portion 101.
  • the method for forming the covering portion 102 is, for example, one type or two or more types from the group consisting of a liquid phase method and a gas phase method.
  • the liquid phase method include a coating method, a dipping method, and a dip coating method.
  • the gas phase method include a vapor deposition method, a sputtering method, and a CVD method.
  • the liquid phase method using a solution (treatment solution) containing a sulfonyl compound is preferable.
  • the covering portion 102 can be easily formed without heating the central portion 101.
  • the treatment solution may be applied to the surface of the central portion 101 and then dried, or after the central portion 101 is immersed in the treatment solution, the central portion 101 is formed. May be lifted from the treatment solution and dried.
  • the formation amount of the covering portion 102 can be adjusted by changing conditions such as the concentration of the treatment solution, the coating amount, and the immersion time.
  • the central portion 101 where the covering portion 102 is formed is stored, and the intensity ratio IS / IF is adjusted so as to satisfy the above-described conditions.
  • the intensity ratio IS / IF can be adjusted to a desired value by changing the storage conditions (storage temperature, storage time, etc.).
  • the intensity ratio IN / IF can be adjusted according to the storage conditions.
  • the intensity ratio IS / IF obtained by negative ion analysis using TOF-SIMS is 0.04 or more.
  • the peak intensity IS caused by SO2 ⁇ that contributes to chemical protection of the central portion responsible for the occlusion / release of the electrode reactant and the intensity of the peak caused by LiF 2 ⁇ that affects the electrical resistance.
  • the balance with IF is optimized. Therefore, the suppression of the decomposition of the electrolytic solution is suppressed, and the electrical resistance of the active material is hardly increased, so that the battery characteristics of the secondary battery using the active material can be improved.
  • the intensity ratio IS / IF can be easily and stably set to satisfy the above-described conditions.
  • the sulfonyl compound has a chemical structure represented by any one of the formulas (1) to (4), and more specifically, the formula (1-1) and the formula (2-1). If the compound is represented by any one of formula (3-1) and formula (4-1), a higher effect can be obtained.
  • the intensity ratio IN / IF calculated by negative ion analysis using TOF-SIMS is 0.03 or more, gas generation is suppressed, so the battery characteristics of the secondary battery using the active material are further improved. Can be made.
  • the intensity ratio IN / IF can be easily and stably satisfied so as to satisfy the above-described condition.
  • the nitrogen-containing sulfonyl compound has a chemical structure represented by either formula (1) or formula (2), more specifically, formula (1-1) and formula (2- If it is a compound shown in any one of 1) etc., a higher effect can be acquired.
  • Secondary battery electrode and secondary battery (cylindrical lithium ion secondary battery)> 2 and 3 show a cross-sectional configuration of the secondary battery.
  • a part of the spirally wound electrode body 20 shown in FIG. 2 is enlarged.
  • a secondary battery electrode is applied to the positive electrode 21.
  • the secondary battery described here is a lithium secondary battery (lithium ion secondary battery) in which the capacity of the negative electrode 22 is obtained by occlusion and release of lithium (lithium ion), which is an electrode reactant, and is a so-called cylindrical type.
  • a pair of insulating plates 12 and 13 and a wound electrode body 20 are housed inside a hollow cylindrical battery can 11.
  • the wound electrode body 20 is wound, for example, after a positive electrode 21 and a negative electrode 22 are laminated via a separator 23.
  • the battery can 11 has, for example, a hollow structure in which one end is closed and the other end is opened.
  • the battery can 11 is formed of one or more of iron, aluminum, and alloys thereof. Has been. Nickel or the like may be plated on the surface of the battery can 11.
  • the pair of insulating plates 12 and 13 are disposed so as to sandwich the wound electrode body 20, and extend perpendicular to the winding peripheral surface of the wound electrode body 20.
  • the battery lid 14 is formed of the same material as the battery can 11, for example.
  • the safety valve mechanism 15 and the thermal resistance element 16 are provided inside the battery lid 14, and the safety valve mechanism 15 is electrically connected to the battery lid 14 via the thermal resistance element 16.
  • the disk plate 15 ⁇ / b> A is inverted to disconnect the electrical connection between the battery lid 14 and the wound electrode body 20. It is like that.
  • the thermal resistance element 16 prevents abnormal heat generation due to a large current, and the resistance of the thermal resistance element 16 increases as the temperature rises.
  • the gasket 17 is formed of, for example, an insulating material, and asphalt may be applied to the surface of the gasket 17.
  • a center pin 24 is inserted into the winding center of the wound electrode body 20.
  • a positive electrode lead 25 formed of a conductive material such as aluminum is connected to the positive electrode 21, and a negative electrode lead 26 formed of a conductive material such as nickel is connected to the negative electrode 22.
  • the positive electrode lead 25 is welded to the safety valve mechanism 15 and is electrically connected to the battery lid 14.
  • the negative electrode lead 26 is welded to the battery can 11 and is electrically connected to the battery can 11.
  • the positive electrode 21 which is an electrode for a secondary battery has a positive electrode active material layer 21B on one or both surfaces of the positive electrode current collector 21A.
  • the positive electrode current collector 21A is formed of any one or more of conductive materials such as aluminum, nickel, and stainless steel, for example.
  • the positive electrode active material layer 21 ⁇ / b> B includes one or more positive electrode materials capable of inserting and extracting lithium as the positive electrode active material, and the positive electrode material includes the active material for the secondary battery described above. It is out.
  • the positive electrode active material layer 21B may further include other materials such as a positive electrode binder and a positive electrode conductive agent.
  • the positive electrode binder contains, for example, any one kind or two kinds or more of synthetic rubber and polymer material.
  • synthetic rubber include styrene butadiene rubber, fluorine rubber, and ethylene propylene diene.
  • polymer material include polyvinylidene fluoride and polyimide.
  • the positive electrode conductive agent includes, for example, one or more of carbon materials.
  • the carbon material include graphite, carbon black, acetylene black, and ketjen black.
  • the positive electrode conductive agent may be a metal material, a conductive polymer, or the like as long as the material has conductivity.
  • the positive electrode active material layer 21B may further include other positive electrode materials as long as the positive electrode active material includes the above-described active material for secondary battery.
  • the other positive electrode material is, for example, any one type or two or more types (excluding those corresponding to an active material for a secondary battery) such as a lithium composite oxide and a lithium phosphate compound.
  • lithium composite oxide examples include LiCoO 2 and LiNiO 2 , and may be a lithium nickel-based composite oxide represented by the following formula (20).
  • lithium phosphate compound examples include LiFePO 4 and LiFe 1-u Mn u PO 4 (u ⁇ 1). This is because high battery capacity is obtained and excellent cycle characteristics are also obtained.
  • LiNi 1-z M z O 2 (20) (M is Co, Mn, Fe, Al, V, Sn, Mg, Ti, Sr, Ca, Zr, Mo, Tc, Ru, Ta, W, Re, Yb, Cu, Zn, Ba, B, Cr, (At least one of Si, Ga, P, Sb, and Nb. Z satisfies 0.005 ⁇ z ⁇ 0.5.)
  • the cathode material may be any one kind or two or more kinds of oxides, disulfides, chalcogenides, conductive polymers, and the like.
  • oxide include titanium oxide, vanadium oxide, and manganese dioxide.
  • disulfide include titanium disulfide and molybdenum sulfide.
  • chalcogenide is niobium selenide.
  • conductive polymer include sulfur, polyaniline, and polythiophene.
  • the positive electrode material is not limited to the series of materials described above, and may be other materials.
  • the negative electrode 22 has a negative electrode active material layer 22B on one surface or both surfaces of a negative electrode current collector 22A.
  • the negative electrode current collector 22A is formed of, for example, one or more of conductive materials such as copper, nickel, and stainless steel.
  • the surface of the negative electrode current collector 22A is preferably roughened. This is because the so-called anchor effect improves the adhesion of the negative electrode active material layer 22B to the negative electrode current collector 22A. In this case, the surface of the negative electrode current collector 22A only needs to be roughened at least in a region facing the negative electrode active material layer 22B.
  • the roughening method is, for example, a method of forming fine particles using electrolytic treatment. This electrolytic treatment is a method of forming irregularities on the surface of the negative electrode current collector 22A by forming fine particles on the surface of the negative electrode current collector 22A using an electrolysis method in an electrolytic cell.
  • a copper foil produced by an electrolytic method is generally called an electrolytic copper foil.
  • the negative electrode active material layer 22B includes one or more negative electrode materials capable of occluding and releasing lithium as a negative electrode active material, and further includes other materials such as a negative electrode binder and a negative electrode conductive agent. May be included. Details regarding the negative electrode binder and the negative electrode conductive agent are the same as, for example, the positive electrode binder and the positive electrode conductive agent. However, the chargeable capacity of the negative electrode material is preferably larger than the discharge capacity of the positive electrode 21 in order to prevent unintentional deposition of lithium metal on the negative electrode 22 during charging. That is, the electrochemical equivalent of the negative electrode material capable of occluding and releasing lithium is preferably larger than the electrochemical equivalent of the positive electrode 21.
  • the negative electrode material is, for example, any one or more of carbon materials. This is because the change in crystal structure at the time of occlusion and release of lithium is very small, so that high energy density and excellent cycle characteristics can be obtained. Moreover, it is because a carbon material functions also as a negative electrode electrically conductive agent. Examples of the carbon material include graphitizable carbon, non-graphitizable carbon, and graphite. However, the interplanar spacing of the (002) plane in non-graphitizable carbon is preferably 0.37 nm or more, and the interplanar spacing of the (002) plane in graphite is preferably 0.34 nm or less.
  • pyrolytic carbons More specifically, pyrolytic carbons, cokes, glassy carbon fibers, organic polymer compound fired bodies, activated carbon and carbon blacks.
  • the cokes include pitch coke, needle coke and petroleum coke.
  • the organic polymer compound fired body is obtained by firing (carbonizing) a polymer compound such as a phenol resin and a furan resin at an appropriate temperature.
  • the carbon material may be low crystalline carbon heat-treated at a temperature of about 1000 ° C. or less, or may be amorphous carbon.
  • the shape of the carbon material may be any of a fibrous shape, a spherical shape, a granular shape, and a scale shape.
  • the negative electrode material is, for example, a material (metal material) containing any one or two of metal elements and metalloid elements as constituent elements. This is because a high energy density can be obtained.
  • the metal-based material may be any of a simple substance, an alloy, and a compound, or two or more kinds thereof, or one having at least a part of one or two or more phases thereof.
  • the alloy includes a material including one or more metal elements and one or more metalloid elements in addition to a material composed of two or more metal elements.
  • the alloy may contain a nonmetallic element.
  • the structure includes a solid solution, a eutectic (eutectic mixture), an intermetallic compound, and two or more kinds of coexisting substances.
  • the metal element and metalloid element described above are, for example, one or more metal elements and metalloid elements capable of forming an alloy with lithium.
  • metal elements and metalloid elements capable of forming an alloy with lithium.
  • Si and Sn is preferable. This is because the ability to occlude and release lithium is excellent, so a high energy density can be obtained.
  • the material containing at least one of Si and Sn as a constituent element may be any of a simple substance, an alloy, and a compound of Si or Sn, or two or more of them, or one or two or more phases thereof. May be at least partially included.
  • the simple substance is a simple substance in a general sense (may contain a small amount of impurities), and does not necessarily mean 100% purity.
  • the alloy of Si is, for example, any one or two of Sn, Ni, Cu, Fe, Co, Mn, Zn, In, Ag, Ti, Ge, Bi, Sb and Cr as constituent elements other than Si. It contains the above elements.
  • the Si compound contains, for example, one or more of C and O as constituent elements other than Si. Note that the Si compound may include, for example, one or more of the elements described for the Si alloy as a constituent element other than Si.
  • Si alloys and compounds include SiB 4 , SiB 6 , Mg 2 Si, Ni 2 Si, TiSi 2 , MoSi 2 , CoSi 2 , NiSi 2 , CaSi 2 , CrSi 2 , Cu 5 Si, FeSi 2 , MnSi 2.
  • v in SiO v may be 0.2 ⁇ v ⁇ 1.4.
  • the alloy of Sn is, for example, any one of elements such as Si, Ni, Cu, Fe, Co, Mn, Zn, In, Ag, Ti, Ge, Bi, Sb and Cr as constituent elements other than Sn or Includes two or more.
  • the compound of Sn contains, for example, any one element or two or more elements such as C and O as a constituent element other than Sn.
  • the Sn compound may contain, for example, one or more of the elements described for the Sn alloy as a constituent element other than Sn. Examples of the alloys and compounds of Sn include SnO w (0 ⁇ w ⁇ 2), SnSiO 3 , LiSnO, and Mg 2 Sn.
  • the material containing Sn as a constituent element is preferably a material containing Sn as a first constituent element and second and third constituent elements in addition thereto, for example.
  • the second constituent elements are, for example, Co, Fe, Mg, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Ag, In, Ce, Hf, Ta, W, Bi and Any one or more of Si and the like.
  • the third constituent element is, for example, any one type or two or more types such as B, C, Al, and P. This is because high battery capacity and excellent cycle characteristics can be obtained by including the second and third constituent elements.
  • SnCoC-containing material a material containing Sn, Co, and C as constituent elements
  • SnCoC-containing material a material containing Sn, Co, and C as constituent elements
  • the C content is 9.9 mass% to 29.7 mass%
  • the ratio of Sn and Co content (Co / (Sn + Co)) is 20 mass% to 70 mass%. It is. This is because a high energy density can be obtained.
  • This SnCoC-containing material has a phase containing Sn, Co, and C, and the phase is preferably low crystalline or amorphous.
  • This phase is a phase capable of reacting with lithium (reaction phase), and excellent characteristics can be obtained by the presence of the reaction phase.
  • the half width of the diffraction peak obtained by X-ray diffraction of this phase is preferably 1 ° or more at a diffraction angle 2 ⁇ when CuK ⁇ ray is used as the specific X-ray and the drawing speed is 1 ° / min. This is because lithium is occluded and released more smoothly and the reactivity with the electrolytic solution is reduced.
  • the SnCoC-containing material may include a phase containing a simple substance or a part of each constituent element in addition to the low crystalline or amorphous phase.
  • a diffraction peak obtained by X-ray diffraction corresponds to a reaction phase capable of reacting with lithium can be easily determined by comparing X-ray diffraction charts before and after electrochemical reaction with lithium. .
  • the position of the diffraction peak changes before and after the electrochemical reaction with lithium, it corresponds to a reaction phase capable of reacting with lithium.
  • Such a reaction phase has, for example, each of the above-described constituent elements, and is considered to be low crystallization or amorphous mainly due to the presence of C.
  • the SnCoC-containing material it is preferable that at least a part of C as a constituent element is bonded to a metal element or a metalloid element as another constituent element. This is because aggregation or crystallization of Sn or the like is suppressed.
  • the bonding state of elements can be confirmed using, for example, X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • Al—K ⁇ ray or Mg—K ⁇ ray is used as the soft X-ray.
  • the C1s peak of the surface contamination carbon is set to 284.8 eV, which is used as the energy standard.
  • the waveform of the C1s peak is obtained in a form that includes the surface contamination carbon peak and the carbon peak in the SnCoC-containing material. Isolate.
  • the position of the main peak existing on the lowest bound energy side is used as the energy reference (284.8 eV).
  • the SnCoC-containing material is not limited to a material (SnCoC) whose constituent elements are composed only of Sn, Co, and C. That is, for example, in addition to Sn, Co, and C, the SnCoC-containing material is any one of Si, Fe, Ni, Cr, In, Nb, Ge, Ti, Mo, Al, P, Ga, and Bi. Alternatively, two or more types may be included as constituent elements.
  • SnCoFeC-containing material a material containing Sn, Co, Fe and C as constituent elements
  • SnCoFeC-containing material a material containing Sn, Co, Fe and C as constituent elements
  • the composition of the SnCoFeC-containing material is arbitrary.
  • the composition when the Fe content is set to be small is as follows.
  • the C content is 9.9 mass% to 29.7 mass%
  • the Fe content is 0.3 mass% to 5.9 mass%
  • the ratio of Sn and Co content (Co / (Sn + Co)) is 30% by mass to 70% by mass.
  • the composition in the case where the Fe content is set to be large is as follows.
  • the content of C is 11.9 mass% to 29.7 mass%, and the ratio of the content of Sn, Co and Fe ((Co + Fe) / (Sn + Co + Fe)) is 26.4 mass% to 48.5 mass%, Co
  • the Fe content ratio (Co / (Co + Fe)) is 9.9 mass% to 79.5 mass%. This is because a high energy density can be obtained in such a composition range.
  • the physical properties (half width, etc.) of this SnCoFeC-containing material are the same as those of the above-described SnCoC-containing material.
  • the negative electrode material may be any one kind or two or more kinds of metal oxides and polymer compounds, for example.
  • the metal oxide include iron oxide, ruthenium oxide, and molybdenum oxide.
  • the polymer compound include polyacetylene, polyaniline, and polypyrrole.
  • the negative electrode material is not limited to the series of materials described above, and may be other materials.
  • the negative electrode active material layer 22B is formed by any one method or two or more methods such as a coating method, a gas phase method, a liquid phase method, a thermal spraying method, and a firing method (sintering method).
  • the application method is, for example, a method in which a negative electrode active material in the form of particles (powder) is mixed with a negative electrode binder and then dispersed in a solvent such as an organic solvent and then applied to the negative electrode current collector 22A.
  • the vapor phase method include a physical deposition method and a chemical deposition method.
  • a vacuum deposition method for example, a vacuum deposition method, a sputtering method, an ion plating method, a laser ablation method, a thermal chemical vapor deposition, a chemical vapor deposition (CVD) method, and a plasma chemical vapor deposition method.
  • the liquid phase method include an electrolytic plating method and an electroless plating method.
  • the thermal spraying method is a method of spraying a molten or semi-molten negative electrode active material onto the negative electrode current collector 22A.
  • the firing method is, for example, a method of applying a heat treatment at a temperature higher than the melting point of the negative electrode binder or the like after being applied to the negative electrode current collector 22A using a coating method.
  • this firing method for example, an atmosphere firing method, a reaction firing method, a hot press firing method, or the like can be used.
  • the electrochemical equivalent of the negative electrode material capable of occluding and releasing lithium is equal to that of the positive electrode. It is preferably larger than the chemical equivalent.
  • the open circuit voltage that is, the battery voltage
  • lithium ions are released per unit mass even when the same positive electrode active material is used as compared with the case of 4.2 V. Since the amount increases, the amounts of the positive electrode active material and the negative electrode active material are adjusted accordingly. Thereby, a high energy density can be obtained.
  • the separator 23 separates the positive electrode 21 and the negative electrode 22, thereby allowing lithium ions to pass through while preventing a short circuit of current caused by contact between the two electrodes.
  • the separator 23 is, for example, a porous film such as a synthetic resin and ceramic, and may be a laminated film in which two or more kinds of porous films are laminated.
  • the synthetic resin include polytetrafluoroethylene, polypropylene, and polyethylene.
  • the separator 23 may have, for example, a polymer compound layer on one side or both sides of the above-described porous film (base material layer). This is because the adhesion of the separator 23 to the positive electrode 21 and the negative electrode 22 is improved, so that the distortion of the wound electrode body 20 is suppressed. As a result, the decomposition reaction of the electrolytic solution is suppressed, and the leakage of the electrolytic solution impregnated in the base material layer is also suppressed. Therefore, the resistance is not easily increased even if charging and discharging are repeated, and the battery swelling is also suppressed. Is done.
  • the polymer compound layer includes, for example, a polymer material such as polyvinylidene fluoride. This is because it has excellent physical strength and is electrochemically stable.
  • the polymer material may be a polymer material other than polyvinylidene fluoride.
  • the separator 23 is impregnated with an electrolytic solution that is a liquid electrolyte.
  • This electrolytic solution contains a solvent and an electrolyte salt, and may further contain other materials such as additives.
  • the solvent includes one or more of non-aqueous solvents such as organic solvents.
  • non-aqueous solvent include a cyclic carbonate ester, a chain carbonate ester, a lactone, a chain carboxylate ester, and a nitrile. This is because excellent battery capacity, cycle characteristics, storage characteristics, and the like can be obtained.
  • the cyclic carbonate include ethylene carbonate, propylene carbonate, and butylene carbonate
  • examples of the chain carbonate include dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and methyl propyl carbonate.
  • lactone include ⁇ -butyrolactone and ⁇ -valerolactone.
  • carboxylic acid ester examples include methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl trimethyl acetate, and ethyl trimethyl acetate.
  • Nitriles include, for example, acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropionitrile and the like.
  • non-aqueous solvents include, for example, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,3-dioxane, 1 , 4-dioxane, N, N-dimethylformamide, N-methylpyrrolidinone, N-methyloxazolidinone, N, N′-dimethylimidazolidinone, nitromethane, nitroethane, sulfolane, trimethyl phosphate and dimethyl sulfoxide. This is because similar advantages can be obtained.
  • ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate are preferred. This is because better battery capacity, cycle characteristics, storage characteristics, and the like can be obtained.
  • high viscosity (high dielectric constant) solvents such as ethylene carbonate and propylene carbonate (for example, dielectric constant ⁇ ⁇ 30) and low viscosity solvents such as dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate (for example, viscosity ⁇ 1 mPas).
  • -A combination with s is more preferred. This is because the dissociation property of the electrolyte salt and the ion mobility are improved.
  • the solvent may contain one kind or two or more kinds of unsaturated cyclic carbonate, halogenated carbonate, sultone (cyclic sulfonate) and acid anhydride.
  • unsaturated cyclic carbonate is a cyclic carbonate having one or more unsaturated bonds (carbon-carbon double bonds), and examples thereof include vinylene carbonate, vinyl ethylene carbonate, and methylene ethylene carbonate.
  • halogenated carbonate is a cyclic or chain carbonate containing one or more halogens as a constituent element.
  • Examples of cyclic halogenated carbonates include 4-fluoro-1,3-dioxolan-2-one and 4,5-difluoro-1,3-dioxolan-2-one.
  • Examples of the chain halogenated carbonate include fluoromethyl methyl carbonate, bis (fluoromethyl) carbonate, and difluoromethyl methyl carbonate.
  • Examples of sultone include propane sultone and propene sultone.
  • Examples of the acid anhydride include succinic anhydride, ethanedisulfonic anhydride, and anhydrous sulfobenzoic acid.
  • the solvent is not limited to the series of materials described above, and other materials may be used.
  • the electrolyte salt includes, for example, one or more of salts such as lithium salt.
  • the electrolyte salt may contain a salt other than the lithium salt, for example.
  • This other salt is, for example, a light metal salt other than a lithium salt.
  • lithium salt examples include lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium perchlorate (LiClO 4 ), lithium hexafluoroarsenate (LiAsF 6 ), and tetraphenyl.
  • Lithium borate LiB (C 6 H 5 ) 4
  • lithium methanesulfonate LiCH 3 SO 3
  • lithium trifluoromethanesulfonate LiCF 3 SO 3
  • lithium tetrachloroaluminate LiAlCl 4
  • hexafluoride examples include dilithium silicate (Li 2 SiF 6 ), lithium chloride (LiCl), and lithium bromide (LiBr). This is because excellent battery capacity, cycle characteristics, storage characteristics, and the like can be obtained.
  • LiPF 6 LiBF 4 , LiClO 4 and LiAsF 6 is preferable, and LiPF 6 is more preferable. This is because a higher effect can be obtained because the internal resistance is lowered.
  • the electrolyte salt is not limited to the series of compounds described above, and may be other compounds.
  • the content of the electrolyte salt is not particularly limited, but is preferably 0.3 mol / kg to 3.0 mol / kg with respect to the solvent. This is because high ionic conductivity is obtained.
  • This secondary battery operates as follows, for example. At the time of charging, lithium ions released from the positive electrode 21 are occluded in the negative electrode 22 through the electrolytic solution. On the other hand, at the time of discharge, lithium ions released from the negative electrode 22 are occluded in the positive electrode 21 through the electrolytic solution.
  • the charging voltage (positive electrode potential: standard lithium metal potential) to a high voltage.
  • the upper limit value of the charging voltage is preferably 4.2 or more, and more preferably 4.4 V or more. This is because a sufficient amount of lithium is released from the positive electrode active material during charging.
  • the charging voltage is not extremely high.
  • the charging voltage is preferably 4.8 V or less, and more preferably 4.6 V or less. preferable.
  • the positive electrode active material contains the above-described active material for a secondary battery
  • the positive electrode active material is stable with respect to the high electromotive force of the positive electrode, and thus the reaction between the positive electrode 21 and the electrolyte is suppressed. Is done. This suppresses the decomposition reaction of the electrolytic solution and makes it difficult to form a film such as LIF having low lithium ion permeability. Therefore, when the secondary battery is charged to a high voltage of 4.2 V or higher, the capacity is increased as the charging voltage increases, and battery characteristics such as cycle characteristics are secured.
  • the discharge voltage (positive electrode potential: standard lithium metal potential) to a low voltage.
  • the lower limit value of the discharge voltage to 3.3 V or less. This is because a sufficient amount of lithium is occluded in the positive electrode active material during discharge.
  • the discharge voltage is not extremely low, and specifically, it is preferably 2.0 V or more.
  • This secondary battery is manufactured by the following procedure, for example.
  • the positive electrode 21 is manufactured.
  • a positive electrode active material including the secondary battery active material described above
  • a positive electrode binder including the secondary battery active material described above
  • a positive electrode conductive agent including the positive electrode conductive agent, and the like
  • the positive electrode mixture is dispersed in an organic solvent or the like to obtain a paste-like positive electrode mixture slurry.
  • the positive electrode mixture slurry is applied to both surfaces of the positive electrode current collector 21A and then dried to form the positive electrode active material layer 21B.
  • the positive electrode active material layer 21B is compression molded using a roll press machine or the like. In this case, compression molding may be performed while heating, or compression molding may be repeated a plurality of times.
  • the negative electrode 22 is produced by the same procedure as that of the positive electrode 21 described above.
  • a negative electrode mixture in which a negative electrode active material, a negative electrode binder, a negative electrode conductive agent, and the like are mixed is dispersed in an organic solvent or the like to obtain a paste-like negative electrode mixture slurry.
  • the negative electrode mixture slurry is applied to both surfaces of the negative electrode current collector 22A and then dried to form the negative electrode active material layer 22B, and then the negative electrode active material layer 22B is compression molded.
  • a secondary battery is assembled using the positive electrode 21 and the negative electrode 22.
  • the positive electrode lead 25 is attached to the positive electrode current collector 21A using a welding method or the like
  • the negative electrode lead 26 is attached to the negative electrode current collector 22A using a welding method or the like.
  • the center pin 24 is inserted into the winding center.
  • the wound electrode body 20 is accommodated in the battery can 11 while being sandwiched between the pair of insulating plates 12 and 13.
  • the tip of the positive electrode lead 25 is attached to the safety valve mechanism 15 using a welding method or the like, and the tip of the negative electrode lead 26 is attached to the battery can 11 using a welding method or the like.
  • an electrolytic solution in which an electrolyte salt is dispersed in a solvent is injected into the battery can 11 and impregnated in the separator 23.
  • the battery lid 14, the safety valve mechanism 15, and the heat sensitive resistance element 16 are caulked to the opening end portion of the battery can 11 through the gasket 17.
  • the positive electrode active material layer 21B of the positive electrode 21 includes the above-described secondary battery active material as the positive electrode active material. Therefore, as described above, the decomposition of the electrolytic solution is suppressed, and the electrical resistance of the positive electrode 21 is reduced, so that excellent battery characteristics can be obtained. Other operations and effects are the same as those of the active material for the secondary battery.
  • FIG. 4 shows an exploded perspective configuration of another secondary battery
  • FIG. 5 is an enlarged cross section taken along line VV of the spirally wound electrode body 30 shown in FIG.
  • FIG. 4 shows a state where the wound electrode body 30 and the two exterior members 40 are separated from each other.
  • the components of the cylindrical secondary battery already described will be referred to as needed.
  • the secondary battery described here is a so-called laminate film type lithium ion secondary battery.
  • the wound electrode body 30 is housed inside a film-shaped exterior member 40. Yes.
  • the wound electrode body 30 is wound after the positive electrode 33 and the negative electrode 34 are stacked via the separator 35 and the electrolyte layer 36.
  • a positive electrode lead 31 is attached to the positive electrode 33, and a negative electrode lead 32 is attached to the negative electrode 34.
  • the outermost peripheral part of the wound electrode body 30 is protected by a protective tape 37.
  • the positive electrode lead 31 and the negative electrode lead 32 are led out in the same direction from the inside of the exterior member 40 to the outside, for example.
  • the positive electrode lead 31 is formed of a conductive material such as aluminum
  • the negative electrode lead 32 is formed of a conductive material such as copper, nickel, or stainless steel. These conductive materials have, for example, a thin plate shape or a mesh shape.
  • the exterior member 40 is, for example, a laminate film in which a fusion layer, a metal layer, and a surface protective layer are laminated in this order.
  • the exterior member 40 is obtained by, for example, laminating two laminated films so that the fusion layer faces the spirally wound electrode body 30 and then fusing the outer peripheral edges of the fusion layers. .
  • the two laminated films may be bonded together with an adhesive or the like.
  • the fusion layer is, for example, a film made of polyethylene or polypropylene.
  • the metal layer is, for example, an aluminum foil.
  • the surface protective layer is, for example, a film such as nylon and polyethylene terephthalate.
  • the exterior member 40 is an aluminum laminate film in which a polyethylene film, an aluminum foil, and a nylon film are laminated in this order.
  • the exterior member 40 may be a laminate film having another laminated structure, a polymer film such as polypropylene, or a metal film.
  • an adhesion film 41 is inserted between the exterior member 40 and the positive electrode lead 31 and the negative electrode lead 32 between the exterior member 40 and the positive electrode lead 31 and the negative electrode lead 32, for example, an adhesion film 41 is inserted to prevent intrusion of outside air.
  • the adhesion film 41 is formed of a material having adhesion to the positive electrode lead 31 and the negative electrode lead 32.
  • the adhesive material is, for example, a polyolefin resin, and more specifically, polyethylene, polypropylene, modified polyethylene, modified polypropylene, and the like.
  • the positive electrode 33 has, for example, a positive electrode active material layer 33B on both surfaces of the positive electrode current collector 33A
  • the negative electrode 34 has, for example, a negative electrode active material layer 34B on both surfaces of the negative electrode current collector 34A.
  • the configurations of the positive electrode current collector 33A, the positive electrode active material layer 33B, the negative electrode current collector 34A, and the negative electrode active material layer 34B are respectively the positive electrode current collector 21A, the positive electrode active material layer 21B, the negative electrode current collector 22A, and the negative electrode active material layer.
  • the configuration is the same as 22B. That is, the positive electrode active material layer 33 ⁇ / b> B of the positive electrode 33 that is a secondary battery electrode contains the above-described secondary battery active material as the positive electrode active material.
  • the configuration of the separator 35 is the same as the configuration of the separator 23.
  • the electrolyte layer 36 is a so-called gel electrolyte in which an electrolytic solution is held by a polymer compound. This is because high ionic conductivity (for example, 1 mS / cm or more at room temperature) is obtained and leakage of the electrolytic solution is prevented.
  • the electrolyte layer 36 may further contain other materials such as additives.
  • the polymer compound includes one kind or two or more kinds of polymer materials.
  • This polymer material is, for example, polyacrylonitrile, polyvinylidene fluoride, polytetrafluoroethylene, polyhexafluoropropylene, polyethylene oxide, polypropylene oxide, polyphosphazene, polysiloxane, polyvinyl fluoride, polyvinyl acetate, polyvinyl alcohol, poly Examples thereof include methyl methacrylate, polyacrylic acid, polymethacrylic acid, styrene-butadiene rubber, nitrile-butadiene rubber, polystyrene and polycarbonate.
  • the polymer material may be a copolymer.
  • This copolymer is, for example, a copolymer of vinylidene fluoride and hexafluoropyrene.
  • polyvinylidene fluoride and a copolymer of vinylidene fluoride and hexafluoropyrene are preferable, and polyvinylidene fluoride is more preferable. This is because it is electrochemically stable.
  • the composition of the electrolytic solution is the same as that of the cylindrical type, for example.
  • the solvent of the electrolytic solution in the electrolyte layer 36 which is a gel electrolyte is a wide concept including not only a liquid solvent but also a material having ion conductivity capable of dissociating the electrolyte salt. Therefore, when using a polymer compound having ion conductivity, the polymer compound is also included in the solvent.
  • the separator 35 is impregnated with the electrolytic solution.
  • This secondary battery operates as follows, for example. During charging, lithium ions released from the positive electrode 33 are occluded in the negative electrode 34 through the electrolyte layer 36. On the other hand, at the time of discharging, lithium ions released from the negative electrode 34 are occluded in the positive electrode 33 through the electrolyte layer 36.
  • the charge / discharge conditions (upper limit value of charge voltage and lower limit value of discharge voltage) in this case are the same as in the case of the cylindrical type.
  • the secondary battery provided with the gel electrolyte layer 36 is manufactured, for example, by the following three types of procedures.
  • the positive electrode 33 and the negative electrode 34 are manufactured by the same manufacturing procedure as that of the positive electrode 21 and the negative electrode 22.
  • the positive electrode active material layer 33B is formed on both surfaces of the positive electrode current collector 33A to produce the positive electrode 33
  • the negative electrode active material layer 34B is formed on both surfaces of the negative electrode current collector 34A to produce the negative electrode 34.
  • the precursor solution is applied to the positive electrode 33 and the negative electrode 34 to form a gel electrolyte layer 36.
  • the positive electrode lead 31 is attached to the positive electrode current collector 33A using a welding method or the like
  • the negative electrode lead 32 is attached to the negative electrode current collector 34A using a welding method or the like.
  • a protective tape 37 is attached to the outermost periphery.
  • the outer peripheral edge portions of the exterior members 40 are bonded to each other using a heat fusion method or the like.
  • the spirally wound electrode body 30 is sealed inside. In this case, the adhesion film 41 is inserted between the positive electrode lead 31 and the negative electrode lead 32 and the exterior member 40.
  • the positive electrode lead 31 is attached to the positive electrode 33 and the negative electrode lead 52 is attached to the negative electrode 34.
  • the positive electrode 33 and the negative electrode 34 are stacked via the separator 35 and wound to produce a wound body that is a precursor of the wound electrode body 30, and then a protective tape 37 is provided on the outermost peripheral portion thereof.
  • a protective tape 37 is provided on the outermost peripheral portion thereof.
  • the wound body is arranged between the two film-like exterior members 40, the remaining outer peripheral edge portion excluding the outer peripheral edge portion on one side is bonded by using a heat sealing method or the like, and the bag The wound body is housed inside the shaped exterior member 40.
  • an electrolytic solution is prepared by mixing an electrolyte, a monomer that is a raw material of the polymer compound, a polymerization initiator, and another material such as a polymerization inhibitor.
  • the electrolyte composition is injected into the bag-shaped exterior member 40, the exterior member 40 is sealed using a heat fusion method or the like.
  • the monomer is thermally polymerized to form a polymer compound.
  • the polymer compound is impregnated with the electrolytic solution, and the polymer compound gels, so that the electrolyte layer 36 is formed.
  • a wound body is produced and stored in the bag-shaped exterior member 40 in the same manner as in the second procedure described above, except that the separator 35 coated with the polymer compound on both sides is used.
  • the polymer compound applied to the separator 35 is, for example, a polymer (a homopolymer, a copolymer, and a multi-component copolymer) containing vinylidene fluoride as a component.
  • the homopolymer is, for example, polyvinylidene fluoride.
  • the copolymer is, for example, a binary copolymer containing vinylidene fluoride and hexafluoropropylene as components.
  • the multi-component copolymer is, for example, a ternary copolymer containing vinylidene fluoride, hexafluoropropylene, and chlorotrifluoroethylene as components.
  • one or more other polymer compounds may be used.
  • the electrolytic solution is prepared and injected into the exterior member 40
  • the opening of the exterior member 40 is sealed using a thermal fusion method or the like.
  • the exterior member 40 is heated while applying a load, and the separator 35 is brought into close contact with the positive electrode 33 and the negative electrode 34 through the polymer compound.
  • the polymer compound is impregnated with the electrolytic solution, and the polymer compound gels, so that the electrolyte layer 36 is formed.
  • the positive electrode active material layer 33B of the positive electrode 33 contains the above-described secondary battery active material as the positive electrode active material, and therefore, excellent for the same reason as in the case of the cylindrical type. Battery characteristics can be obtained. Other operations and effects are the same as in the case of the cylindrical type.
  • the secondary battery described here is a lithium secondary battery (lithium metal secondary battery) in which the capacity of the negative electrode 22 is obtained by precipitation and dissolution of lithium metal.
  • This secondary battery has the same configuration as the above-described cylindrical lithium ion secondary battery except that the negative electrode active material layer 22B is made of lithium metal, and is manufactured by the same procedure.
  • the negative electrode active material layer 22B may already exist from the time of assembly, but does not exist at the time of assembly, and may be composed of lithium metal deposited at the time of charging. Further, the negative electrode current collector 22A may be omitted by using the negative electrode active material layer 22B as a current collector.
  • This secondary battery operates as follows, for example. At the time of charging, lithium ions are released from the positive electrode 21 and deposited as lithium metal on the surface of the negative electrode current collector 22A through the electrolytic solution. On the other hand, at the time of discharge, lithium metal elutes as lithium ions from the negative electrode active material layer 22B and is occluded by the positive electrode 21 through the electrolytic solution.
  • the charge / discharge conditions (upper limit value of charge voltage and lower limit value of discharge voltage) in this case are the same as in the case of the cylindrical type.
  • the positive electrode active material layer 21B of the positive electrode 21 contains the above-described secondary battery active material as the positive electrode active material. Therefore, the lithium metal secondary battery is excellent for the same reason as the lithium ion secondary battery. Battery characteristics can be obtained. Other operations and effects are the same as those of the lithium ion secondary battery.
  • the secondary battery described here is not limited to the cylindrical type, and may be applied to a laminate film type.
  • Secondary batteries can be used in machines, equipment, instruments, devices and systems (aggregates of multiple equipment) that can be used as a power source for driving or a power storage source for power storage. If there is, it will not be specifically limited.
  • the secondary battery used as a power source may be a main power source (a power source used preferentially) or an auxiliary power source (a power source used in place of the main power source or switched from the main power source).
  • the type of the main power source is not limited to the secondary battery.
  • the usage of the secondary battery is, for example, as follows.
  • Electronic devices including portable electronic devices
  • portable electronic devices such as video cameras, digital still cameras, mobile phones, notebook computers, cordless phones, headphone stereos, portable radios, portable televisions, and portable information terminals.
  • It is a portable living device such as an electric shaver.
  • Storage devices such as backup power supplies and memory cards.
  • Electric tools such as electric drills and electric saws.
  • It is a battery pack used in a notebook computer or the like as a detachable power source.
  • Medical electronic devices such as pacemakers and hearing aids.
  • An electric vehicle such as an electric vehicle (including a hybrid vehicle).
  • It is an electric power storage system such as a home battery system that stores electric power in case of an emergency. Of course, applications other than those described above may be used.
  • the battery pack is a power source using a secondary battery, and is a so-called assembled battery.
  • An electric vehicle is a vehicle that operates (runs) using a secondary battery as a driving power source, and may be an automobile (such as a hybrid automobile) that includes a drive source other than the secondary battery as described above.
  • the power storage system is a system that uses a secondary battery as a power storage source.
  • a secondary battery which is a power storage source
  • An electric power tool is a tool in which a movable part (for example, a drill etc.) moves, using a secondary battery as a driving power source.
  • An electronic device is a device that exhibits various functions using a secondary battery as a driving power source (power supply source).
  • FIG. 6 shows a block configuration of the battery pack.
  • This battery pack includes, for example, a control unit 61, a power source 62, a switch unit 63, a current measurement unit 64, a temperature detection unit 65, and a voltage detection unit inside a housing 60 formed of a plastic material or the like.
  • 66 a switch control unit 67, a memory 68, a temperature detection element 69, a current detection resistor 70, a positive terminal 71 and a negative terminal 72.
  • the control unit 61 controls the operation of the entire battery pack (including the usage state of the power supply 62), and includes, for example, a central processing unit (CPU).
  • the power source 62 includes one or more secondary batteries (not shown).
  • the power source 62 is, for example, an assembled battery including two or more secondary batteries, and the connection form of these secondary batteries may be in series, in parallel, or a mixture of both.
  • the power source 62 includes six secondary batteries connected in two parallel three series.
  • the switch unit 63 switches the usage state of the power source 62 (whether or not the power source 62 can be connected to an external device) according to an instruction from the control unit 61.
  • the switch unit 63 includes, for example, a charge control switch, a discharge control switch, a charging diode, a discharging diode (all not shown), and the like.
  • the charge control switch and the discharge control switch are semiconductor switches such as a field effect transistor (MOSFET) using a metal oxide semiconductor, for example.
  • the current measurement unit 64 measures current using the current detection resistor 70 and outputs the measurement result to the control unit 61.
  • the temperature detection unit 65 measures the temperature using the temperature detection element 69 and outputs the measurement result to the control unit 61. This temperature measurement result is used, for example, when the control unit 61 performs charge / discharge control during abnormal heat generation, or when the control unit 61 performs correction processing when calculating the remaining capacity.
  • the voltage detection unit 66 measures the voltage of the secondary battery in the power supply 62, converts the measured voltage from analog to digital, and supplies the converted voltage to the control unit 61.
  • the switch control unit 67 controls the operation of the switch unit 63 in accordance with signals input from the current measurement unit 64 and the voltage detection unit 66.
  • the switch control unit 67 disconnects the switch unit 63 (charge control switch) and controls the charging current not to flow through the current path of the power source 62. .
  • the power source 62 can only discharge through the discharging diode.
  • the switch control unit 67 is configured to cut off the charging current when a large current flows during charging, for example.
  • the switch control unit 67 disconnects the switch unit 63 (discharge control switch) so that the discharge current does not flow in the current path of the power source 62 when the battery voltage reaches the overdischarge detection voltage, for example. .
  • the power source 62 can only be charged via the charging diode.
  • the switch control unit 67 is configured to cut off the discharge current when a large current flows during discharging.
  • the overcharge detection voltage is 4.2V ⁇ 0.05V, and the overdischarge detection voltage is 2.4V ⁇ 0.1V.
  • the memory 68 is, for example, an EEPROM which is a nonvolatile memory.
  • the memory 68 stores, for example, numerical values calculated by the control unit 61 and information (for example, internal resistance in the initial state) of the secondary battery measured in the manufacturing process stage. If the full charge capacity of the secondary battery is stored in the memory 68, the control unit 61 can grasp information such as the remaining capacity.
  • the temperature detection element 69 measures the temperature of the power supply 62 and outputs the measurement result to the control unit 61, and is, for example, a thermistor.
  • the positive electrode terminal 71 and the negative electrode terminal 72 are connected to an external device (for example, a notebook personal computer) operated using a battery pack, an external device (for example, a charger) used to charge the battery pack, or the like. Terminal. Charging / discharging of the power source 62 is performed via the positive terminal 71 and the negative terminal 72.
  • an external device for example, a notebook personal computer
  • an external device for example, a charger
  • FIG. 7 shows a block configuration of a hybrid vehicle which is an example of an electric vehicle.
  • This electric vehicle includes, for example, a control unit 74, an engine 75, a power source 76, a driving motor 77, a differential device 78, a generator 79, and a transmission 80 inside a metal casing 73. And a clutch 81, inverters 82 and 83, and various sensors 84.
  • the electric vehicle includes, for example, a front wheel drive shaft 85 and a front wheel 86 connected to the differential device 78 and the transmission 80, and a rear wheel drive shaft 87 and a rear wheel 88.
  • This electric vehicle can run using, for example, either the engine 75 or the motor 77 as a drive source.
  • the engine 75 is a main power source, such as a gasoline engine.
  • the driving force (rotational force) of the engine 75 is transmitted to the front wheels 86 or the rear wheels 88 via, for example, a differential device 78, a transmission 80, and a clutch 81 which are driving units.
  • the rotational force of the engine 75 is also transmitted to the generator 79, and the generator 79 generates AC power using the rotational force.
  • the AC power is converted into DC power via the inverter 83, and the power source 76.
  • the motor 77 which is the conversion unit when used as a power source, the power (DC power) supplied from the power source 76 is converted into AC power via the inverter 82, and the motor 77 is driven using the AC power. .
  • the driving force (rotational force) converted from electric power by the motor 77 is transmitted to the front wheels 86 or the rear wheels 88 via, for example, a differential device 78, a transmission 80, and a clutch 81, which are driving units.
  • the resistance force at the time of deceleration is transmitted as a rotational force to the motor 77, and the motor 77 generates AC power using the rotational force. Good.
  • This AC power is preferably converted into DC power via the inverter 82, and the DC regenerative power is preferably stored in the power source 76.
  • the control unit 74 controls the operation of the entire electric vehicle and includes, for example, a CPU.
  • the power source 76 includes one or more secondary batteries (not shown).
  • the power source 76 may be connected to an external power source and can store power by receiving power supply from the external power source.
  • the various sensors 84 are used, for example, to control the rotational speed of the engine 75 and to control the opening (throttle opening) of a throttle valve (not shown).
  • the various sensors 84 include, for example, a speed sensor, an acceleration sensor, an engine speed sensor, and the like.
  • the electric vehicle may be a vehicle (electric vehicle) that operates using only the power source 76 and the motor 77 without using the engine 75.
  • FIG. 8 shows a block configuration of the power storage system.
  • This power storage system includes, for example, a control unit 90, a power source 91, a smart meter 92, and a power hub 93 in a house 89 such as a general house and a commercial building.
  • the power source 91 is connected to, for example, an electric device 94 installed inside the house 89 and can be connected to an electric vehicle 96 stopped outside the house 89.
  • the power source 91 is connected to, for example, a private generator 95 installed in a house 89 via a power hub 93 and can be connected to an external centralized power system 97 via the smart meter 92 and the power hub 93. It has become.
  • the electric device 94 includes, for example, one or more home appliances, and the home appliances are, for example, a refrigerator, an air conditioner, a television, and a water heater.
  • the private power generator 95 is, for example, any one type or two or more types such as a solar power generator and a wind power generator.
  • the electric vehicle 96 is, for example, one type or two or more types such as an electric vehicle, an electric motorcycle, and a hybrid vehicle.
  • the centralized electric power system 97 is, for example, one type or two or more types such as a thermal power plant, a nuclear power plant, a hydroelectric power plant, and a wind power plant.
  • the control unit 90 controls the operation of the entire power storage system (including the usage state of the power supply 91), and includes, for example, a CPU.
  • the power source 91 includes one or more secondary batteries (not shown).
  • the smart meter 92 is, for example, a network-compatible power meter installed in a power consumer's house 89 and can communicate with the power supplier. Accordingly, for example, the smart meter 92 enables efficient and stable energy supply by controlling the balance between supply and demand in the house 89 while communicating with the outside.
  • the power storage system for example, power is accumulated in the power source 91 from the centralized power system 97 that is an external power source via the smart meter 92 and the power hub 93, and the power hub 93 is connected from the solar power generator 95 that is an independent power source. Power is accumulated in the power source 91 via Since the electric power stored in the power source 91 is supplied to the electric device 94 and the electric vehicle 96 in accordance with an instruction from the control unit 90, the electric device 94 can be operated and the electric vehicle 96 can be charged. .
  • the power storage system is a system that makes it possible to store and supply power in the house 89 using the power source 91.
  • the power stored in the power supply 91 can be used arbitrarily. For this reason, for example, power is stored in the power source 91 from the centralized power system 97 at midnight when the amount of electricity used is low, and the power stored in the power source 91 is used during the day when the amount of electricity used is high. it can.
  • the power storage system described above may be installed for each house (one household), or may be installed for each of a plurality of houses (multiple households).
  • FIG. 9 shows a block configuration of the electric power tool.
  • This electric tool is, for example, an electric drill, and includes a control unit 99 and a power supply 100 inside a tool main body 98 formed of a plastic material or the like.
  • a drill portion 101 which is a movable portion is attached to the tool body 98 so as to be operable (rotatable).
  • the control unit 99 controls the operation of the entire power tool (including the usage state of the power supply 100), and includes, for example, a CPU.
  • the power supply 100 includes one or more secondary batteries (not shown).
  • the control unit 99 supplies power from the power supply 100 to the drill unit 101 in response to an operation switch (not shown).
  • the positive electrode 33 was produced.
  • the central portion 101 A lithium composite oxide powder having an average composition represented by LiCo 0.98 Al 0.01 Mg 0.01 O 2 (LiCAMO) was prepared.
  • the average particle diameter of the central portion 101 measured by the laser scattering method was about 13 ⁇ m.
  • coated part 102 shown in Table 1 and Table 2 was prepared.
  • the solvent of this treatment solution was 4-chlorophenol and the concentration was 1% by weight.
  • the central portion 101 was immersed in the treatment solution for several seconds, the treatment solution was stirred.
  • the central portion 101 was taken out of the treatment solution, and the central portion 101 was dried in a reduced pressure environment at 60 ° C. Thereby, since the coating
  • the central portion 101 was used as it was without forming the covering portion 102 for comparison. Further, instead of forming the covering portion 102, a sulfonyl compound was contained in the electrolytic solution. In this case, the content of the sulfonyl compound in the electrolytic solution was equivalent to 10% by weight of the weight of the electrolyte salt.
  • the positive electrode active material 98 parts by mass of the positive electrode active material, 1.2 parts by mass of the positive electrode binder (polyvinylidene fluoride), and 0.8 parts by mass of the positive electrode conductive agent (Ketjen Black, which is amorphous carbon powder) are mixed.
  • a positive electrode mixture was obtained.
  • the positive electrode mixture was dispersed in an organic solvent (N-methyl-2-pyrrolidone) to obtain a positive electrode mixture slurry.
  • the positive electrode mixture slurry was uniformly applied to both surfaces of the belt-like positive electrode current collector 33A (20 ⁇ m thick aluminum foil) and then dried with warm air to form the positive electrode active material layer 33B.
  • the positive electrode active material layer 33B was compression molded using a roll press.
  • the negative electrode 34 was produced.
  • the negative electrode active material layer 34B was formed by depositing a negative electrode active material (carbon) on both surfaces of the strip-shaped negative electrode current collector 34A (10 ⁇ m thick electrolytic copper foil) using an electron beam evaporation method. .
  • the thickness of the negative electrode active material layer 34B on one side of the negative electrode current collector 34A was 5 ⁇ m.
  • the charge capacity of the negative electrode active material was made larger than the charge capacity of the positive electrode.
  • an electrolyte salt LiPF 6
  • a solvent ethylene carbonate and diethyl carbonate
  • the concentration of the electrolyte salt in the electrolytic solution was 1 mol / kg.
  • the positive electrode lead 31 made of aluminum was welded to the positive electrode current collector 33A of the positive electrode 33, and the negative electrode lead 32 made of nickel was welded to the negative electrode current collector 34A of the negative electrode 34.
  • the positive electrode 33 and the negative electrode 34 are laminated via the separator 35 (25 ⁇ m-thick microporous polypropylene film) and then wound in the longitudinal direction to produce the wound electrode body 30, and then the wound electrode A protective tape 37 was attached to the outermost periphery of the body 30.
  • the exterior member 40 is a moisture-resistant aluminum laminate film (total thickness 100 ⁇ m) in which a nylon film (30 ⁇ m thickness), an aluminum foil (40 ⁇ m thickness), and a polypropylene film (30 ⁇ m thickness) are laminated from the outside.
  • the charged secondary battery was stored under the storage conditions shown in Tables 1 and 2.
  • the battery was charged at a current density of 1 mA / cm 2 until the battery voltage reached the charging voltage (V) shown in Tables 1 and 2.
  • intensity ratio IS / IF and IN / IF were changed by changing storage conditions (storage temperature and storage time).
  • discharge capacity retention ratio (%) (discharge capacity at the 100th cycle / discharge capacity at the second cycle) ⁇ 100 was calculated.
  • V charging voltage
  • the procedure for preparing a sample for analysis in order to perform negative ion analysis using the TOF-SIMS apparatus is as follows.
  • the secondary battery was disassembled inside the argon glove box.
  • a charged secondary battery was put into an argon glove box, and then the secondary battery was disassembled and the positive electrode 33 was taken out.
  • the positive electrode 33 was cut using a ceramic scissor so that a sample of about 1 cm square was obtained.
  • the sample was immersed in dimethyl carbonate for about 30 seconds, and the sample was washed.
  • the sample was transported inside the TOF-SIMS device in an argon atmosphere, and the inside of the device was evacuated overnight. As a result, unnecessary dimethyl carbonate volatilized, and a sample for analysis was obtained.
  • the intensity ratio IS / IF is 0.04 or more
  • the discharge capacity retention ratio and the high output discharge capacity are remarkably increased and the swelling ratio is remarkably reduced as compared with the case where the intensity ratio IS / IF is less than 0.04.
  • the intensity ratio IS / IF was 0.04 or more, a high discharge capacity retention ratio and a high output discharge capacity were obtained even when the charge voltage was increased.
  • the discharge capacity retention rate is higher than that when it is less than 0.03.
  • the swelling rate decreased while maintaining a high output discharge capacity.
  • the above results show that the sulfonyl compound is preferable for improving the discharge capacity retention rate and the high output discharge capacity for the forming material of the covering portion 102, but the nitrogen-containing sulfonyl compound is preferable for improving the swelling rate. It is more preferable.
  • the active material capable of occluding and releasing the electrode reactive material has an intensity ratio IS / IF of 0.04 or more determined by negative ion analysis of the active material using TOF-SIMS. Excellent battery characteristics were obtained.
  • the active material for secondary battery and the electrode for secondary battery of the present technology may be applied to an electrochemical device other than the secondary battery.
  • An electrochemical device other than the secondary battery is, for example, a capacitor.
  • the appropriate range derived from the results of the examples is described.
  • the explanation does not completely deny the possibility that the intensity ratio IS / IF is outside the above range. That is, the appropriate range described above is a particularly preferable range for obtaining the effects of the present technology to the last, so that the intensity ratio IS / IF may slightly deviate from the above ranges as long as the effects of the present technology are obtained. .
  • This technique can also take the following structures.
  • An electrolyte is provided together with the positive electrode and the negative electrode,
  • the positive electrode includes an active material capable of occluding and releasing an electrode reactant,
  • the ratio IS / IF between the peak intensity IS caused by SO 2 ⁇ and the peak intensity IF caused by LiF 2 ⁇ obtained by negative ion analysis of the active material using time-of-flight secondary ion mass spectrometry is 0.04 or more.
  • Secondary battery (2)
  • the active material includes a central portion capable of occluding and releasing the electrode reactive material, and a covering portion provided in the central portion,
  • the covering portion includes a compound having a sulfonyl group (> SO 2 ).
  • the secondary battery as described in said (1).
  • the compound having a sulfonyl group includes at least one member selected from the group consisting of compounds represented by the following formulas (1) to (4).
  • R1 to R4 are each a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, or a group in which two or more of them are bonded.
  • R1 to R4 may be bonded to each other.
  • R5 and R6 are each a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, or a group in which two or more of them are bonded.
  • R5 and R6 may be bonded to each other, and M is a metal element.
  • R7 to R12 are each a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, or a group in which two or more of them are bonded.
  • R7 to R12 may be bonded to each other.
  • R13 to R16 are each a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, or a group in which two or more of them are bonded.
  • the compound represented by the formula (1) includes at least one selected from the group consisting of compounds represented by the following formulas (1-1) to (1-13),
  • the compound represented by the formula (2) includes at least one selected from the group consisting of compounds represented by the following formulas (2-1) to (2-11),
  • the compound represented by the formula (3) includes at least one selected from the group consisting of compounds represented by the following formulas (3-1) to (3-11),
  • the compound represented by the formula (4) includes at least one selected from the group consisting of compounds represented by the following formulas (4-1) to (4-11).
  • the secondary battery as described in (3) above.
  • the ratio IN / IF between the peak intensity IN due to SNO 2 ⁇ and the peak intensity IF due to LiF 2 ⁇ obtained by negative ion analysis of the active material using time-of-flight secondary ion mass spectrometry is 0.03 or more.
  • the active material includes a central portion capable of occluding and releasing the electrode reactive material, and a covering portion provided in the central portion, The covering portion includes a compound having a sulfonyl group (> SO 2 and a nitrogen bond (> N—).
  • the compound having a sulfonyl group and a nitrogen bond includes at least one selected from the group consisting of compounds represented by each of the following formulas (1) and (2).
  • R1 to R4 are each a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, or a group in which two or more of them are bonded.
  • R5 and R6 are each a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, or a group in which two or more of them are bonded. And R5 and R6 may be bonded to each other, and M is a metal element.
  • the compound represented by the formula (1) includes at least one selected from the group consisting of compounds represented by the following formulas (1-1) to (1-13),
  • the compound represented by the formula (2) includes at least one member selected from the group represented by the following formulas (2-1) to (2-11): The secondary battery according to (7) above.
  • the active material includes a lithium composite oxide,
  • the lithium composite oxide includes lithium (Li) and one or more transition metal elements as constituent elements.
  • the lithium composite oxide includes cobalt (Co) as the transition metal element and has a layered rock salt type crystal structure.
  • the lithium composite oxide has, on its surface, one or more elements that are different from the transition metal element.
  • the upper limit of the charging voltage is 4.2V or more and 4.8V or less,
  • the lower limit of the discharge voltage is 2.0V or more and 3.3V or less,
  • Lithium secondary battery The secondary battery according to any one of (1) to (12).
  • An active material capable of occluding and releasing the electrode reactant The ratio IS / IF between the peak intensity IS caused by SO 2 ⁇ and the peak intensity IF caused by LiF 2 ⁇ obtained by negative ion analysis of the active material using time-of-flight secondary ion mass spectrometry is 0.04 or more.
  • Secondary battery electrode (15) Electrode reactant can be occluded and released, The ratio IS / IF between the peak intensity IS caused by SO 2 ⁇ and the peak intensity IF caused by LiF 2 ⁇ obtained by negative ion analysis using time-of-flight secondary ion mass spectrometry is 0.04. That's it, Active material for secondary batteries.
  • An electronic device comprising the secondary battery according to any one of (1) to (13) as a power supply source.

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PCT/JP2014/050188 2013-01-17 2014-01-09 二次電池用活物質、二次電池用電極、二次電池、電池パック、電動車両、電力貯蔵システム、電動工具および電子機器 Ceased WO2014112420A1 (ja)

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CN114284561A (zh) * 2022-01-05 2022-04-05 合肥国轩高科动力能源有限公司 一种电解液防过充添加剂、包含添加剂的电解液、锂二次电池
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