Classifications

• • 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
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
  • H01M4/46—Alloys based on magnesium or aluminium
• • 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
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
• • 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
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
  • H01M4/386—Silicon or alloys based on silicon
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/134—Electrodes based on metals, Si or alloys
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to a non-aqueous electrolyte secondary battery, and more particularly, to a negative electrode material used therein.
• lithium secondary batteries have high electromotive force and high energy density.
• Lithium secondary batteries are used in portable information terminals, mobile communication devices, portable electronic devices, small home power storage devices, motorcycles, electric vehicles, vehicles, and hybrid electric vehicles.
• a lithium secondary battery using lithium metal as a negative electrode material has a high energy density.
• dendrite deposits on the negative electrode and repeats charging and discharging, piercing through the dendrite array and reaching the positive electrode side, which may cause an internal short-circuit force. there were.
• the precipitated dendrite has a large specific surface area, and thus has high reaction activity. Therefore, the dendrite precipitated on the surface of the negative electrode reacts with the solvent in the electrolytic solution, and a solid electrolyte-like interface male lacking electron conductivity is formed on the surface of the negative electrode.
• the internal resistance of the battery increases, and particles isolated from the electron conduction network become present. These factors are factors that lower the charging and discharging efficiency.
• the compound containing silicon (S i) and lithium contains the most lithium.
• the composition formula of the compound is Li 22 S. In this range, metallic lithium does not usually precipitate. Therefore, no internal occurs due to dendrite.
• the electrochemical capacity between these compounds and each single material is 4199 mAh / g, which is larger than the theoretical capacity of graphite.
• a non-ferrous metal silicide composed of a transition element is disclosed in JP-A-7-240201.
• a negative electrode material composed of an intermetallic compound containing a Group 4B element and at least one of P and Sb and having a crystal structure of any one of a CaF 2 type, a ZnS type, and an Al Li Si type is a special feature. It is disclosed in Kohei 9-63651.
• the intermetallic compound represented by the type 2 AB is disclosed in JP-A-10- 312804 and JP No. 10- 302770.
• negative electrode materials such as intermetallic compounds and alloys based on Si or Sn are disclosed in JP-A-10-162823, JP-A-10-294112, JP-A-10-302770, It is proposed in Japanese Unexamined Patent Publication No. 10-312804.
• a negative electrode material having a higher capacity than the above-described carbon material has the following problems.
• Anode materials of a simple metal material and a simple nonmetal material capable of forming a compound with lithium commonly have inferior charge / discharge cycle characteristics as compared with a carbon anode material. The reason is not clear, but I think as follows.
• a gay element contains eight key elements in its crystallographic unit cell (cubic, space group Fd-3 m).
• lattice constant a 0. 5420 ⁇ m
• unit cell volume is 0. 1592 nm 3
• the volume occupied by one Kei atom is 19. 9X 10- 3 nm 3.
• the volume per silicon atom is the value obtained by dividing the unit cell # ⁇ by the number of silicon atoms in the unit cell. Calculating from this value, when the compound is changed from Ga to Li 12 Si 7 , the material expands by 2.19 times. In the two-phase coexistence reaction between silicon and the compound L i I2S i 7 , since the silicon partially changes to the compound L i 12 S, these # ⁇ become large and the material becomes large.
• the reason that the simple metal material and the simple nonmetal material that can form a compound with lithium have poor charge / discharge cycle characteristics compared to the carbon anode material is due to the above-described volume change and the volume change.
• a battery using a non-ferrous metal silicide negative electrode material comprising a transition element disclosed in JP-A-7-240201 has improved charge / discharge cycle characteristics as compared to a battery using a lithium metal negative electrode material. . This is inferred from the battery capacity at the first cycle, the 50th cycle, and the 100th cycle of the examples and the comparative examples described in the related art. However, using the silicide anode material In comparison with batteries using natural graphite negative electrode material, the battery capacity increased by only about 12% at the maximum. That is, although not explicitly stated in the description of the prior art, it is considered that the non-ferrous metal silicide negative electrode material composed of a transition element does not have a large increase in capacity as compared with the graphite negative electrode material.
• the battery using the negative electrode material disclosed in the above-mentioned JP-A-9-163651 has improved charge / discharge cycle characteristics compared to the battery using the Li-Pb alloy negative electrode material. It has higher capacity than batteries using graphite negative electrode material. However, in the cycle of 10 to 20 cycles, the discharge capacity is significantly reduced. The discharge capacity of the battery using the best Mg 2 Sn decreased to about 70% of the initial capacity after about 20 cycles.
• the materials disclosed in Japanese Patent Application Laid-Open No. H10-162,823 and Japanese Patent Application Laid-Open No. H10-294,112 are materials containing Sn or Si, And it has a content of about 50 atm% or more of the entire Sn or Si force material.
• a high capacity battery can be obtained.
• the cycle characteristics can be improved more than the battery using only Sn or Si.
• a battery with a Sn or Si content ratio of at least 50 atm% when charge and discharge are repeated for more than 100 cycles, the expansion and contraction of the material that occurs in each cycle causes the battery characteristics to decrease. Cycle deterioration becomes remarkable.
• JP-A 1 0 3 0 2 7 7 0 and JP, Hei 1 0 3 1 2 8 0 4 No. indicates material in Japanese is an intermetallic compound of AB 2 type, Has excellent Coulomb efficiency and rate characteristics.
• batteries using this material also have higher initial discharge capacity than batteries using conventional graphite.
• the discharge capacity at the 10th cycle of the battery using this material has already been reduced to a capacity retention ratio of the order of 90%, and this material is not a material having excellent cycle characteristics. Absent. Disclosure of the invention
• the non-aqueous electrolyte secondary battery of the present invention includes a negative electrode, a positive electrode, and a non-aqueous electrolyte.
• the negative electrode has an alloy containing Si, a first element, and a second element,
• the first element is at least one element selected from the group consisting of two elements except Mg, transition elements, 12 elements, 13 elements except B, and 14 elements except Si in the periodic table.
• the second element has at least one element of B and Mg.
• the first element is at least one element selected from the group consisting of diatomic element excluding Mg, transition element, 12 element, 13 element excluding B, and 14 element excluding Si in the periodic table.
• the second element has at least one element of B and Mg.
• the first element is at least one element of Ni and Co.
• the second element contains 0.1 to 30 parts by weight based on 100 parts by weight of the sum of the weight of the S1 and the first element. You. With this configuration, a secondary battery having excellent high capacity and excellent charge / discharge cycle characteristics can be obtained.
• FIG. 1 is a longitudinal sectional view of a nonaqueous electrolyte secondary battery according to one embodiment of the present invention. DESCRIPTION OF THE BEST EMBODIMENT OF THE INVENTION
• a non-aqueous electrolyte secondary battery includes a non-aqueous electrolyte, a separator, and a positive electrode and a negative electrode capable of inserting and extracting lithium.
• the negative electrode includes a negative electrode material, and the negative electrode includes at least one or more elements selected from silicon (S i) and M 1, which is similar to the first element group, and a second element group. (Hereinafter referred to as M2) It has an alloy composed of at least one or more elements selected from the group.
• the constituent elements of M1 are Group II elements, transition elements, Group II elements, and boron (B) except magnesium (Mg) in the periodic table. Contains at least one element selected from the group consisting of 13 elements excluding Si and 14 elements excluding Si.
• M2 contains at least one element of B and Mg.
• the negative electrode has a negative electrode current collector and a negative electrode mixture provided on the negative electrode current collector.
• the negative electrode mixture has a negative electrode material, a negative electrode conductive material, and a negative electrode binder.
• the negative electrode forms a plate-shaped negative electrode plate.
• the positive electrode has a positive electrode current collector and a positive electrode mixture provided on the positive electrode current collector.
• the positive electrode mixture has a positive electrode material, a positive electrode conductive material, and a positive electrode binder.
• the positive electrode forms a plate-shaped positive electrode plate.
• At least one element (Ml) selected from the group consisting of Group 2 elements, transition elements, Groups 12 and 13 elements of the periodic table, and 14 elements other than Si is added to Si.
• the non-aqueous electrolyte secondary battery using the negative electrode material thus obtained was able to suppress the expansion and contraction during charging and discharging more than the battery using Si alone as the negative electrode material.
• excellent charge / discharge cycle characteristics are obtained.
• the cycle characteristics of a non-aqueous electrolyte secondary battery using a negative electrode material with this element Ml added to Si are inferior to those of a conventional non-aqueous electrolyte secondary battery using a graphite material for the negative electrode.
• a nonaqueous electrolyte secondary battery was prepared using a negative electrode material obtained by adding at least one element (M2) of B and Mg to an alloy of the elements Si and Ml.
• M2 element
• Mg element of the elements
• S2 element of the nonaqueous electrolyte secondary battery
• better charge / discharge cycle characteristics were obtained than a battery using an alloy having Si and Ml as a negative electrode material.
• EPMA E1 ectron P 1 obe Xray Microanalyzer
• the negative electrode material used in the non-aqueous electrolyte secondary battery according to one embodiment of the present invention includes each element constituting the negative electrode material.
• a negative electrode material prepared by a method other than the above cooling method can be prepared by a method capable of sufficiently cooling.
• the negative electrode material is prepared by mechanical alloying, in which each element constituting the negative electrode material is charged into a high-energy mill such as a planetary ball mill or a stirring mill and mixed.
• a material having electron conductivity is used as the conductive material used for the negative electrode of the secondary battery of this embodiment.
• a material having electron conductivity is used.
• the conductive material for example, graphites, carbon blacks, conductive fibers, organic conductive materials, or a mixture thereof can be used.
• the graphite natural graphite (eg, flaky graphite), artificial graphite, graphite and the like are used.
• Carbon blacks include acetylene black, Ketjen black, channel black, furnace black, lamp black, and black.
• —Mal black is used.
• metal powders conductive materials such as carbon, metal, etc., copper, nickel and the like are used.
• organic conductive material a force such as a polyphenylene derivative is used.
• artificial graphite, acetylene black, and carbon fiber are particularly preferred.
• the amount of the conductive material to be added is not particularly limited, but is preferably in the range of 1 to 50 parts by weight, more preferably in the range of 1 to 30 parts by weight, based on 100 parts by weight of the negative electrode material. preferable. Further, since the negative electrode material itself has electronic conductivity, a configuration in which the negative electrode does not contain a conductive material is also possible.
• thermoplastic resin a volatile resin, or the like
• examples of the binder include polyethylene, polypropylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), styrene-butadiene rubber, tetrafluoroethylene-hexafluoroethylene copolymer, and tetrafluoroethylene.
• FEP Hexafluoro mouth propylene copolymer
• PFA tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer
• EPF tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer
• EPTFE resin ethylene-tetrafluoroethylene copolymer
• PCTFE polychloroethylene trifluorethylene
• ECTFE ethylene-cyclotrifluoroethylene copolymer
• ECTFE vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer
• resins can be used in combat or mixtures.
• Particularly preferred materials are styrene-butadiene rubber, vinylidene polyfluoride, ethylene-monoacrylic acid copolymer or (Na +) ion of the above-mentioned material, ethylene-methacrylic acid copolymer or (Na +) ion-crosslinking of the above-mentioned material.
• an ethylene-methyl acrylate copolymer or a (Na +) ion crosslinked product of the above-mentioned material an ethylene-methyl methacrylate copolymer or a (Na +) ion crosslinked product of the above material.
• an electron conductor that does not cause a chemical change in the configured battery can be used.
• stainless steel, nickel, copper, titanium, carbon, and conductive resin are used as the material of the current collector.
• a current collector material a material obtained by treating carbon, nickel or titanium on the surface of copper or stainless steel is used. Particularly, copper or copper alloy is preferable. Further, a material obtained by oxidizing the surface of these materials can also be used.
• the current collector preferably has an uneven surface, and the uneven surface is formed by, for example, surface treatment. Examples of the shape of the current collector include oils, films, sheets, nets, punched bodies, lath bodies, porous bodies, foams, and molded bodies of group (1).
• the thickness of the current collector is not particularly limited, but is 1 m to 55 ⁇ .
• a lithium-containing compound or a lithium-free compound can be used as the positive electrode material used for the positive electrode of the secondary battery of this embodiment.
• the positive electrode material include Li x Co ⁇ 2 and Li x N i 0 2 , L i x M n 0 2 , L i X C o y N i to y 0 2 , L i x C o y M, _ y O z , L i X N i y M y O z , L i x Mn 2 ⁇ 4 , L i Where M is at least one of Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, B It is a kind.
• the above x value is a value before the start of charge / discharge, and the x value increases / decreases by charge / discharge.
• the cathode material include transition metal chalcogenides, vanadium oxides, lithium compounds of vanadium oxides, niobium oxides, lithium compounds of niobium oxides, conjugated polymers using organic conductive materials, and Chevrel phase compounds. used. Further, a mixed material of a plurality of different materials can be used as the positive electrode.
• the positive electrode material as the positive electrode active material is not particularly limited, but has, for example, a powder having a flat: vertical diameter in the range of 1 to 30 m.
• a powder having a flat: vertical diameter in the range of 1 to 30 m As the conductive material for the positive electrode used for the positive electrode of the secondary battery of this embodiment, an electron conductive material that does not cause a chemical change at the charge / discharge potential of the positive electrode material used is used.
• Examples of the conductive material for the positive electrode include graphites, carbon blacks, conductive materials, metal powders, conductive whiskers, conductive metal oxides, fluorinated carbon, and organic conductive materials. Used alone or as a mixture of materials. Graphites include natural graphite, flaky graphite, etc.), and artificial graphite.
• carbon blacks acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal black and the like are used.
• conductive fibers propylenes, carbon fibers, and metal fibers are used.
• metal powders aluminum is used.
• Conductive whiskers are commonly used such as lead oxide and potassium titanate.
• conductive metal oxide for example, titanium oxide is used.
• organic conductive material a polyphenylene derivative or the like is used. Among these conductive agents, artificial graphite and acetylene black are particularly preferred.
• the amount of the conductive agent to be added is not particularly limited, but is preferably, for example, in the range of 1 to 50 parts by weight, more preferably 1 to 30 parts by weight, per 100 parts by weight of the positive electrode material. preferable. Also, 2 to 15 parts by weight of carbon or graphite are particularly preferred.
• a thermoplastic resin, a curable resin, or the like is used as the binder.
• the binder for example, polyethylene, polypropylene, polyteto Lafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), styrene butadiene rubber, tetrafluoroethylene-hexafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkylvinyl ether copolymer (PFA), vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-chloro-trifluoroethylene copolymer, Ethylene-tetrafluoroethylene copolymer (ETFE resin), polyvinyl chloride trifluoroethylene (PCTFE), vinyliden
• the positive electrode current collector used for the positive electrode of the secondary battery of this example an electron conductor that does not cause a chemical change in the charging potential of the positive electrode material to be used is used.
• an electron conductor that does not cause a chemical change in the charging potential of the positive electrode material to be used is used.
• stainless steel, aluminum, titanium, carbon, conductive resin, and the like are used as the material of the current collector for the positive electrode.
• a material obtained by treating aluminum or stainless steel with stainless steel or titanium is used.
• the current collector for the positive electrode aluminum or an aluminum alloy is particularly preferable.
• a current collector formed by oxidizing the surface of these materials can also be used.
• the current collector preferably has an uneven surface. The uneven surface is formed, for example, by a surface treatment.
• the current collector for example, oil, a film, a sheet, a net, a punched body, a lath body, a porous body, a foam, a fiber group, a molded article of a nonwoven fabric, and the like are used.
• the thickness of the current collector is not particularly limited, but is 1 m to 500 m.
• the electrode mixture has a filler, a dispersant, an ion conductor, a pressure booster, and various other additives. These are added to the above-mentioned conductive agent and binder.
• a filter a fiber-like material that does not cause a chemical change in the constructed battery is used.
• an olefin polymer such as polypropylene or polyethylene, glass or carbon is used.
• the amount of the filler to be added is not particularly limited, but is preferably, for example, 0 to 30 parts by weight with respect to 100 parts by weight of the electrode mixture.
• the negative electrode plate having the negative electrode mixture is provided so as to face the positive electrode plate having the positive electrode mixture.
• the non-aqueous electrolyte used in this example has a non-aqueous solvent and a supporting salt dissolved in the solvent.
• a supporting salt a lithium salt is used.
• the non-aqueous electrolyte has a non-aqueous electrolyte.
• the non-aqueous solvent for example, cyclic monoponates, chain carbonates, fatty carboxylic acid esters, chain ethers, cyclic ethers, aprotic organic solvents and the like are used.
• cyclic carbonates ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC;), vinylene carbonate (VC) and the like are used.
• chain carbonates include dimethyl carbonate (DMC), getyl carbonate (DEC), ethyl methyl carbonate (EMC), and dipropyl carbonate (DPC).
• DMC dimethyl carbonate
• DEC getyl carbonate
• EMC ethyl methyl carbonate
• DPC dipropyl carbonate
• aliphatic carboxylic acid esters methyl formate, methyl acetate, methyl propionate, ethyl propionate and the like are used.
• Arptyrolactone and the like are used as the arlactones.
• DME 1,2-dimethoxyethane
• DEE 1,2-diethoxyethane
• EME ethoxymethoxyethane
• cyclic ethers tetrahydrofuran, 2-methyltetrahydrofuran and the like are used.
• aprotic organic solvents include dimethyl sulfoxide, 1,3-dioxolane, formamide, acetateamide, dimethylformamide, dioxolane, acetonitrile, propyl nitrile, nitromethane, ethyl monoglyme, phosphate triester, trimethoxymethane, Dioxolane derivatives, sulfolane, methylsulfolane, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, pro Pyrene carbonate derivatives, tetrahydrofuran derivatives, ethyl ether, 1,3-propansaltone, anisol, dimethylsulfoxide, N-methylpyrrolidone, etc.
• a mixed solvent of cyclic carbonate and chain force carbonate or a mixed system of cyclic carbonate, chain force carbonate and aliphatic carboxylic acid ester is preferable.
• the lithium salt used in the present embodiment for example, L i C 10 4, L i BF 4, L i PF 6, L iAl C l 4, L i SbF 6 L i SCN, L i Cl, L i CF 3 S ⁇ 3 , Li CF 3 C0 2 ,
• L i (CF 3 SO z ) 2 , L i As F 6 , L i N (CF 3 S ⁇ 2 ) 2 , L i B 10 C 1, Lithium carbonate, LiCl, LiBr, LiI, lithium chloroborane, lithium tetraphenylborate, imides and the like are used. These compounds can be used alone or in combination of two or more. In particular, a lithium salt having L i PF 6 is preferable.
• the non-aqueous electrolyte also includes a least ethylene carbonate and E chill methyl carbonate, including L i PF 6 as ⁇ .
• the required amounts of these electrolytes are used depending on the amounts of the positive electrode material and the negative electrode material and the size of the battery.
• the amount of the supporting salt dissolved in the non-aqueous solvent is not particularly limited, but is preferably, for example, in the range of 0.2 mol 1 to 2 mol 1/1. In particular, a range from 0.5551101 / 1 to 1.5mo1-1 is more preferable.
• ⁇ is effective to add another compound to the electrolyte for the purpose of improving the discharge characteristics and the charge / discharge characteristics.
• other compounds to be added include triethyl phosphite, triethanolamine, cyclic ether, ethylenediamine, n-glyme, pyridine, hexyl triamide, nitrobenzene derivatives, crown ethers, quaternary ammonium salts,
• ethylene glycol dialkyl ether is used.
• a microporous thin film having a high ionization degree, a predetermined mechanical and organic solvent resistance, and properties such as hydrophobic electric resistance is used.
• a material having a function of increasing the resistance by closing the holes when the separation exceeds a certain level is used.
• Separee-In the evening for example, sheets made of olefin polymer or glass fiber Non-pulmonary or As the olefin polymer, polypropylene and polyethylene, or an olefin polymer in which these are combined are used.
• the separator has pores, and the pore diameter of each of the pores is preferably in such a range that the positive and negative electrode materials, binder, and conductive agent detached from the electrode do not exert any force.
• the pore size is, for example, in the range of 0.01 im to 1;
• the thickness of the separator is 10 to 300 m.
• the porosity of the pores is determined according to the permeability of electrons and ions, the material and the film pressure, and is generally preferably 30% to 80%.
• Another non-aqueous electrolyte secondary battery of the present embodiment includes a negative electrode, a positive electrode, a separator disposed between the negative electrode and the positive electrode, and an organic electrolyte.
• the organic electrolyte has an organic solvent and a lithium salt dissolved in the organic solvent. Separation is installed between the negative electrode and the positive electrode.
• the negative electrode includes a negative electrode mixture including a negative electrode material and a first polymer material. The organic is absorbed and held in the first polymer.
• the positive electrode has a positive electrode mixture including a positive electrode material and a second polymer. The organic electrolyte is absorbed and held in the second polymer.
• the separator has a third polymer material capable of absorbing the organic electrolyte and has porosity.
• the separator, the positive electrode, and the negative electrode are integrated.
• the polymer material a material capable of absorbing and holding the organic electrolyte is used.
• a copolymer of vinylidene fluoride and hexafluoropropylene is particularly preferred.
• the shape of the battery coin type, button type, sheet type, laminated type, cylindrical type, flat type, square type, etc. are used. Also, a battery having a large shape used for an electric vehicle or the like is used.
• nonaqueous electrolyte secondary battery of the present invention can be used for portable information terminals, portable electronic devices, small household electric power storage devices, motorcycles, electric vehicles, hybrid electric vehicles, and the like.
• the non-aqueous electrolyte secondary battery of the present invention is not limited to these.
• the present invention will be described in more detail by way of typical examples. However, the invention is not limited to these exemplary embodiments. Typical Example 1
• FIG. 1 is a longitudinal sectional view of a nonaqueous electrolyte secondary battery according to one embodiment of the present invention.
• a positive electrode plate 5 and a negative electrode plate 6 are spirally wound a plurality of times via a force separator 7 and housed in a battery case 1.
• Battery case 1 has a cylindrical shape.
• the positive electrode lead 5a is pulled out of the positive electrode plate 5, and is connected to the other end of the positive electrode lead 5a.
• the negative electrode lead 6 a is pulled out from the negative electrode plate 6, and the other end of the negative electrode lead 6 a is connected to the bottom of the battery case 1.
• the battery case 1 and the leads 5a and 6a are made of a metal or an alloy having an organic electrolyte resistance and electron conductivity.
• the leads 5a and 6a are made of, for example, a metal such as iron, nickel, titanium, chromium, molybdenum, copper, or aluminum, or an alloy thereof.
• the battery case 1 is made by processing a stainless steel plate or an A1-Mn alloy plate
• the positive electrode lead 5a is made of aluminum
• the negative electrode lead 6a is made of nickel.
• the battery case can be made of various engineering plastics or a combination material of plastic and metal in order to reduce the weight.
• the upper ring 8a is installed above the electrode group 4, and the lower insulating ring 8b is installed between the electrode group 4 and the bottom of the battery case 1.
• the electrolyte is injected into the battery case 1.
• the sealing plate 2 is set in the opening of the battery case 1.
• the battery can have various conventionally known safety elements in addition to the safety valve.
• a safety element for example, a fuse, a bimetal, a PTC element or the like for an overcurrent prevention element can be used.
• a method of forming a cut in the battery case 1 a method of cracking the gasket, a method of forming a crack in the sealing plate, or a method of cutting the lead plate is used. Methods are available.
• a safety measure it is also possible to install a protection circuit that incorporates measures for overcharging and overdischarging in the battery can.
• the charger can have the above-described protection circuit.
• a measure against overcharging a method to cut off the current by increasing the internal pressure of the battery shall be provided. Can be. In this case, a compound for increasing the internal pressure can be contained in the mixture or in the electrolyte.
• Examples of the compound raising the internal pressure is L i 2 C_ ⁇ 3, L i HC_ ⁇ 3, N a 2 C 0 3 , N aHC0 3, C a C0 3, and carbonates, such as Mg C_ ⁇ 3 force 'used .
• Known methods such as DC or AC electric welding, laser welding, and ultrasonic welding are used as the welding method for the cap, the battery case, the sheet, the lead plate, and the like.
• a sealant used when installing the sealing plate a known compound such as asphalt or a mixture thereof is used.
• the first element is designated by M1.
• the second element is designated by M2.
• Nickel (Ni) was used as the first element Ml.
• the M2 element was weighed so as to have a weight ratio shown in Table 1, and the raw material compositions having the respective charging ratios were measured.
• Table 1 Table 1, and the raw material compositions having the respective charging ratios were measured.
• boron (B) was used as the M 2 element.
• these raw material compositions were put into a melting tank, and melted and mixed at a temperature at which each composition could be sufficiently melted to obtain a melt.
• the melt was quenched by a rapid quenching method and solidified to obtain a solidified product. Subsequently, the solidified product was subjected to a heat treatment for 20 hours in an inert atmosphere at 900 ° C. This heat-treated product was pulverized with a ball mill and then classified with a sieve. Thus, the respective negative electrode materials A1 to A6 of particles having a size of about 45 m or less were obtained. Each of the negative electrode materials A1 to A6 has a different boron content ratio.
• each of the negative electrode materials 75 parts by weight of each of the negative electrode materials, 20 parts by weight of carbon powder as a conductive agent, and 5 parts by weight of polyvinylidene fluoride resin as a binder were mixed.
• the mixture was dispersed in dehydrated N-methylpiridinone to prepare a slurry.
• the slurry was applied on a negative electrode current collector made of copper foil, dried, and then rolled. Thus, negative electrode plate 6 was produced.
• lithium cobaltate powder 85 parts by weight of lithium cobaltate powder, 10 parts by weight of carbon powder as a conductive agent, and 5 parts by weight of polyvinylidene fluoride resin as a binder were mixed. These mixtures were dispersed in dehydrated N-methylpyrrolidinone to prepare a slurry. The slurry was applied on a positive electrode current collector made of aluminum foil, dried, and then rolled. Thus, the positive electrode plate 5 was produced.
• body ⁇ 1 I have a mixed solution of 1 ethylene force one Poneto and E chill methyl carbonate, and L i PF 6 of 1.5 mole / liter dissolved in a mixture thereof Organic electricity was used.
• negative electrodes using negative electrode materials A1 to A6 having different boron contents were prepared. Further, cylindrical secondary batteries were prepared using the respective negative electrode materials A1 to A6 to obtain batteries A1 to A6.
• the fabricated cylindrical battery has a shape of 18 mm in diameter and 650 mm in height. These batteries were charged at a constant current of 100 mA until the voltage reached 4. IV, and then discharged at a constant current of 100 mA until the voltage reached 2.0 V. Such a cycle of charging and discharging was repeated. Charging and discharging were performed in a thermostat at 20 ° C. In addition, the charge and discharge cycle was repeated up to 100 cycles. Then, the holding ratio was calculated.
• the capacity retention ratio is the ratio of the discharge capacity at the 100th cycle to the initial discharge capacity. Table 1 shows the measurement results.
• each of the batteries Al, A2, A3, A4, and A5 had an excellent initial discharge capacity of 190 OmAh or more and an excellent capacity retention rate of 90% or more.
• battery A1 had a small discharge capacity at the 100th cycle and exhibited a small dose maintenance rate.
• Battery A6 had a slightly lower initial discharge capacity.
• the same cylindrical battery as described above was produced using a graphite material as the negative electrode material, and the cycle characteristics of charging and discharging were measured. As a result, the initial discharge capacity was 151 OmAh, and the capacity retention rate at the 100th cycle was 95%. That is, the initial discharge capacity of the battery using the negative electrode material containing the graphite material is smaller than that of the batteries A2 to A5 of the present example.
• Magnesium “Mg” was used as the second element M 2 included in the negative electrode material in Typical Example 1. That is, negative electrode materials B2 to B6 containing Si, Ni and Mg were prepared, and cylindrical batteries B2, B3, B4, B5 and B6 using the negative electrode materials were prepared. Except for the negative electrode material, the configuration is the same as that of the first exemplary embodiment. The capacity retention of each of the obtained batteries was measured in the same manner as in the typical example 1. Table 2 shows the measurement results. Table 2
• each of batteries B2, B3, B4, and B5 had an excellent initial discharge capacity of 190 OmAh or more and an excellent capacity retention rate of 90% or more.
• battery B6 had a slightly smaller initial discharge capacity.
• Co Co
• the M2 element was weighed so as to have a weight ratio shown in Table 1, to prepare a raw material composition having each charging ratio.
• boron (B) was used as the M 2 element.
• these raw material compositions were put into a melt, and the respective compositions were sufficiently melted and dissolved and mixed to obtain a melt.
• the melt was quenched by a roll quenching method and solidified to obtain a solidified product.
• the solidified product was heat-treated for 20 hours in an inert atmosphere at 900 ° C.
• This heat-treated product was powder-framed with a ball mill, and then classified with a sieve.
• the respective negative electrode materials C 1 to C 6 of particles having a size of about 45 im or less were obtained.
• Each of the negative electrode materials C1 to C6 has a different hole ratio.
• batteries C2, C3, C4, and C5 each had an excellent initial discharge capacity of 190 OmAh or more and an excellent capacity retention rate of 90% or more.
• battery C1 It had a small capacity retention.
• Battery C6 had a slightly lower initial discharge capacity.
• Magnesium “Mg” was used as the second element M 2 contained in the negative electrode material in Typical Example 3. That is, negative electrode materials F2 to F6 containing Si, Co, and Mg were prepared. On the other hand, a negative electrode material E1 containing Si and Co without containing Mg was prepared. Cylindrical batteries El, F2, F3, F4, F5, and F6 using the respective negative electrode materials were created. Except for the negative electrode material, the configuration is the same as that of the typical example 1. For each of the obtained batteries, the volume retention rate was measured in the same manner as in the typical example 1. The measurement result is shown in FIG. Table 4
• each of the batteries F2, F3, F4 and F5 had an excellent initial discharge capacity of 190 OmAh or more and an excellent capacity retention rate of 90% or more.
• battery E1 had a small capacity retention rate.
• Battery F6 had a slightly lower initial discharge capacity.
• Ml both cobalt (Co) and nickel (Ni) were used.
• the M 2 element was weighed so as to have a weight ratio shown in Table 1, and raw material compositions having respective charging ratios were prepared.
• boron (B) was used as the M2 element.
• these raw material compositions were put into a smelt and melted and mixed with a sculpture capable of sufficiently melting the respective components to obtain a melt.
• negative electrode materials G2 to G6 containing Si, Ni, Co, and B were prepared.
• a negative electrode material G1 containing Si, Ni, and Co containing no B was prepared.
• Cylindrical batteries Gl, G, G3, G4, G5, and G6 using each negative electrode material were created. Except for the negative electrode material, the configuration is the same as that of the typical example 1. The capacity retention of each of the obtained batteries was measured in the same manner as in the typical example 1. Table 5 shows the measurement results. Table 5
• each of batteries G2, G3, G4, and G5 has an excellent capacity of 190 OmAh or more. It had an initial discharge capacity of 90% and an excellent capacity retention rate of 90% or more. On the other hand, battery G1 had a small capacity retention rate. Battery G6 had a slightly lower initial discharge capacity. Typical Example 6
• Magnesium “Mg” was used as the M 2 element contained in the negative electrode material in Typical Example 5. That is, negative electrode materials H2 to H6 containing Si, Ni, Co, and Mg were prepared. On the other hand, a negative electrode material G1 containing no Mg, but containing Si, Ni, and Co was prepared. Cylindrical batteries Gl, H2, H3, H4, H5, and H6 using each negative electrode material were created. Except for the negative electrode material, the configuration is the same as that of the typical example 1. For each of the obtained batteries, the capacity retention was measured in the same manner as in the typical example 1. Table 4 shows the measurement results. Table 6
• each of batteries H2, H3, H4, and H5 had an excellent initial discharge capacity of 190 OmAh or more and an excellent capacity retention rate of 90% or more.
• battery HI had a small capacity retention rate.
• Battery H6 had a slightly lower initial discharge capacity.
• the negative electrode material is Si and the second element M 2 is B or
• Mg contains Mg and Ni or Co as the first element
• a battery having an excellent capacity retention of 90% or more can be obtained.
• the content ratio of the second element M2 is in the weight range of 0.1 to 30 parts by weight, the excellent initial discharge capacity of 190 O mAh or more and the excellent initial discharge capacity of 90% or more A battery with a high comfort rate is obtained.
• a battery using a negative electrode material containing Si, the first element M i, and the second element M 2 has a higher initial capacity than a battery using a negative electrode material having a graphite material. I do.
• the negative electrode material containing Si, the first element Mi, and the second element M2 when the content ratio of the second element M2 is 40 parts by weight, the initial capacity is slightly reduced. Therefore, as the content of the second element M 2, a force S in a range from 0.1 part by weight to 30 parts by weight is particularly desirable.
• At least one of Ni and Co was used as the first element Ml, but the present invention is not limited thereto.
• At least one element selected from the group consisting of elementary elements other than Mg in the periodic table, transition elements, elements of group 12 and elements of group 13 excluding Si, and elements of group 14 excluding Si is there.
• Various batteries using such a negative electrode material having the first element M1 were prepared, and the initial discharge capacity of each of the obtained batteries, the amount in the 100th cycle, the volume, and the volume * The retention rate was measured. Then, the same effect was obtained.
• each of the obtained batteries had an excellent initial charge capacity and an excellent capacity retention rate.
• the mixed composition of the first element can use any mixed composition power. Also in this case, the same results as those of the above-described typical examples 5 and 6 were obtained.
• the second element M2 B alone or Mg alone was used, but the second element is not limited to this composition. Any mixture of B and Mg can be used. In this case, the same result as in the above-mentioned typical examples 1-6 was obtained. Further, in the above-described exemplary embodiment 1 to 6, the weight ratio of Si to the first element M 1 is CT / JP00 / 00498
• the expansion and contraction of particles due to the cycle of charging and discharging can be suppressed. Therefore, an excellent retention rate can be obtained in the cycle of charging and discharging. As a result, the charge / discharge cycle characteristics of the battery are improved. Furthermore, excellent initial discharge capacity is obtained.

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