WO2013187176A1 - Procédé de production d'un accumulateur lithium-ion et accumulateur lithium-ion - Google Patents

Procédé de production d'un accumulateur lithium-ion et accumulateur lithium-ion Download PDF

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WO2013187176A1
WO2013187176A1 PCT/JP2013/063558 JP2013063558W WO2013187176A1 WO 2013187176 A1 WO2013187176 A1 WO 2013187176A1 JP 2013063558 W JP2013063558 W JP 2013063558W WO 2013187176 A1 WO2013187176 A1 WO 2013187176A1
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lithium
negative electrode
secondary battery
active material
metal
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PCT/JP2013/063558
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English (en)
Japanese (ja)
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慎 芹澤
恵美子 藤井
入山　次郎
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日本電気株式会社
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Priority to JP2014521214A priority Critical patent/JP6112111B2/ja
Publication of WO2013187176A1 publication Critical patent/WO2013187176A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • 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
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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

Definitions

  • the present invention relates to a method for manufacturing a lithium ion secondary battery, and more particularly to a method for manufacturing a lithium ion secondary battery including a step of performing a lithium pre-doping process in the manufacturing process.
  • Patent Document 1 discloses that silicon oxide or a silicate compound is used as a negative electrode active material of a secondary battery as a negative electrode material having a large capacity.
  • a secondary battery using the oxide of silicon described in Patent Document 1 as a negative electrode active material is charged and discharged at 45 ° C. or higher, there is a problem that the capacity reduction accompanying the cycle is large.
  • Patent Document 2 and Patent Document 3 metal lithium foil is attached to a non-carbon negative electrode and heated. It is disclosed that lithium is diffused into a non-carbon negative electrode.
  • the non-carbon-based negative electrode described in Patent Document 2 is a method in which a lithium metal foil is pasted and diffused into the active material by a heating method so that the active material particles sufficiently occlude lithium before charging. This is a means of solving the problem of “lithium depletion” during charging and discharging.
  • lithium and a negative electrode are obtained by contacting a metal film mainly composed of lithium under heating and pressure on the surface of a layer containing a non-carbon negative electrode active material.
  • This is a means for solving the large irreversible capacity of the negative electrode active material such as silicon oxide by reacting with the active material and occluding lithium in the active material.
  • Patent Document 4 discloses a secondary battery including an active material layer including carbon material particles that can occlude and release lithium ions, metal particles that can be alloyed with lithium ions, and oxide particles that can occlude and release lithium ions.
  • a negative electrode is disclosed.
  • the negative electrode for a secondary battery described in Patent Document 4 has an effect of relaxing the volume change of the entire negative electrode when lithium is occluded and released due to the difference in charge / discharge potential of the three components.
  • a technique for forming a lithium metal film on the negative electrode surface is disclosed.
  • a lithium metal layer is provided on the active material layer to provide a means for solving the large irreversible capacity of the negative electrode active material.
  • a method for forming a lithium metal layer As a method for forming a lithium metal layer, a method for forming a film by bonding lithium metal to the negative electrode surface and melting it is shown in addition to a melt cooling method, a vacuum deposition method, a sputtering method, and the like.
  • Patent Documents 5 and 6 disclose a technique of doping lithium into silicon-silicon oxide composite particles coated with carbon.
  • Patent Documents 7 and 8 describe a method for producing lithium nitride.
  • Patent Document 9 describes a negative electrode in which a lithium nitride protective film is formed on a lithium metal surface.
  • Patent Documents 2 to 4 using a lithium metal foil or a metal film mainly composed of lithium as a lithium source, the negative electrode active material before battery completion is doped with lithium, that is, lithium pre-doped. It is disclosed. However, when lithium or a metal foil, piece, or molded product mainly composed of lithium is used as a pre-doped lithium source, there is a problem that the lithium doping amount is not stable within the electrode surface, for each electrode, and for each lot.
  • the energy density and cycle characteristics may not be sufficiently improved.
  • the present invention has been made to solve this problem, and is a lithium ion secondary battery in which irreversible capacity is reduced, cycle characteristics are improved with high energy density, by stably performing lithium pre-doping.
  • An object of the present invention is to provide a method of producing
  • the present invention is a method for producing a lithium ion secondary battery comprising a laminated electrode body in which a negative electrode and a positive electrode containing an active material capable of inserting and extracting lithium are arranged opposite to each other,
  • the present invention relates to a method for manufacturing a lithium ion secondary battery, comprising a step of bringing a lithium source having a surface layer containing 30% by mass or more of lithium nitride into contact with a negative electrode active material.
  • a secondary battery having a high energy density and good cycle characteristics can be provided.
  • An example of a laminated electrode elements included in the secondary battery according to the present embodiment is a cross-sectional view schematically showing.
  • An example of a lithium source used in the lithium pre-doping of the present embodiment is a cross-sectional view schematically showing. It is sectional drawing which shows typically an example of the lithium source which has a base material used for the lithium pre dope concerning this embodiment. It is sectional drawing which shows typically an example of the lithium source used for the conventional lithium pre dope.
  • the lithium pre-doping means that the negative electrode active material occludes lithium (doping with lithium) regardless of the charge after the battery is manufactured. Typically, in the process before the battery is completed. Means that the negative electrode active material occludes lithium (dope lithium).
  • an electrode body in which at least a pair of a positive electrode and a negative electrode are arranged to face each other, and an electrolytic solution are included in the exterior body.
  • the shape of the secondary battery may be any of a cylindrical type, a flat wound square type, a laminated square type, a coin type, a flat wound laminated type, and a laminated laminate type, and a laminated laminate type is preferable.
  • a laminated laminate type secondary battery will be described.
  • FIG. 1 shows a schematic cross-sectional view of an example of a laminated electrode body 1 included in a laminated laminate type secondary battery.
  • a plurality of positive electrodes 2 and a plurality of negative electrodes 3 are alternately stacked with the separator 4 interposed therebetween.
  • an active material uncoated portion where the positive electrode current collector 5 and the negative electrode current collector 6 are not covered with the active material is provided.
  • the positive electrode 2 and the negative electrode 3 are stacked with the active material uncoated portions facing in opposite directions.
  • the positive electrode current collector 5 is electrically connected to each other at an active material uncoated portion, and a positive electrode lead terminal 7 is further connected to the connection portion.
  • the negative electrode current collector 6 is electrically connected to each other at an active material uncoated portion, and a negative electrode lead terminal 8 is further connected to the connection portion.
  • a laminated laminate type secondary battery is manufactured by wrapping a laminated electrode body 1 with an exterior body such as an aluminum laminated film, injecting an electrolyte into the inside, and then sealing under reduced pressure.
  • the negative electrode 3 provided in the laminated electrode body 1 according to the present embodiment includes a negative electrode active material, a negative electrode binder, and a negative electrode current collector, and lithium before the production of the secondary battery or before electrode lamination.
  • a negative electrode for a secondary battery doped with it does not specifically limit as a negative electrode active material contained in the negative electrode 3,
  • As an active material of this embodiment only 1 type of these may be used, and 2 or more types may be mixed and used.
  • metals that can be alloyed with lithium include Al, Si, Pb, Sn, In, Bi, Ag, Ba, Ca, Hg, Pd, Pt, Te, Zn, La, and alloys of two or more of these. It is done.
  • silicon (Si) is preferably included as a metal that can be alloyed with lithium.
  • the metal content in the negative electrode active material is preferably 5% by mass to 95% by mass, more preferably 10% by mass to 90% by mass, and more preferably 20% by mass to 50% by mass. More preferably.
  • metal oxides that can occlude and release lithium ions include aluminum oxide, silicon oxide, tin oxide, indium oxide, zinc oxide, lithium oxide, and composites thereof.
  • silicon oxide is preferably included as a metal oxide capable of inserting and extracting lithium ions.
  • one or more elements selected from nitrogen, boron, phosphorus and sulfur can be added to the metal oxide. By carrying out like this, the electrical conductivity of a metal oxide can be improved.
  • the content of the metal oxide in the negative electrode active material may be 0% by mass or 100% by mass, but is preferably 5% by mass or more and 100% by mass or less, and 40% by mass or more and 95% by mass or less. Is more preferable, and it is further more preferable to set it as 50 to 90 mass%.
  • these metal oxides is preferably in whole or in part has an amorphous structure. Since the metal oxide has an amorphous structure, it suppresses volume changes of other negative electrode active materials such as metals that can be alloyed with lithium and carbon materials that can occlude and release lithium ions, and suppresses decomposition of the electrolyte. Can be. Although this mechanism is not clear, it is presumed that the formation of a film on the interface between the carbon material and the electrolytic solution has some influence due to the amorphous structure of the metal oxide.
  • the amorphous structure is considered to have relatively few elements due to non-uniformity such as crystal grain boundaries and defects.
  • the metal oxide has an amorphous structure. Specifically, when the metal oxide does not have an amorphous structure, a peak specific to the metal oxide is observed. However, the metal oxide may have a case where all or part of the metal oxide has an amorphous structure. Inherent peaks are broad and observed.
  • the negative electrode active material contains a metal that can be alloyed with lithium and a metal oxide that can occlude and release lithium ions
  • all or a part of the alloyable metal is dispersed in the metal oxide.
  • the volume change as the whole negative electrode can be suppressed, and decomposition
  • all or part of the metal is dispersed in the metal oxide because transmission electron microscope observation (general TEM observation) and energy dispersive X-ray spectroscopy measurement (general EDX measurement). It can confirm by using together. Specifically, the cross section of the sample containing metal particles is observed, the oxygen concentration of the metal particles dispersed in the metal oxide is measured, and the metal constituting the metal particles is not an oxide. Can be confirmed.
  • the metal oxide is preferably an oxide of a metal constituting the metal.
  • the negative electrode active material containing a metal and a metal oxide is not particularly limited to the proportion of metals and metal oxides.
  • the metal is preferably 5% by mass or more and 90% by mass or less, and more preferably 30% by mass or more and 60% by mass or less, based on the total of the metal and the metal oxide.
  • the metal oxide is preferably 10% by mass or more and 95% by mass or less, and more preferably 40% by mass or more and 70% by mass or less, with respect to the total of the metal and the metal oxide.
  • Examples of carbon materials that can occlude and release lithium ions include graphite, amorphous carbon, diamond-like carbon, carbon nanotubes, and composites thereof.
  • graphite has high crystallinity, high electrical conductivity, and excellent adhesion to a current collector made of a metal such as copper and voltage flatness.
  • Amorphous carbon has low crystallinity and a relatively small volume change, so that the volume change of the entire negative electrode can be mitigated, and deterioration due to nonuniformity such as crystal agglomerates and defects occurs. Hateful.
  • the content of the carbon material in the negative electrode active material may be 0% by mass, but is preferably 1% by mass to 50% by mass, and more preferably 2% by mass to 30% by mass.
  • the negative electrode active material contains a metal that can be alloyed with lithium, a metal oxide that can occlude and release lithium ions, and a carbon material that can occlude and release lithium ions
  • the metal is preferably 5% by mass or more and 90% by mass or less, and more preferably 20% by mass or more and 50% by mass or less with respect to the total of the metal, the metal oxide, and the carbon material.
  • the metal oxide is preferably 5% by mass or more and 90% by mass or less, and more preferably 40% by mass or more and 70% by mass or less with respect to the total of the metal, the metal oxide, and the carbon material.
  • the carbon material is preferably 1% by mass or more and 50% by mass or less, and more preferably 2% by mass or more and 30% by mass or less with respect to the total of the metal, the metal oxide, and the carbon material.
  • the metal, metal oxide, and carbon material are not particularly limited, but particulate materials can be used.
  • the average particle size of the metal can be smaller than the average particle size of the metal oxide and the average particle size of the carbon material. In this way, metals with a large volume change during charge / discharge have a relatively small particle size, and metal oxides and carbon materials with a small volume change have a relatively large particle size. Micronization is more effectively suppressed.
  • lithium is occluded and released in the order of large-diameter particles, small-diameter particles, and large-diameter particles during the charge / discharge process. This also suppresses the occurrence of residual stress and residual strain. Is done.
  • the average particle diameter of the metal can be, for example, 10 ⁇ m or less, and is preferably 5 ⁇ m or less.
  • the carbon material may be localized near the surface of the particle in a state of covering the metal and the metal oxide. By localizing in the vicinity of the surface in this way, the aggregation of the metal and the metal oxide can be suppressed, the volume change of the negative electrode as a whole can be reduced, and further, the electron conductivity can be made uniform.
  • the negative electrode active material includes a metal, a metal oxide, and a carbon material, all or part of the metal oxide has an amorphous structure, all or part of the metal is dispersed in the metal oxide, and the carbon material is
  • a localized negative electrode active material can be produced by a method as disclosed in, for example, Japanese Patent Application Laid-Open No. 2004-47404. That is, by performing a CVD process in an atmosphere containing an organic gas such as methane gas, a metal oxide in which metal in the metal oxide is nanoclustered and a surface is coated with a carbon material can be obtained. .
  • the said negative electrode active material is producible also by mixing a metal, a metal oxide, and a carbon material in steps by mechanical milling.
  • the negative electrode active material is preferably a negative electrode active material mainly composed of silicon.
  • Lithium silicate can be formed by performing lithium pre-doping on silicon and silicon oxide as described later. At that time, by controlling the valence of silicon, a negative electrode having a high capacity and a long life can be produced. Specifically, by forming silicon having an oxidation number of 0, a silicon compound having a silicon atom having an oxidation number of +4, and a silicon lower oxide having a silicon atom having an oxidation number of greater than 0 and less than +4, A negative electrode having a capacity and a long life can be produced.
  • the negative electrode active material may be doped with lithium in the form of a powder, and for example, it can be produced by the techniques described in Patent Document 5 and Patent Document 6.
  • a powdered active material and a lithium source for example, lithium metal, an organic lithium compound, lithium hydride, lithium aluminum hydride, etc. are mentioned, and lithium hydride and lithium aluminum hydride are preferable). They were mixed in a predetermined molar ratio, 100 °C ⁇ 800 °C, preferably heated at 200 °C ⁇ 800 °C.
  • lithium pre-doping treatment of the present embodiment described later (a step of bringing a lithium source having a predetermined surface layer into contact with the negative electrode active material) ) Can be implemented. Therefore, lithium pre-doping may be performed at least twice.
  • Negative electrode binders include polyvinylidene fluoride, modified polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene-butadiene copolymer rubber, polytetrafluoroethylene.
  • Polypropylene polyethylene, polyacrylic acid, metal salt of polyacrylic acid, polyimide, polyamideimide and the like. In the present embodiment, it is preferable to include polyimide or polyamideimide.
  • the content of the binder for the negative electrode to be used is preferably 5 to 20% by mass with respect to the total mass of the negative electrode active material from the viewpoints of “sufficient binding force” and “high energy” which are in a trade-off relationship. 8 to 15% by mass is preferable.
  • Examples of the negative electrode current collector include aluminum, nickel, copper, silver, alloys thereof, and stainless steel.
  • Examples of the shape of the current collector include a foil, a flat plate, and a mesh.
  • a negative electrode active material, a conductivity imparting agent, and a binder are dispersed and kneaded in a solvent such as N-methyl-2-pyrrolidone (NMP) to prepare a negative electrode slurry.
  • NMP N-methyl-2-pyrrolidone
  • the conductive agent, carbon black, graphite, carbonaceous fine particles such as acetylene black When the carbon material is previously localized on the surface of the negative electrode active material, the conductivity imparting agent may not be included.
  • a negative electrode before lithium pre-doping can be prepared by applying the negative electrode slurry onto a negative electrode current collector such as a copper foil and drying the solvent. Examples of the coating method include a doctor blade method and a die coater method.
  • a thin film of aluminum, nickel, or an alloy thereof may be formed by a method such as vapor deposition or sputtering to form a negative electrode current collector.
  • a method such as vapor deposition or sputtering to form a negative electrode current collector.
  • desired heat processing can be performed as needed.
  • the polyamide precursor or a polyimide precursor preferably it contains the polyamic acid.
  • the negative electrode before lithium pre-doping may be manufactured by growing a negative electrode active material or the like on the negative electrode current collector by a vapor phase method such as vapor deposition or sputtering.
  • the negative electrode (before lithium pre-doping) is lithium pre-doped as described below to produce the negative electrode of this embodiment.
  • Lithium pre-doping is a means for reducing the large irreversible capacity of the negative electrode active material by occluding lithium in the active material. Lithium pre-doping is classified according to the contact time between the negative electrode active material and lithium. (I) Dope lithium in the state of the negative electrode active material powder or negative electrode slurry before the negative electrode preparation.
  • the lithium pre-doping prior to the preparation of the negative electrode includes lithium metal, an organic lithium compound, lithium hydride, lithium aluminum hydride and the like (preferably lithium hydride and hydrogen) in the state of negative electrode active material powder or negative electrode slurry.
  • a doping agent lithium aluminum phosphide
  • a method of doping lithium preferably by heating for example, Patent Document 5 and Patent Document 6 may be mentioned.
  • the pre-doping performed between the preparation of the negative electrode and before the preparation of the electrode body is a state in which only the negative electrode is formed at a time before the electrode body in which the negative electrode, the positive electrode, and the separator are combined by winding or stacking.
  • Lithium pre-doping is preferably performed in a state where the negative electrode is in an electrode plate state.
  • (ii-1) a method in which a negative electrode and a lithium source are arranged in an electrolytic solution, and lithium is doped by a potential difference between the electrode and the lithium source, and (ii-2) an electrode and a lithium source are used.
  • doping in a lithium state by diffusing lithium by heat There is a method of doping in a lithium state by diffusing lithium by heat.
  • the (iii) pre-doping performed during the preparation of the electrode body is, for example, a lithium metal foil on at least one surface, preferably both surfaces of the negative electrode covered with the negative electrode active material when laminating the negative electrode, the positive electrode, and the separator. And a method of laminating the lithium source.
  • the negative electrode constituting the electrode body has two or more layers, it is sufficient that at least one of the surfaces of the negative electrode covered with the negative electrode active material is in contact with the lithium source.
  • a lithium source is laminated on both sides of all the negative electrodes to be formed. Thereafter, heating may be carried out to dope lithium, and this electrode body in the secondary battery touches the electrolyte to form a kind of local battery, which self-discharges and electrochemically lithium is the negative electrode active material. To be doped.
  • the (iv) pre-doping performed after the electrode body is manufactured is preferably performed in a step of completing the secondary battery by enclosing the electrode body and the electrolytic solution in the exterior body after the electrode body is manufactured. And a method of laminating a lithium source such as a lithium metal foil on the outermost negative electrode.
  • the electrode body touches the electrolyte in the secondary battery to form a kind of local battery, self-discharges, and lithium is doped electrochemically into the negative electrode active material. Moreover, you may advance dope by a heat
  • the invention of the present embodiment can be applied to any method that involves a treatment in which a lithium source and a negative electrode active material are brought into direct contact with each other in the lithium pre-dope.
  • the method is preferably applied to the methods (ii-2), (iii) and (iv).
  • the present embodiment will be described taking the method (ii-2) as an example, but the present embodiment is also effective in other methods.
  • the lithium source brought into contact with the negative electrode is preferably made of a metal containing 80% by mass or more of lithium.
  • the metal containing 80% by mass or more of lithium may be a lithium alloy, but the lithium content is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and most preferably Pure lithium metal.
  • metal elements other than lithium contained in the metal having lithium as a main component include sodium, magnesium, silicon, calcium, copper, and cesium.
  • the form of the metal containing 80% by mass or more of lithium may be an arbitrary form such as a foil or piece, but preferably has a larger area that can be in contact with the negative electrode.
  • the lithium metal foil can be manufactured by, for example, extrusion or rolling. It can also be produced by vapor deposition.
  • the lithium metal foil may be in the form of a single foil, or may be in a form in which the lithium metal foil is formed on the substrate 12 as shown in FIG.
  • the substrate metal foil that does not alloy with lithium such as copper, polyester such as polyethylene terephthalate (PET), plastic film such as polypropylene (PP), and the like are used.
  • the base material has flexibility capable of being in close contact with the electrode.
  • the electrode This has the effect of relaxing the shape change. Therefore, for example, the copper foil preferably has a thickness of 10 ⁇ m to 40 ⁇ m.
  • a metal containing 80% by mass or more of lithium is highly reactive, and its surface generates oxides, nitrides, and other lithium reaction products depending on the manufacturing environment, storage environment, and working environment. Further, it is difficult to keep the surface in a pure lithium state because there is a possibility that a surfactant during production is likely to remain. Further, since the reaction generated by these proceeds even in an environment with a low dew point atmosphere, the lithium source is made of nitride, oxide, or other reaction product on the surface of the lithium metal 9 as shown in FIG. There is a non-uniform surface layer 11.
  • lithium oxides and nitrides have different characteristics such as ionic conductivity and different reactions to heat and pressure.
  • lithium carbonate or the like has a lower ionic conductivity than lithium nitride and is disadvantageous for electric conduction, so that it is necessary to suppress diffusion into the electrode.
  • the non-uniform (composition and morphology) surface layer formed on the surface of the lithium metal Due to the non-uniform (composition and morphology) surface layer formed on the surface of the lithium metal, the uniformity and reproducibility of the contact interface between the negative electrode and the lithium source, and non-uniform pre-doping to the negative electrode occur. As a result, there arises a problem that a sufficient amount of lithium cannot be doped, or that more than the required amount of lithium is doped, causing dendrites to occur. Furthermore, unstable lithium pre-doping for the negative electrode reduces the effect of pre-doping on the energy density, cycle characteristics, etc. of the secondary battery.
  • the present inventor made a negative electrode doped with a uniform and sufficient amount of lithium by performing lithium pre-doping by bringing a lithium source having a predetermined surface layer into contact with the negative electrode active material. It has been found that it can be produced.
  • the lithium source used for lithium doping of the negative electrode has a surface layer 10 containing 30% by mass or more of lithium nitride, as shown in FIGS. That is, the method for manufacturing a lithium ion secondary battery according to this embodiment includes a step of bringing a lithium source having a surface layer containing 30% by mass or more of lithium nitride into contact with the negative electrode active material.
  • the surface layer containing 30% by mass or more of lithium nitride may be referred to as “a surface layer mainly containing lithium nitride”.
  • the lithium source is preferably a metal containing 80% by mass or more of lithium as already described, and the form thereof is an arbitrary form such as a foil or a piece, preferably a foil.
  • the lithium source shown in FIG. 2 is a single foil of lithium metal, and has a surface layer 10 mainly containing lithium nitride on both surfaces of the lithium metal 9.
  • the lithium source shown in FIG. 3 has a surface layer 10 mainly containing lithium nitride on the surface of the lithium metal 9 formed on the substrate 12 (on the side opposite to the substrate).
  • the thickness of the surface layer 10 is preferably 30% or less of the thickness of the lithium source. Desirably, the thickness of the surface layer 10 is preferably 3 ⁇ m or less and / or 20% or less of the thickness of the lithium source. It is particularly desirable that the thickness of the surface layer 10 is 1 ⁇ m or less and / or 10% or less of the thickness of the lithium source.
  • the "thickness" to the contact surface between the lithium source and the negative electrode the thickness in the vertical direction.
  • the thickness of the lithium source is not particularly limited, and may be 20 mm or less, for example, 5 mm or less, and preferably about 1 mm or less. In particular, when the lithium source is in the form of a foil, the thickness of the foil is more preferably 500 ⁇ m or less. Further, the thickness of the lithium source is usually preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, and further preferably 5 ⁇ m or more.
  • the thickness of the lithium source is not particularly limited, but is preferably adjusted according to the composition and thickness of the negative electrode.
  • a lithium source whose surface layer 10 has a thickness in the above range, non-uniformity at the contact interface between the electrode and the lithium source is improved.
  • the surface layer is pierced by irregularities on the surface of the negative electrode, so that the ratio of contact between the lithium metal portion below the surface layer and the negative electrode is particularly preferable.
  • the surface layer of the lithium source is an impurity layer formed by reaction of lithium metal, it is originally preferred that the surface layer is extremely thin.
  • the surface layer of the lithium source needs to be uniform on the surface of the lithium source, it is at least 0.03 ⁇ m or more. It is preferable that it is the thickness of this.
  • the surface layer 10 mainly containing lithium nitride contains lithium nitride in an amount of 40% by mass or more, more preferably 50% by mass or more. Since lithium nitride has a higher ionic conductivity (about 6 mS / cm) than lithium carbonate or the like, the electrical conductivity of the surface layer is improved by increasing the proportion of the surface in the surface layer. Moreover, even when it is taken into the electrode in the state of lithium nitride, the possibility of deteriorating the conductivity of the electrode is low. In particular, when the amount of lithium pre-doping is small, the proportion of lithium nitride in the surface layer is preferably 70% by mass or more.
  • a substance having an ionic conductivity lower than that of lithium nitride such as lithium oxide and lithium carbonate, is not included as much as possible.
  • the content of these substances having low ionic conductivity is preferably 20% by mass or less, and more preferably 10% by mass or less. More preferably, it is 1 mass% or less.
  • a method for forming a surface layer mainly containing lithium nitride on the surface of the lithium source is not particularly limited.
  • a method is generally used in which lithium metal is reacted with N 2 gas and reacted.
  • the reaction temperature is preferably less than the melting point of lithium (180.5 ° C.), preferably about room temperature (20 ° C.) to about 120 ° C.
  • an ion beam having an ion energy of 50 to 300 eV is operated on a lithium metal surface in an atmosphere containing nitrogen (for example, a mixture of nitrogen and argon).
  • nitrogen for example, a mixture of nitrogen and argon.
  • lithium metal can be thermally deposited to form a surface layer mainly containing lithium nitride on the lithium metal surface.
  • the surface of the lithium source formed a surface layer it is preferable that such impurity layer is not as much as possible there, it is preferable to form a surface layer continuously with forming the lithium source due rolling or deposition.
  • the surface layer can be formed by removing the impurity layer by a physical or chemical method and then contacting with N 2 gas.
  • the negative electrode and the lithium source may be in close contact with each other, and the method is not particularly limited.
  • the method is not particularly limited.
  • the method of pressurizing the superimposed negative electrode and lithium source it is necessary to apply a pressure within a range in which relatively soft lithium does not protrude beyond the electrode. Specifically, 0.5 kgf / cm 2 to 30 kgf / cm A pressure of 2 is preferred. In particular, when the thickness of the lithium source is 100 ⁇ m or less, pressurization of 15 kgf / cm 2 or less is preferable. Further, in order to perform uniform lithium pre-doping in the electrode surface, it is preferable to apply pressure uniformly to the electrode surface.
  • the electrode and the lithium source are arranged in a deformable decompression container such as a bag in a state where the contact can be maintained, and the decompression container of the atmospheric pressure received from the outside is received. While the electrode and the lithium source are pressed against each other due to the deformation, the pressure is reduced within a range where there is no excess gap at the interface.
  • the electrode and lithium may be put in a sealable bag such as a laminate to reduce pressure, and sealed under reduced pressure.
  • the pressure be reduced under a reduced pressure of ⁇ 0.05 MPa to ⁇ 0.1 MPa.
  • the methods (1) and (2) may be combined, and if the contact between the negative electrode and the lithium source is good, it is not necessary to pressurize or depressurize. Since diffusion (doping) from the lithium source to the negative electrode proceeds at the part where the lithium and the electrode are in contact, the contact area between the lithium and the electrode when the lithium negative electrode and the lithium source are in sufficient contact and there is no excess gap The lithium pre-doping tends to proceed uniformly.
  • the temperature at which the negative electrode and the lithium source are heated needs to be within a temperature range in which lithium diffusion proceeds stably and does not exceed the melting point of metallic lithium (180.5 ° C.), for example, from room temperature (20 ° C.). A range of 180 ° C. is preferred. At a temperature exceeding the melting point of metallic lithium, the molten lithium protrudes beyond the electrode and cannot be doped efficiently. In addition, when good contact is obtained by the method of bringing the negative electrode and the lithium source into contact with each other, dope is likely to proceed, and room temperature (20 ° C) to 130 ° C is more preferable. In particular, when the negative electrode and the lithium source are in close contact with each other with no extra space, room temperature (20 ° C.) to 80 ° C. is particularly preferable. Although the heating time depends on the required dope amount and the heating temperature, pre-doping can be generally completed within the range of 1 hour to 100 hours, preferably 2 hours to 12 hours.
  • the heating may be performed while applying pressure while maintaining the close contact between the negative electrode and the lithium source.
  • lithium After completing the required amount of lithium pre-doping, if lithium remains on the electrode, it may be removed. When a lithium foil or the like formed on a substrate is used as a lithium source, it can be easily removed.
  • metallic lithium is a highly reactive metal and reacts violently with moisture. Therefore, it is preferable to carry out the work related to lithium pre-doping in a low-humidity environment, and to suppress deterioration of the lithium source, argon It is preferable to work in a gas atmosphere inert to lithium.
  • the positive electrode 2 It does not specifically limit as the positive electrode 2 with which the laminated electrode body 1 which concerns on this embodiment is equipped, A normal positive electrode for secondary batteries can be used.
  • the positive electrode active material contained in the positive electrode 2 include lithium manganate having a layered structure such as LiMnO 2 and Li x Mn 2 O 2 (0 ⁇ x ⁇ 2) or lithium manganate having a spinel structure; LiCoO 2 , LiNiO 2 or a part of these transition metals replaced with other metals; lithium transition metal oxides with less than half of specific transition metals such as LiNi 1/3 Co 1/3 Mn 1/3 O 2 ; Examples of these lithium transition metal oxides include those in which Li is excessive in comparison with the stoichiometric composition.
  • the positive electrode active material contained in the positive electrode one kind may be used alone, or two or more kinds may be used in combination.
  • the positive electrode 2 As a method for producing the positive electrode 2, for example, at least a positive electrode active material, a conductivity imparting agent, and a binder are dispersed and kneaded in a solvent such as N-methyl-2-pyrrolidone that can dissolve the binder.
  • a positive electrode slurry is prepared.
  • the binder the same as the negative electrode can be used.
  • the positive electrode slurry can be prepared by applying the positive electrode slurry onto a positive electrode current collector such as aluminum and drying the solvent. Further, the porosity may be adjusted by pressing the dried positive electrode.
  • the positive electrode current collector the same as the negative electrode current collector can be used.
  • the positive electrode may be manufactured by growing a positive electrode active material or the like on the positive electrode current collector by a vapor phase method such as vapor deposition or sputtering.
  • Examples of the material of the negative electrode lead terminal 7 and the positive electrode lead terminal 7 according to the present embodiment include Al, Cu, Ni, Ti, Fe, phosphor bronze, brass, and stainless steel. These may be used alone or in combination of two or more or as an alloy.
  • the negative electrode lead terminal 4 and the positive electrode lead terminal 5 may be annealed.
  • a normal secondary battery separator can be used.
  • a woven fabric, a nonwoven fabric, a porous film, etc. can be used.
  • polypropylene, polyethylene, and a polyamide-based porous film having a molecular skeleton made of aromatic are preferable from the viewpoints of thinning and large area, and film strength and film resistance.
  • the surface of the separator 4 may be coated with an oxide such as aluminum oxide.
  • the separator 4 what laminated
  • the electrolytic solution used in the present embodiment is not particularly limited, and a normal secondary battery electrolytic solution can be used.
  • a nonaqueous electrolytic solution in which a lithium salt is dissolved as an electrolyte in a nonaqueous solvent can be used.
  • lithium salt examples include LiPF 6 , LiAsF 6 , LiAlCl 4 , LiClO 4 , LiBF 4 , LiSbF 6 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , Li (CF 3 SO 2 ) 2 , LiN (CF 3 SO 2) 2, LiN (SO 2 F) 2 and the like.
  • the lithium salt as the supporting salt is preferably LiPF 6 or LiBF 4 . These supporting salts may be used alone or in combination of two or more.
  • non-aqueous solvent examples include at least one selected from the group consisting of cyclic carbonates, chain carbonates, aliphatic carboxylic acid esters, cyclic ethers, chain ethers, ⁇ -lactones, and derivatives thereof.
  • the above organic solvents are mentioned.
  • Specific examples of the cyclic carbonates include propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), vinylene carbonate (VC), and derivatives thereof.
  • chain carbonates include dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (MEC), dipropyl carbonate (DPC), and derivatives thereof.
  • aliphatic carboxylic acid esters include methyl formate, methyl acetate, ethyl propionate, and derivatives thereof.
  • cyclic ethers include tetrahydrofuran, 2-methyltetrahydrofuran and the like.
  • chain ethers include 1,2-ethoxyethane (DEE), ethoxymethoxyethane (EME), diethyl ether, and derivatives thereof.
  • DEE 1,2-ethoxyethane
  • EME ethoxymethoxyethane
  • diethyl ether and derivatives thereof.
  • non-aqueous solvents include dimethyl sulfoxide, formamide, acetamide, dimethylformamide, dioxolane such as 1,3-dioxolane, dioxolane derivatives, acetonitrile, propylnitrile, nitromethane, ethyl monoglyme, phosphate triester, Trimethoxymethane, sulfolane, methylsulfolane, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2-oxozolidinone, propylene carbonate derivative, tetrahydrofuran derivative, ethyl ether, 1,3-propane sultone, anisole, N- Examples thereof include methyl pyrrolidone and fluorinated carboxylic acid esters. These non-aqueous solvents may be used alone or in combination of two or more.
  • an ionic liquid can be used as the electrolytic solution.
  • the ionic liquid include quaternary ammonium-imide salts.
  • phosphate ester can also be used as electrolyte solution. Examples of the phosphate ester include triethyl phosphate.
  • a solid electrolyte may be used instead of a liquid electrolyte.
  • a gel electrolyte may be used.
  • the exterior body according to the present embodiment is stable to the electrolytic solution, and has a sufficient barrier property against water vapor, if further electrolyte as it can seal the laminated electrode body 1 without leaking, and in particular Without being limited, a laminate outer body such as a laminate film, a metal can, or the like can be used.
  • a laminate film such as polyethylene coated with aluminum or silica can be used as the outer package.
  • Example 1 [Production of negative electrode] SiO (trade name: “SIO19PB”, High-Purity Chemical Research Laboratory), carbon black (trade name: “# 3030B”, manufactured by Mitsubishi Chemical Corporation), and polyamic acid (trade name: “U-Varnish”) A ”and Ube Industries, Ltd.) were weighed at a mass ratio of 75: 5: 20, respectively. These and n-methylpyrrolidone (NMP) were mixed using a homogenizer to form a slurry. The mass ratio of NMP to solid content was 57:43. The slurry was applied onto a copper foil using a doctor blade. Then, it heated at 120 degreeC for 7 minute (s), and dried NMP. Then, it heated at 350 degreeC for 1 hour using the electric furnace in nitrogen atmosphere, and produced the negative electrode.
  • NMP n-methylpyrrolidone
  • Lithium pre-dope A lithium foil having a thickness of 20 ⁇ m was prepared as a lithium source. A surface layer (about 90% by mass of lithium nitride) mainly made of lithium nitride having a thickness of about 0.1 ⁇ m covers 90% or more of the lithium foil surface.
  • the lithium foil was placed on the negative electrode in an aluminum laminate bag and sealed while reducing the pressure to -0.1 MPa.
  • the aluminum laminate bag was heat-treated at 100 ° C. for 24 hours in a thermostatic bath. After the heat treatment was completed, the electrode was taken out from the bag after the aluminum laminate bag was completely returned to room temperature (23 ° C.) or lower, and lithium pre-doping was completed.
  • all lithium sources were doped in the electrode after the heat treatment.
  • Lithium transition metal oxide LiNi 0.80 Co 0.15 Al 0.15 O 2
  • carbon black as a conductivity imparting agent
  • polyvinylidene fluoride as a positive electrode binder
  • the produced laminated electrode element was wrapped with an aluminum laminate film as an outer package, and an electrolytic solution was injected therein, and then sealed in a state where the pressure was reduced to 0.1 atm. Thus, a secondary battery was produced.
  • Example 2 [Preparation of negative electrode] A negative electrode was produced in the same manner as in Example 1.
  • Lithium pre-dope A lithium foil having a thickness of 20 ⁇ m was prepared as a lithium source. A surface layer (about 90% by mass of lithium nitride) mainly made of lithium nitride having a thickness of about 1 ⁇ m covers 90% or more of the lithium foil surface.
  • the lithium foil was placed on the negative electrode in an aluminum laminate bag and sealed while reducing the pressure to -0.1 MPa.
  • the aluminum laminate bag was heat-treated at 100 ° C. for 24 hours in a thermostatic bath. After the heat treatment was completed, the electrode was taken out from the bag after the aluminum laminate bag was completely returned to room temperature (23 ° C.) or lower, and lithium pre-doping was completed.
  • all lithium sources were doped in the electrode after the heat treatment.
  • a positive electrode was produced in the same manner as in Example 1.
  • a secondary battery was fabricated in the same manner as in Example 1.
  • the fabricated negative electrode and secondary battery were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
  • Example 3 [Preparation of negative electrode] A negative electrode was produced in the same manner as in Example 1.
  • Lithium pre-dope As a lithium source, a 20 ⁇ m thick lithium foil formed on a 15 ⁇ m copper foil (base material) was prepared. A surface layer (about 90% by mass of lithium nitride) mainly made of lithium nitride having a thickness of about 1 ⁇ m covers 90% or more of the lithium foil surface.
  • the lithium foil was placed on the negative electrode in an aluminum laminate bag and sealed while reducing the pressure to -0.1 MPa. It was then subjected to heat treatment 100 ° C. 24 hours aluminum laminated bag in a thermostat. After the heat treatment was completed, after the aluminum laminate bag was completely returned to room temperature (23 ° C.) or lower, the electrode was taken out from the bag and the copper foil as the base material of the lithium source was removed to complete the lithium pre-doping. In the negative electrode produced in this example, all lithium sources were doped in the electrode after the heat treatment.
  • a positive electrode was produced in the same manner as in Example 1.
  • a secondary battery was fabricated in the same manner as in Example 1.
  • the fabricated negative electrode and secondary battery were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
  • Example 4 [Preparation of negative electrode] A negative electrode was produced in the same manner as in Example 1.
  • Lithium pre-dope As a lithium source, a 50 ⁇ m thick lithium foil formed on a 15 ⁇ m copper foil (base material) was prepared. It is a surface layer (about 90% by mass of lithium nitride) mainly made of lithium nitride having a thickness of about 1 ⁇ m and covers 90% or more of the lithium foil surface.
  • the lithium foil was placed on the negative electrode in an aluminum laminate bag and sealed while reducing the pressure to -0.1 MPa.
  • the aluminum laminate bag was heat-treated at 100 ° C. for 24 hours in a thermostatic bath. After the heat treatment is completed, after the aluminum laminate bag is completely returned to room temperature (23 ° C.) or lower, the electrode is taken out of the bag, and the copper foil that is the base material of the lithium source and the lithium remaining on the copper foil are removed. Completed pre-doping. In the negative electrode produced in this example, surplus lithium with respect to the doping amount remained on the copper foil of the base material.
  • a positive electrode was produced in the same manner as in Example 1.
  • a secondary battery was fabricated in the same manner as in Example 1.
  • the fabricated negative electrode and secondary battery were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
  • Example 5 [Production of negative electrode] A negative electrode was produced in the same manner as in Example 1.
  • Lithium pre-doping As a lithium source, a 50 ⁇ m thick lithium foil formed on a 15 ⁇ m copper foil (base material) was prepared. A surface layer (about 90% by mass of lithium nitride) mainly made of lithium nitride having a thickness of about 1 ⁇ m covers 90% or more of the lithium foil surface.
  • the entire surface of the lithium source and the negative electrode was uniformly pressurized at 5 kgf / cm 2 .
  • the lithium source and the negative electrode that were brought into close contact by pressurization were accommodated in an aluminum laminate bag and sealed under reduced pressure.
  • the aluminum laminate bag was heat-treated at 100 ° C. for 24 hours in a thermostatic bath. After the heat treatment is completed, after the aluminum laminate bag is completely returned to room temperature (23 ° C.) or lower, the electrode is taken out of the bag, and the copper foil that is the base material of the lithium source and the lithium remaining on the copper foil are removed. Completed pre-doping. In the negative electrode produced in this example, surplus lithium with respect to the doping amount remained on the copper foil of the base material.
  • a positive electrode was produced in the same manner as in Example 1.
  • a secondary battery was fabricated in the same manner as in Example 1.
  • the fabricated negative electrode and secondary battery were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
  • Example 6 [Preparation of negative electrode] A negative electrode was produced in the same manner as in Example 1.
  • Lithium pre-dope As a lithium source, a 50 ⁇ m thick lithium foil formed on a 15 ⁇ m copper foil (base material) was prepared. A surface layer (about 90% by mass of lithium nitride) mainly made of lithium nitride having a thickness of about 1 ⁇ m covers 90% or more of the lithium foil surface.
  • the entire surface of the lithium source and the negative electrode was uniformly pressurized at 10 kgf / cm 2 .
  • the lithium source and the negative electrode that were brought into close contact by pressurization were accommodated in an aluminum laminate bag and sealed under reduced pressure.
  • the aluminum laminate bag was heat-treated at 100 ° C. for 16 hours in a thermostatic bath. After the heat treatment is completed, after the aluminum laminate bag is completely returned to room temperature (23 ° C.) or lower, the electrode is taken out of the bag, and the copper foil that is the base material of the lithium source and the lithium remaining on the copper foil are removed. Completed pre-doping. In the negative electrode produced in this example, surplus lithium with respect to the doping amount remained on the copper foil of the base material.
  • a positive electrode was produced in the same manner as in Example 1.
  • a secondary battery was fabricated in the same manner as in Example 1.
  • the fabricated negative electrode and secondary battery were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
  • Example 7 [Preparation of negative electrode] A negative electrode was produced in the same manner as in Example 1.
  • Lithium pre-dope As a lithium source, a 50 ⁇ m thick lithium foil formed on a 15 ⁇ m copper foil (base material) was prepared. A surface layer (about 90% by mass of lithium nitride) mainly made of lithium nitride having a thickness of about 1 ⁇ m covers 90% or more of the lithium foil surface.
  • the entire surface of the lithium source and the negative electrode was uniformly pressurized at 5 kgf / cm 2 .
  • the lithium source and the negative electrode that were brought into close contact by pressurization were accommodated in an aluminum laminate bag and sealed under reduced pressure.
  • the aluminum laminate bag was heat-treated at 60 ° C. for 24 hours in a thermostatic bath. After the heat treatment is completed, after the aluminum laminate bag is completely returned to room temperature (23 ° C.) or lower, the electrode is taken out of the bag, and the copper foil that is the base material of the lithium source and the lithium remaining on the copper foil are removed. Completed pre-doping. In the negative electrode produced in this example, surplus lithium with respect to the doping amount remained on the copper foil of the base material.
  • a positive electrode was produced in the same manner as in Example 1.
  • a secondary battery was fabricated in the same manner as in Example 1.
  • the fabricated negative electrode and secondary battery were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
  • Lithium pre-dope A lithium foil having a thickness of 20 ⁇ m was prepared as a lithium source. On the surface of the lithium foil, which is mainly the surface layer having a thickness of about 2 ⁇ m consisting of lithium carbonate and lithium nitride is formed, in the surface layer, the proportion of lithium nitride is 25% by weight, the proportion of lithium carbonate is from about 70 weight %, And the proportion of lithium oxide was about 5%. The surface layer covers 90% or more of the lithium foil surface.
  • the lithium foil was placed on the negative electrode in an aluminum laminate bag and sealed while reducing the pressure to -0.1 MPa. It was then subjected to heat treatment 100 ° C. 24 hours aluminum laminated bag in a thermostat. After the heat treatment was completed, the electrode was taken out from the bag after the aluminum laminate bag was completely returned to room temperature (23 ° C.) or lower, and lithium pre-doping was completed. In the negative electrode produced in this example, to remove the lithium source left on the electrode after the heat treatment.
  • a positive electrode was produced in the same manner as in Example 1.
  • a secondary battery was fabricated in the same manner as in Example 1.
  • the fabricated negative electrode and secondary battery were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
  • Example 3 it was confirmed that the same effect was obtained even when pre-doping was performed using a lithium source formed on a substrate (Example 3). Further, it was confirmed that the same effect was obtained when the thickness of the lithium source was changed and the lithium source remaining after the lithium pre-doping was removed (Example 4). Furthermore, it was confirmed that the same effect was obtained when the lithium source and the electrode were brought into close contact with each other using pressure (Examples 5 and 6). Further, it was confirmed that the same effect can be obtained even if the heating temperature and time are changed in the lithium pre-doping step (Examples 5 to 7).
  • Example 8> [Preparation of negative electrode] After the surface of SiO (trade name: “SIO19PB”, High-Purity Chemical Laboratory Co., Ltd.) is uniformly coated with carbon by chemical vapor deposition (coating amount is about 5/75 by mass with respect to SiO), carbon The coated SiO and polyamic acid (trade name: “U-Varnish A”, manufactured by Ube Industries, Ltd.) were weighed at a mass ratio of 80:20, respectively. These and n-methylpyrrolidone (NMP) were mixed using a homogenizer to form a slurry. The mass ratio of NMP to solid content was 57:43. The slurry was applied onto a copper foil using a doctor blade. Then, it heated at 120 degreeC for 7 minute (s), and dried NMP. Then, it heated at 350 degreeC for 1 hour using the electric furnace in nitrogen atmosphere, and produced the negative electrode.
  • SiO trade name: “SIO19PB”, High-Purity Chemical Laboratory Co., Ltd.
  • Lithium pre-doping was performed in the same manner as in Example 1. The amount of lithium pre-doping was 1.1 mg / cm 2 .
  • a positive electrode was produced in the same manner as in Example 1.
  • a secondary battery was fabricated in the same manner as in Example 1.
  • the fabricated negative electrode and secondary battery were evaluated in the same manner as in Example 1.
  • the capacity retention rate was 88%.
  • the secondary battery of the present invention is a secondary battery having high energy density and good cycle characteristics, and is used in all industrial fields that require a power source and industrial fields related to transportation, storage and supply of electrical energy. can do. Specifically, it can be used for a power source of a mobile device, a power source of a moving / transport medium, a backup power source, a solar power generation, a wind power generation, and a power storage facility for storing power generated by the power generation.

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Abstract

L'invention concerne un accumulateur lithium-ion, lequel comporte un corps d'électrode multicouche (1), une électrode positive (2) et une électrode négative (3) contenant un matériau actif qui est capable d'adsorber et de désorber du lithium étant agencées face à face, qui est produit par un procédé qui comprend une étape dans laquelle une source de lithium ayant une couche de surface qui contient 30 % en masse ou plus de nitrure de lithium est mise en contact avec le matériau actif d'électrode négative. L'accumulateur lithium-ion ainsi obtenu a une densité d'énergie élevée et de bonnes caractéristiques de cycle.
PCT/JP2013/063558 2012-06-12 2013-05-15 Procédé de production d'un accumulateur lithium-ion et accumulateur lithium-ion WO2013187176A1 (fr)

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JP2022517987A (ja) * 2019-01-14 2022-03-11 バテル メモリアル インスティチュート ケイ素アノード用の局在化超高濃度電解質
CN111952517A (zh) * 2020-08-26 2020-11-17 复阳固态储能科技(溧阳)有限公司 一种含氮化锂薄膜层的隔膜及其制备方法和应用

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