WO2011152244A1 - Alloy negative electrode for lithium battery and process for production thereof, and lithium battery - Google Patents

Alloy negative electrode for lithium battery and process for production thereof, and lithium battery Download PDF

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WO2011152244A1
WO2011152244A1 PCT/JP2011/061834 JP2011061834W WO2011152244A1 WO 2011152244 A1 WO2011152244 A1 WO 2011152244A1 JP 2011061834 W JP2011061834 W JP 2011061834W WO 2011152244 A1 WO2011152244 A1 WO 2011152244A1
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Prior art keywords
aluminum
negative electrode
lithium battery
resin
alloy negative
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PCT/JP2011/061834
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French (fr)
Japanese (ja)
Inventor
進啓 太田
上村　卓
細江　晃久
真嶋　正利
新田　耕司
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住友電気工業株式会社
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Priority to KR1020127029168A priority Critical patent/KR20130042487A/en
Priority to CN2011800254727A priority patent/CN102906906A/en
Publication of WO2011152244A1 publication Critical patent/WO2011152244A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • H01M4/808—Foamed, spongy materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • 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
    • H01M4/36—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
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • H01M4/463—Aluminium based
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • 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 an alloy negative electrode for a lithium battery using a porous aluminum body, a method for producing the same, and a lithium battery.
  • lithium secondary batteries such as lithium ion batteries used for portable information terminals, electric vehicles, and household power storage devices have been actively researched.
  • Non-Patent Document 1 discloses a Li—Al (negative electrode) / MnO 2 (positive electrode) lithium secondary battery.
  • the lithium secondary battery described above has difficulty in achieving industrial mass production because the Li—Al alloy as the negative electrode is fragile.
  • An alloy negative electrode for a lithium battery according to the present invention comprises: An alloy negative electrode for a lithium battery using a non-aqueous electrolyte, The aluminum porous body is filled with lithium metal.
  • the present inventor has intensively studied to solve the above problems. As a result, the present inventors have found that it is effective to use a Li—Al alloy produced by filling lithium metal in a porous aluminum body as a negative electrode instead of the conventional plate-like Li—Al alloy.
  • the Li—Al alloy negative electrode filled with lithium metal in the aluminum porous body has a skeleton as a core, and is not as brittle as the conventional Li—Al alloy negative electrode. Is preferred.
  • the Al concentration decreases as the distance from the skeleton of the porous body increases, that is, the central portion of the skeleton of the porous body becomes thinner. Therefore, the expansion and contraction stress accompanying the charge / discharge cycle is dispersed and relaxed. As a result, even when the depth of discharge is increased, cracking of the electrode and the like are suppressed, generation of pulverization is suppressed, and a sufficient charge / discharge cycle can be ensured.
  • the alloy negative electrode for lithium battery A skeleton of the aluminum porous body is formed of aluminum.
  • the skeleton of the aluminum porous body itself is made of aluminum, a Li—Al alloy can be formed using only the skeleton. For this reason, the alloy negative electrode for lithium batteries with a high porosity and a larger capacity density can be provided.
  • the lithium battery alloy negative electrode is The skeleton of the aluminum porous body is formed by an aluminum coating material in which an aluminum layer is formed on the surface of a core material made of any metal of copper, nickel, and iron.
  • the alloy negative electrode for lithium batteries of the present invention uses a metal of copper, nickel, or iron as the core material of the aluminum porous body. These metals are not alloyed with lithium or aluminum, but have high mechanical strength, so that a porous body having excellent strength can be formed. For this reason, the porous body in which the aluminum layer is formed on the surface of the core material made of these metals can provide an alloy negative electrode for a lithium battery that is strong against expansion and contraction.
  • the ratio of the volume of the lithium metal in the pores of the aluminum porous body is 50% or more and less than 100%.
  • the volume ratio of lithium metal is less than 100%, and vacancies remain in the porous aluminum body after filling Li, so even when dendrites are produced, the dendrites are mainly produced in the vacancies. . For this reason, a dendrite short is suppressed effectively.
  • the volume ratio of the lithium metal is less than 50%, there is a possibility that the practical action as an alloy negative electrode for a lithium battery cannot be sufficiently exhibited.
  • the amount of oxygen on the surface of aluminum forming the skeleton of the aluminum porous body or the aluminum layer of the aluminum covering material is 3.1% by mass or less.
  • the aluminum porous body of the alloy negative electrode for lithium batteries of the present invention has an oxygen content of 3.1% by mass or less on the surface of aluminum forming the skeleton of the aluminum porous body or the aluminum layer of the aluminum coating material. It is possible to provide a battery alloy negative electrode having an unprecedented higher capacity density.
  • Al Since Al is easily oxidized from the beginning, there has been no porous aluminum body having a sufficiently small amount of oxygen on the surface.
  • aluminum prepared by applying Al powder on the surface of an Al eutectic alloy film formed on the surface of a foamed resin described in JP-A-8-170126 and then heat-treating it in a non-oxidizing atmosphere.
  • the amount of oxygen on the surface is large.
  • the filled Li is oxidized by oxygen (O 2 ) and changed to Li 2 O that does not function as an active material, so that a large capacity density cannot be obtained. Further, the generated Li 2 O becomes a resistance layer, and the characteristics are deteriorated.
  • the present inventor has researched an aluminum porous body having a small amount of oxygen and succeeded in developing an aluminum porous body having an oxygen content of 3.1% by mass or less.
  • the present invention is characterized by using such an aluminum porous body. Since an aluminum porous body having a surface oxygen content of 3.1% by mass or less is used, an alloy negative electrode for a lithium battery having a higher capacity density can be obtained. .
  • FIG. 1A to 1C are schematic diagrams showing an outline of the first stage.
  • FIG. 1A is an enlarged schematic view showing a part of a cross section of a resin 1 having communication holes, and shows a state in which holes are formed using the resin 1 as a skeleton.
  • FIG. 1B shows a state (aluminum layer coating resin 3) in which an aluminum layer 2 is formed on the surface of the resin 1 having communication holes.
  • FIG. 1C shows a state (resin aluminum porous body 4) after the resin 1 is thermally decomposed and disappeared from the aluminum layer coating resin 3.
  • FIG. 2 shows a process of thermally decomposing the resin 1 from the aluminum layer coating resin 3.
  • the aluminum layer coating resin 3 and the positive electrode 5 are immersed in the molten salt 6, and the aluminum layer 2 is kept at a lower potential than the standard electrode potential of aluminum.
  • the positive electrode 5 can be appropriately selected as long as it shows insolubility in the molten salt.
  • an electrode made of platinum, titanium, or the like is used.
  • the aluminum porous body 4 manufactured by this method has a hollow fiber shape due to the characteristics of the manufacturing method. In this respect, it differs from the structure of the aluminum foam as disclosed in JP-A-2002-371327.
  • the heating temperature is set to be equal to or lower than the melting point of aluminum in order to prevent melting of aluminum. Specifically, it is preferable to heat at 660 ° C. or lower, which is the melting point of aluminum.
  • any resin can be selected as the resin in the present invention as long as it thermally decomposes at a temperature lower than the melting point of aluminum.
  • urethane foam is a raw material with high porosity and is easy to thermally decompose, urethane foam is preferable as resin used for the manufacturing method of this invention.
  • the resin preferably has a porosity of 80% to 98% and a pore diameter of about 50 ⁇ m to 500 ⁇ m.
  • the resin preferably has a communication hole. Thereby, the aluminum porous body without a closed pore is obtained.
  • the aluminum on the surface of the porous aluminum body described above had an extremely low oxygen content and was 3.1% by mass or less, which is the precipitation limit of EDX analysis.
  • the communication hole is formed of only aluminum because it has a closed hole but does not have a closed pore and does not use a eutectic alloy.
  • the aluminum porous body 4 is filled with Li metal.
  • the method for filling is not particularly limited, and for example, a known method such as a method of inclusion, a vacuum deposition method, or an electroplating method can be used.
  • the alloy negative electrode for lithium batteries described above is
  • the aluminum porous body has communication holes, no closed pores, Furthermore, it consists only of aluminum.
  • a conventional aluminum porous body for example, an aluminum porous body which is foamed by adding a foaming agent in a molten state described in JP-A-2002-371327 has many closed pores.
  • the aluminum porous body described in JP-A-8-170126 is a eutectic metal, it contains Bi, Ca and other metals other than Al.
  • a sufficient amount of Li cannot be filled, so that a large capacity density cannot be obtained.
  • a metal other than Al is contained, the function of the Li—Al alloy as a negative electrode is lowered.
  • the alloy negative electrode for lithium batteries of the present invention can be filled with a sufficient amount of Li metal, so that an alloy negative electrode for lithium batteries having a higher capacity density can be obtained. Further, since the aluminum porous body is made of only aluminum, the function as the negative electrode can be sufficiently exhibited.
  • the lithium battery according to the present invention is It is characterized by including the lithium battery alloy negative electrode described in (1) to (6) above.
  • the lithium battery of the present invention uses the lithium battery alloy having the above characteristics as the negative electrode, it is possible to provide a lithium battery having a large capacity density and excellent charge / discharge cycle characteristics.
  • a method for producing an alloy negative electrode for a lithium battery according to the present invention comprises: An aluminum layer forming step of forming an aluminum layer on the surface of the resin having communication holes; While the resin layer is immersed in the molten salt, the resin layer is heated to a temperature below the melting point of aluminum while maintaining the aluminum layer at a potential lower than the standard electrode potential of aluminum, and the resin is thermally decomposed to form porous aluminum.
  • the amount of oxygen on the surface of the aluminum layer is 3.1% by mass or less, has communication holes, does not have closed pores, It is possible to provide an alloy negative electrode for a lithium battery having a large capacity density using an aluminum porous body made only of aluminum and having a high effect of suppressing pulverization and dendrite short.
  • a method for producing an alloy negative electrode for a lithium battery according to the present invention comprises: A metal layer forming step of forming a metal layer made of one of copper, nickel, and iron on the surface of the resin having communication holes; An aluminum layer forming step of forming an aluminum layer on the surface of the metal layer; In a state where the resin is immersed in the molten salt, the resin is heated to a temperature below the melting point of aluminum while maintaining the aluminum layer at a potential lower than the standard electrode potential of aluminum, and the resin is thermally decomposed to form porous aluminum.
  • the amount of oxygen on the surface of the aluminum layer is 3.1% by mass or less, and has an open pore and no closed pores.
  • a lithium battery alloy negative electrode with a large capacity density using a body and an excellent charge / discharge cycle can be provided.
  • the porous aluminum body has a skeleton made of a metal made of copper, nickel, or iron. Therefore, it is possible to provide a lithium battery alloy negative electrode having high strength.
  • the manufacturing method of the said alloy negative electrode for lithium batteries is as follows.
  • the method for forming the aluminum layer is a vacuum deposition method, a sputtering method, a laser ablation method, or a plasma CVD method.
  • an aluminum metal layer is formed by irradiating an aluminum beam as a raw material with an electron beam to melt and evaporate the aluminum metal and adhere the aluminum metal to the resin surface of the resin body having communication holes.
  • an aluminum metal target can be vaporized by plasma irradiation on an aluminum metal target, and an aluminum alloy is adhered to the resin surface of a resin body having communication holes, whereby an aluminum metal layer can be formed.
  • an aluminum metal layer can be formed by melting and evaporating aluminum metal by laser irradiation and attaching the aluminum metal to the resin surface of the resin body having the communication holes.
  • an aluminum metal layer can be formed by applying a high frequency to an aluminum compound as a raw material to form a plasma and attaching it to the surface of a resin having communication holes.
  • the manufacturing method of the said alloy negative electrode for lithium batteries is as follows.
  • the method for forming the aluminum layer is a plating method in which aluminum is plated after the surface of the resin is subjected to a conductive treatment.
  • the manufacturing method of the alloy negative electrode for lithium batteries of this invention is a plating method for plating aluminum on the surface of the metal layer.
  • molten salt electroplating in which aluminum is plated in molten salt is performed.
  • the molten salt used here may be the same as or different from the molten salt to be used in the step of thermally decomposing the resin. Specifically, molten salts such as potassium chloride, aluminum chloride, and sodium chloride are used. Further, a salt of two or more components may be used and used as a eutectic molten salt. The eutectic molten salt is preferable because the melting temperature is lowered. This molten salt needs to contain at least aluminum ions.
  • the manufacturing method of the said alloy negative electrode for lithium batteries is as follows.
  • the method for forming the aluminum layer is a coating method in which an aluminum paste is applied to the surface of the resin or the surface of the metal layer.
  • the aluminum paste When the aluminum paste is applied to the resin surface, the aluminum paste is a mixture of, for example, aluminum powder, a binder (binder resin) and an organic solvent. Specifically, after the aluminum paste is applied to the surface of the resin, it is heated to eliminate the organic solvent and the binder resin, and the aluminum paste is sintered. Heating at the time of sintering may be performed in one step or in multiple steps. For example, the aluminum paste may be sintered at the same time as the resin decomposition by applying aluminum paste and heating at a low temperature to eliminate the organic solvent and then immersing in molten salt and heating.
  • the present invention it is possible to provide a lithium battery alloy negative electrode having a large capacity density and excellent charge / discharge cycle, a method for producing the same, and a lithium battery.
  • FIG. 1A is a schematic view showing a part of a cross section of a resin having a communication hole in a manufacturing process of an aluminum porous body.
  • FIG. 1B is a schematic view showing a state (aluminum layer coating resin) in which an aluminum layer is formed on the surface of a resin having communication holes in the manufacturing process of the aluminum porous body.
  • FIG. 1C is a schematic diagram illustrating a state (aluminum porous body) after the resin is thermally decomposed and disappeared from the aluminum layer coating resin in the manufacturing process of the aluminum porous body.
  • FIG. 2 is a schematic view for explaining a decomposition process of the resin in the molten salt.
  • FIG. 3 is a SEM photograph of the porous aluminum body of the present invention.
  • FIG. 4 is a view showing an EDX analysis result of the aluminum porous body according to the present invention.
  • FIG. 5 is a diagram illustrating a lithium battery according to the present invention.
  • (Embodiment 1) A. Lithium battery alloy negative electrode
  • an aluminum porous body is filled with lithium metal, and the skeleton of the aluminum porous body is formed of aluminum. Then, the lithium battery alloy negative electrode in the present embodiment is manufactured by the following manufacturing method (see FIGS. 1A to 1C).
  • porous resin 1 a foamed resin or nonwoven fabric having communication holes is used, and a resin having a porosity of 80% to 98% and a pore diameter of about 50 ⁇ m to 500 ⁇ m is particularly preferable.
  • Foam urethane is preferably used.
  • the manufacturing method of the alloy negative electrode for lithium batteries is demonstrated in order of an aluminum layer formation process, an aluminum porous body preparation process, and a lithium metal containing (filling) process.
  • An aluminum layer 2 is directly formed on the surface of the resin 1 by a vapor deposition method such as vacuum deposition, sputtering, laser ablation or plasma CVD, plating, aluminum paste coating, or the like.
  • the aluminum layer coating resin 3 is produced.
  • the surface of the resin 1 is subjected to a conductive treatment in advance.
  • a conductive treatment an arbitrary method such as electroless plating of a conductive metal such as nickel, vapor deposition or sputtering of aluminum or the like, or application of a conductive paint containing conductive particles such as carbon is selected.
  • a plating bath for aluminum plating for example, a multi-component molten salt of AlCl 3 —XCl (X: alkali metal) -MCl X (M is an additive element selected from Cr, Mn, and a transition metal element) Is used.
  • Resin 1 is immersed in the molten salt, and electroplating is performed using the conductive resin as the negative electrode.
  • the formation of the aluminum layer can also be performed by applying an aluminum paste as described above.
  • the aluminum paste is a mixture of aluminum powder, a binder (binder resin), and an organic solvent. After applying a predetermined amount of aluminum paste to the surface of the resin 1, it is sintered in a non-oxidizing atmosphere.
  • FIG. 2 is a schematic diagram for explaining a decomposition process of the porous resin in the molten salt 6.
  • Resin i.e., the aluminum layer coating resin 3
  • a salt containing one or more selected from the group consisting of AlCl 3 aluminum below the melting point, preferably Is heated at a temperature of 500 ° C. to 600 ° C., and a predetermined voltage is applied between the positive electrode 5 made of platinum or titanium, so that the aluminum layer of the aluminum layer coating resin 3 has a lower potential than the standard electrode potential of aluminum.
  • the porous resin 1 is thermally decomposed and removed while maintaining at (a potential nobler than the reduction potential of Li, K, Na), and the porous aluminum body 4 of FIG. 1C is produced.
  • a predetermined amount of lithium metal is contained in the produced porous aluminum body to produce an alloy of lithium and aluminum (Li—Al alloy) to form an alloy negative electrode for a lithium battery.
  • an aluminum porous body and a lithium foil having a predetermined thickness are bonded together, and then heated to 180 ° C. or higher to melt the lithium foil and permeate the pores of the aluminum porous body.
  • the aluminum porous body may be immersed in a molten lithium bath heated to 180 ° C. or higher.
  • the amount of lithium to be included is adjusted so that the ratio of the volume of lithium metal in the pores of the aluminum porous body is 50% or more and less than 100%. For example, when an aluminum porous body having a porosity of 97% and a lithium foil having a thickness of 1 ⁇ 2 of an aluminum porous body are bonded together, the ratio of the volume of lithium metal in the pores is 51.5%.
  • the resulting Li—Al alloy has a high aluminum concentration near the skeleton and a lower concentration gradient as the distance from the skeleton increases. For this reason, even when the Li—Al alloy expands and contracts during charge / discharge, the stress is easily relaxed, and pulverization is suppressed.
  • the ratio of the volume of lithium metal in the pores of the aluminum porous body is 50% or more, a sufficiently high capacity density is ensured, while in the aluminum porous body after filling Li by setting it to less than 100% As a result, the dendrite short circuit is suppressed even when lithium dendrite is generated.
  • the skeleton of the aluminum porous body is an aluminum covering material in which an aluminum layer is formed on the surface of the core material.
  • the core is made of copper, nickel, or iron, and is formed by applying carbon powder to the surface of the resin having the communication holes and conducting a conductive treatment, followed by plating with a predetermined thickness. Is done.
  • Embodiment 2 manufactures an alloy negative electrode for lithium batteries and a lithium battery in the same manner as Embodiment 1, except that the skeleton of the porous aluminum body is an aluminum coating material.
  • the lithium metal inclusion is not limited to the penetration of the porous aluminum body into the pores, but may be formed on the surface of the porous aluminum body.
  • the lithium metal does not have to be a single element, and may be an alloy with another metal.
  • Li—Si (silicon) and Li—Sn (tin) are suitable as an alloy negative electrode.
  • an alloy layer of Li and Si or Sn may be formed on the surface of the aluminum porous body, or “aluminum skeleton”
  • a Si or Sn metal layer may be provided on an “aluminum layer formed on the surface of a core material such as copper”, and a Li metal layer may be further stacked.
  • Example 1 is a lithium secondary battery having a negative electrode formed by including lithium metal in an aluminum porous body having a skeleton formed of aluminum.
  • Example 2 is a lithium secondary battery having a negative electrode formed by including lithium metal in an aluminum porous body that is an aluminum coating material in which an aluminum layer is formed on the surface of a core material having a skeleton made of Cu.
  • Example 1 Production of porous aluminum body
  • An aluminum layer having a thickness of about 50 ⁇ m is formed on the surface of the polyurethane foam by a vacuum deposition method, and then immersed in a LiCl—KCl eutectic molten salt at a temperature of 500 ° C., so that the aluminum layer has a lower potential than the standard electrode potential of aluminum. For 30 minutes.
  • Example 2 a polyurethane foam having a porosity of 97% and a pore diameter of about 300 ⁇ m was prepared. After applying carbon powder on the surface of this polyurethane foam and conducting a conductive treatment, copper plating with a thickness of 20 ⁇ m was applied to form a core material. A surface layer of aluminum having a thickness of about 50 ⁇ m is formed thereon by vacuum deposition, and then immersed in a LiCl—KCl eutectic molten salt at a temperature of 500 ° C., and the aluminum layer is 30 bases lower than the standard electrode potential of aluminum. Hold for a minute.
  • a foamed urethane foam having a pore diameter of 200 ⁇ m to 500 ⁇ m, a porosity of 97%, and a thickness of 1.0 mm was prepared.
  • This foamed urethane foam was placed in a vacuum deposition apparatus.
  • An aluminum film was deposited on the surface of the foamed urethane resin by a vacuum deposition method in which aluminum metal was melted and evaporated. Thereafter, the foamed urethane foam was removed by heat treatment at 550 ° C. in the atmosphere. This obtained the aluminum porous body which is a reference example.
  • the surface of the aluminum porous body of Example 1 was subjected to EDX analysis at an acceleration voltage of 15 kV. The result is shown in FIG. No oxygen peak was observed. Therefore, it was found that the oxygen content of the aluminum porous body was below the detection limit of EDX.
  • the detection limit by EDX is an oxygen content of 3.1% by mass, it can be said that the oxygen content on the surface of the porous aluminum body of Example 1 is 3.1% by mass or less.
  • Example 2 SEM photography and EDX analysis were performed, and it was confirmed that the result was the same as Example 1.
  • the surface of the aluminum porous body of the reference example was also subjected to EDX analysis under the same conditions. As a result, an oxygen peak was observed, and it was found that the oxygen content of the aluminum porous body exceeded at least 3.1 mass%. This is because the surface of the aluminum porous body was oxidized during the heat treatment.
  • EDAX Phonenix manufactured by EDAX
  • HIT22 136-2.5 HIT22 136-2.5.
  • An aluminum porous body in which lithium metal was infiltrated into pores was formed into a circle having a diameter of 15 mm to produce an alloy negative electrode for a lithium battery.
  • FIG. 5 is a diagram for explaining the configuration of the lithium battery of this embodiment.
  • 11 is a lithium secondary battery
  • 12 is a positive electrode for a lithium battery
  • 13 is a separator
  • 14 is an alloy negative electrode for a lithium battery.
  • an electrolyte made of a mixed solution of propylene carbonate / ethylene carbonate / dimethoxyethane in which 1 mol% of LiClO 4 was dissolved by laminating a polypropylene separator 13 between the positive electrode 12 and the negative electrode 14. It assembled using the liquid.
  • a comparative example is a lithium secondary battery having a negative electrode of an Al—Li alloy foil.
  • An Al—Li alloy foil having an aluminum ratio of 50 atomic% and a diameter of 15 mm was prepared as an alloy negative electrode for a lithium battery, and this negative electrode and a positive electrode for a lithium battery prepared in the same manner as in the examples were used.
  • a lithium secondary battery was produced in the same manner as in the example.
  • Test results Table 1 shows the test results of Examples 1 and 2 and the comparative example.
  • Table 1 shows that Examples 1 and 2 have excellent cycle characteristics.
  • the reason why the cycle characteristics of the examples are excellent in this way is that an alloy negative electrode for a lithium battery having a high effect of suppressing pulverization and dendrite short is used.
  • the example is a lithium secondary battery having a lithium battery alloy negative electrode having a high capacity density because Li is contained in an aluminum porous body having no closed pores and a small amount of oxygen.
  • lithium is contained in an aluminum porous body having no closed pores and a small amount of oxygen, and therefore, an alloy negative electrode for a lithium battery having a large capacity density and an excellent charge / discharge cycle and a method for producing the same And a lithium battery can be provided.

Abstract

Disclosed are: an alloy negative electrode for a lithium battery, which has a high capacity density and excellent charge-discharge cycle properties; a process for producing the alloy negative electrode; and a lithium battery. Specifically disclosed is an alloy negative electrode for a lithium battery, which utilizes a non-aqueous electrolytic solution, wherein metal lithium is filled in an aluminum porous material, the backbone of the aluminum porous material is formed with aluminum, and the backbone of the aluminum porous material is formed with an aluminum coating material which comprises a core material composed of any one metal selected from copper, nickel and iron and an aluminum layer formed on the surface of the core material.

Description

リチウム電池用合金負極とその製造方法およびリチウム電池Alloy negative electrode for lithium battery, method for producing the same, and lithium battery
　本発明は、アルミニウム多孔体を用いたリチウム電池用合金負極とその製造方法およびリチウム電池に関する。 The present invention relates to an alloy negative electrode for a lithium battery using a porous aluminum body, a method for producing the same, and a lithium battery.
　近年、携帯情報端末、電動車両及び家庭用電力貯蔵装置に用いられるリチウムイオン電池等のリチウム二次電池が活発に研究されている。 In recent years, lithium secondary batteries such as lithium ion batteries used for portable information terminals, electric vehicles, and household power storage devices have been actively researched.
　このリチウム二次電池の代表的な例の一つとして、Ｌｉ－Ａｌ（負極）／ＭｎＯ２（正極）リチウム二次電池が非特許文献１に示されている。 As a representative example of this lithium secondary battery, Non-Patent Document 1 discloses a Li—Al (negative electrode) / MnO 2 (positive electrode) lithium secondary battery.
　しかし、上記のリチウム二次電池は、負極であるＬｉ－Ａｌ合金が脆弱であるため、工業的量産を図ることに困難性がある。 However, the lithium secondary battery described above has difficulty in achieving industrial mass production because the Li—Al alloy as the negative electrode is fragile.
　また、放電深度を上げて充放電を行った場合、少ない数の充放電サイクルで大幅な放電容量の劣化を招いていた。例えば、１００％の放電深度で充放電を行った場合、そのサイクル寿命は、数十サイクル程度が限度であった。このため、通常は、１０％程度での放電深度で充放電が行われていた。 In addition, when charging / discharging was performed by increasing the depth of discharge, a small number of charging / discharging cycles caused a significant deterioration of the discharge capacity. For example, when charging / discharging was performed at a discharge depth of 100%, the cycle life was limited to about several tens of cycles. For this reason, charging / discharging is usually performed at a discharge depth of about 10%.
　これらの問題点に鑑み、工業的量産に好適であると共に、放電深度を上げて大きな数の充放電サイクルで充放電を行った場合でも、放電容量の劣化を招く恐れがないリチウム電池用合金負極の開発が望まれていた。 In view of these problems, it is suitable for industrial mass production, and even when charging / discharging is performed with a large number of charging / discharging cycles by increasing the depth of discharge, there is no risk of causing deterioration of the discharge capacity. Development of was desired.
　上記の課題は、以下に示す各発明により解決することができる。 The above problems can be solved by the following inventions.
（１）本発明に係るリチウム電池用合金負極は、
　非水電解液を用いるリチウム電池用合金負極であって、
　アルミニウム多孔体中にリチウム金属が充填されていることを特徴とする。 (1) An alloy negative electrode for a lithium battery according to the present invention comprises:
An alloy negative electrode for a lithium battery using a non-aqueous electrolyte,
The aluminum porous body is filled with lithium metal.
　本発明者は、上記の課題の解決につき、鋭意検討を行った。その結果、従来の板状体のＬｉ－Ａｌ合金に替えて、アルミニウム多孔体中にリチウム金属を充填して作製したＬｉ－Ａｌ合金を負極として用いることが有効であることを見出した。 The present inventor has intensively studied to solve the above problems. As a result, the present inventors have found that it is effective to use a Li—Al alloy produced by filling lithium metal in a porous aluminum body as a negative electrode instead of the conventional plate-like Li—Al alloy.
　即ち、アルミニウム多孔体中にリチウム金属が充填されたＬｉ－Ａｌ合金負極は、芯となる骨格を有しているため、従来のＬｉ－Ａｌ合金負極のような脆弱性がなく、工業的量産に好適である。 In other words, the Li—Al alloy negative electrode filled with lithium metal in the aluminum porous body has a skeleton as a core, and is not as brittle as the conventional Li—Al alloy negative electrode. Is preferred.
　また、高い放電深度であっても充分なサイクル寿命を確保することができる。 In addition, a sufficient cycle life can be secured even at a high discharge depth.
　即ち、本発明者が検討した結果、充放電サイクルに伴って、充電時はＡｌが膨張し、放電時はＡｌが収縮し、電極全体の膨張収縮が起こるため、電極界面に割れなどを生じ、微粉化を発生させ、活物質の脱離を招き、これが、放電深度を上げた場合の充放電サイクル特性に悪影響を与えていることが分かった。 In other words, as a result of the study by the present inventors, along with the charge / discharge cycle, Al expands during charging, Al contracts during discharge, and the entire electrode expands and contracts, resulting in cracks at the electrode interface, It was found that micronization occurred and the active material was desorbed, which had an adverse effect on the charge / discharge cycle characteristics when the discharge depth was increased.
　これに対して、本発明に係るアルミニウム多孔体中にリチウム金属が充填されたＬｉ－Ａｌ合金負極では、Ａｌ濃度が多孔体の骨格から離れるに従い、即ち、多孔体の骨格の中央部ほど薄くなるという濃度勾配が形成されているため、充放電サイクルに伴う膨張収縮の応力が分散して緩和される。この結果、放電深度を上げた場合であっても、電極の割れなどが抑制され、微粉化の発生が抑制され、充分な充放電サイクルを確保することができる。 On the other hand, in the Li—Al alloy negative electrode in which the lithium metal is filled in the aluminum porous body according to the present invention, the Al concentration decreases as the distance from the skeleton of the porous body increases, that is, the central portion of the skeleton of the porous body becomes thinner. Therefore, the expansion and contraction stress accompanying the charge / discharge cycle is dispersed and relaxed. As a result, even when the depth of discharge is increased, cracking of the electrode and the like are suppressed, generation of pulverization is suppressed, and a sufficient charge / discharge cycle can be ensured.
　また、充放電サイクル寿命の低下は、Ｌｉ金属負極に係わるＬｉデンドライト成長により、長時間使用した場合に短絡が発生することにも原因があることが分かった。この点、本発明に係るアルミニウム多孔体中にリチウム金属が充填されたＬｉ－Ａｌ合金負極では、このＬｉデンドライト成長が多孔内に留まるため、短絡によるサイクル寿命の低下が抑制される。 It was also found that the decrease in the charge / discharge cycle life is caused by the occurrence of a short circuit when used for a long time due to Li dendrite growth related to the Li metal negative electrode. In this regard, in the Li—Al alloy negative electrode in which the lithium metal is filled in the aluminum porous body according to the present invention, this Li dendrite growth stays in the pores, so that a reduction in cycle life due to a short circuit is suppressed.
（２）また、前記のリチウム電池用合金負極は、
　前記アルミニウム多孔体の骨格が、アルミニウムによって形成されていることを特徴とする。 (2) In addition, the alloy negative electrode for lithium battery,
A skeleton of the aluminum porous body is formed of aluminum.
　アルミニウム多孔体の骨格自体がアルミニウムによって形成されているため、骨格のみでＬｉ－Ａｌ合金を形成することができる。このため、気孔率が高く、より容量密度の大きなリチウム電池用合金負極を提供することができる。 Since the skeleton of the aluminum porous body itself is made of aluminum, a Li—Al alloy can be formed using only the skeleton. For this reason, the alloy negative electrode for lithium batteries with a high porosity and a larger capacity density can be provided.
（３）また、前記のリチウム電池用合金負極は、
　前記アルミニウム多孔体の骨格が、銅、ニッケル、鉄のいずれかの金属からなる芯材の表面にアルミニウム層が形成されたアルミニウム被覆材によって形成されていることを特徴とする。 (3) The lithium battery alloy negative electrode is
The skeleton of the aluminum porous body is formed by an aluminum coating material in which an aluminum layer is formed on the surface of a core material made of any metal of copper, nickel, and iron.
　本発明のリチウム電池用合金負極は、アルミニウム多孔体の骨格の芯材として、銅、ニッケル、鉄のいずれかの金属が用いられている。これらの金属は、リチウムやアルミニウムと合金化しない一方、機械的強度が高いため、強度に優れた多孔体を形成することができる。このため、これらの金属からなる芯材の表面にアルミニウム層が形成された多孔体は、膨張収縮に対して強いリチウム電池用合金負極を提供することができる。 The alloy negative electrode for lithium batteries of the present invention uses a metal of copper, nickel, or iron as the core material of the aluminum porous body. These metals are not alloyed with lithium or aluminum, but have high mechanical strength, so that a porous body having excellent strength can be formed. For this reason, the porous body in which the aluminum layer is formed on the surface of the core material made of these metals can provide an alloy negative electrode for a lithium battery that is strong against expansion and contraction.
（４）また、前記のリチウム電池用合金負極は、
　前記アルミニウム多孔体の空孔に占める前記リチウム金属の体積の比率が、５０％以上１００％未満であることを特徴とする。 (4) In addition, the alloy negative electrode for lithium battery,
The ratio of the volume of the lithium metal in the pores of the aluminum porous body is 50% or more and less than 100%.
　本発明においては、リチウム金属の体積比率が１００％未満であり、Ｌｉ充填後のアルミニウム多孔体に空孔が残されているため、デンドライトが生成した場合でも、デンドライトは主として空孔内に生成する。このため、デンドライトショートが効果的に抑制される。一方、リチウム金属の体積比率が５０％未満になると、リチウム電池用合金負極としての実用的な作用が充分に発揮できない恐れがある。 In the present invention, the volume ratio of lithium metal is less than 100%, and vacancies remain in the porous aluminum body after filling Li, so even when dendrites are produced, the dendrites are mainly produced in the vacancies. . For this reason, a dendrite short is suppressed effectively. On the other hand, when the volume ratio of the lithium metal is less than 50%, there is a possibility that the practical action as an alloy negative electrode for a lithium battery cannot be sufficiently exhibited.
（５）また、前記のリチウム電池用合金負極は、
　前記アルミニウム多孔体の骨格を形成するアルミニウム、または前記アルミニウム被覆材のアルミニウム層の表面の酸素量が、３．１質量％以下であることを特徴とする。 (5) In addition, the alloy negative electrode for lithium battery,
The amount of oxygen on the surface of aluminum forming the skeleton of the aluminum porous body or the aluminum layer of the aluminum covering material is 3.1% by mass or less.
　本発明のリチウム電池用合金負極のアルミニウム多孔体は、アルミニウム多孔体の骨格を形成するアルミニウム、あるいは前記アルミニウム被覆材のアルミニウム層の表面の酸素量が、３．１質量％以下であるため、これまでにない一層容量密度が大きい電池用合金負極を提供することができる。 The aluminum porous body of the alloy negative electrode for lithium batteries of the present invention has an oxygen content of 3.1% by mass or less on the surface of aluminum forming the skeleton of the aluminum porous body or the aluminum layer of the aluminum coating material. It is possible to provide a battery alloy negative electrode having an unprecedented higher capacity density.
　Ａｌは、もともと酸化され易いため、これまで表面の酸素量が充分に少ないアルミニウム多孔体が無かった。例えば特開平８－１７０１２６号公報に記載の発泡樹脂の表面に形成させたＡｌの共晶合金の皮膜の表面にＡｌ粉末を塗着後、非酸化性の雰囲気中で熱処理して作製されたアルミニウム多孔体の場合は、表面に酸化皮膜が生成するため、表面の酸素量が多い。表面の酸素量が多い場合には、充填されたＬｉが酸素（Ｏ２）によって酸化され活物質として機能しないＬｉ２Ｏに変化してしまうため、大きな容量密度が得られない。また、生成したＬｉ２Ｏは、抵抗層となるため特性が低下する。 Since Al is easily oxidized from the beginning, there has been no porous aluminum body having a sufficiently small amount of oxygen on the surface. For example, aluminum prepared by applying Al powder on the surface of an Al eutectic alloy film formed on the surface of a foamed resin described in JP-A-8-170126 and then heat-treating it in a non-oxidizing atmosphere. In the case of a porous body, since an oxide film is formed on the surface, the amount of oxygen on the surface is large. When the amount of oxygen on the surface is large, the filled Li is oxidized by oxygen (O 2 ) and changed to Li 2 O that does not function as an active material, so that a large capacity density cannot be obtained. Further, the generated Li 2 O becomes a resistance layer, and the characteristics are deteriorated.
　このため、本発明者は、酸素量の少ないアルミニウム多孔体を研究し、酸素量３．１質量％以下のアルミニウム多孔体の開発に成功した。 For this reason, the present inventor has researched an aluminum porous body having a small amount of oxygen and succeeded in developing an aluminum porous body having an oxygen content of 3.1% by mass or less.
　本発明は、このようなアルミニウム多孔体を用いることを特徴としており、表面の酸素量が３．１質量％以下のアルミニウム多孔体を用いるため、一層容量密度が大きいリチウム電池用合金負極が得られる。 The present invention is characterized by using such an aluminum porous body. Since an aluminum porous body having a surface oxygen content of 3.1% by mass or less is used, an alloy negative electrode for a lithium battery having a higher capacity density can be obtained. .
　ここで、本発明のリチウム電池用合金負極の製造方法について、図面を参照しながら詳細に説明する。製造方法の第一段階では、連通孔を有するアルミニウム多孔体を製造し、第二段階では、そのアルミニウム多孔体にＬｉ金属を充填する。 Here, the method for producing an alloy negative electrode for a lithium battery of the present invention will be described in detail with reference to the drawings. In the first stage of the manufacturing method, an aluminum porous body having communication holes is manufactured, and in the second stage, the aluminum porous body is filled with Li metal.
　図１Ａ～１Ｃは、その第一段階の概略を示す模式図である。図１Ａは、連通孔を有する樹脂１の断面の一部を示す拡大模式図であり、樹脂１を骨格として孔が形成されている様子を示している。図１Ｂは、連通孔を有する樹脂１の表面にアルミニウム層２が形成された様子（アルミニウム層被膜樹脂３）を示している。図１Ｃは、アルミニウム層被膜樹脂３から樹脂１を熱分解させて消失させた後の様子（アルミニウム多孔体４）を示している。 1A to 1C are schematic diagrams showing an outline of the first stage. FIG. 1A is an enlarged schematic view showing a part of a cross section of a resin 1 having communication holes, and shows a state in which holes are formed using the resin 1 as a skeleton. FIG. 1B shows a state (aluminum layer coating resin 3) in which an aluminum layer 2 is formed on the surface of the resin 1 having communication holes. FIG. 1C shows a state (resin aluminum porous body 4) after the resin 1 is thermally decomposed and disappeared from the aluminum layer coating resin 3.
　図２は、アルミニウム層被膜樹脂３から、樹脂１を熱分解して消失させる工程を示す。アルミニウム層被膜樹脂３及び正極５を溶融塩６に浸漬し、アルミニウム層２をアルミニウムの標準電極電位より卑な電位に保つ。溶融塩中に浸漬してアルミニウム層２をアルミニウムの標準電極電位より卑な電位に保つことにより、アルミニウム層２の酸化が抑制される。なお、正極５には、溶融塩に不溶性を示せば適宜選択することができるが、たとえば、白金、チタンなどからなる電極が用いられる。 FIG. 2 shows a process of thermally decomposing the resin 1 from the aluminum layer coating resin 3. The aluminum layer coating resin 3 and the positive electrode 5 are immersed in the molten salt 6, and the aluminum layer 2 is kept at a lower potential than the standard electrode potential of aluminum. By immersing in the molten salt to keep the aluminum layer 2 at a lower potential than the standard electrode potential of aluminum, the oxidation of the aluminum layer 2 is suppressed. The positive electrode 5 can be appropriately selected as long as it shows insolubility in the molten salt. For example, an electrode made of platinum, titanium, or the like is used.
　この状態で、樹脂１の分解温度以上に溶融塩６を加熱すると、アルミニウム層被膜樹脂３のうち樹脂１のみが分解して消失する。その結果、アルミニウム多孔体４が得られる。この方法により製造されたアルミニウム多孔体４は、製造法の特質上、中空糸状である。この点において、特開２００２－３７１３２７で開示するようなアルミニウム発泡体の構造とは異なっている。なお、樹脂１を分解させるに際しては、アルミニウムの溶融を防ぐため、加熱温度は、アルミニウムの融点以下とする。具体的には、アルミニウムの融点である６６０℃以下で加熱することが好ましい。 In this state, when the molten salt 6 is heated to a temperature equal to or higher than the decomposition temperature of the resin 1, only the resin 1 of the aluminum layer coating resin 3 decomposes and disappears. As a result, the aluminum porous body 4 is obtained. The aluminum porous body 4 manufactured by this method has a hollow fiber shape due to the characteristics of the manufacturing method. In this respect, it differs from the structure of the aluminum foam as disclosed in JP-A-2002-371327. When the resin 1 is decomposed, the heating temperature is set to be equal to or lower than the melting point of aluminum in order to prevent melting of aluminum. Specifically, it is preferable to heat at 660 ° C. or lower, which is the melting point of aluminum.
　本発明における樹脂には、アルミニウムの融点以下の温度で熱分解するものであれば、任意の樹脂を選択できる。たとえば、ポリウレタン、ポリプロピレン、ポリエチレン等がある。なかでも、発泡ウレタンは、気孔率が高いし、熱分解しやすい素材であるので、発泡ウレタンが本発明の製造方法に用いる樹脂として好ましい。また、樹脂の気孔率は８０％～９８％、気孔径は５０μｍ～５００μｍ程度のものが好ましい。樹脂は、連通孔を有することが好ましい。これにより、閉気孔が無いアルミニウム多孔体が得られる。 Any resin can be selected as the resin in the present invention as long as it thermally decomposes at a temperature lower than the melting point of aluminum. For example, there are polyurethane, polypropylene, polyethylene and the like. Especially, since urethane foam is a raw material with high porosity and is easy to thermally decompose, urethane foam is preferable as resin used for the manufacturing method of this invention. The resin preferably has a porosity of 80% to 98% and a pore diameter of about 50 μm to 500 μm. The resin preferably has a communication hole. Thereby, the aluminum porous body without a closed pore is obtained.
　以上に説明したアルミニウム多孔体の表面のアルミニウムは、酸素量が極めて低く、ＥＤＸ分析の析出限界である３．１質量％以下であった。また、連通孔は、有するが閉気孔が無く、さらに共晶合金などを用いないため、アルミニウムのみから構成されている。 The aluminum on the surface of the porous aluminum body described above had an extremely low oxygen content and was 3.1% by mass or less, which is the precipitation limit of EDX analysis. In addition, the communication hole is formed of only aluminum because it has a closed hole but does not have a closed pore and does not use a eutectic alloy.
　次に、第二段階として、アルミニウム多孔体４に、Ｌｉ金属を充填する。充填するための方法は、特に限定されず、例えば、含入による方法や真空蒸着法、電気メッキ法などの公知の方法を用いることができる。 Next, as a second step, the aluminum porous body 4 is filled with Li metal. The method for filling is not particularly limited, and for example, a known method such as a method of inclusion, a vacuum deposition method, or an electroplating method can be used.
（６）また、前記のリチウム電池用合金負極は、
　前記アルミニウム多孔体が、連通孔を有し、閉気孔を有さず、
　さらにアルミニウムのみからなることを特徴とする。 (6) Moreover, the alloy negative electrode for lithium batteries described above is
The aluminum porous body has communication holes, no closed pores,
Furthermore, it consists only of aluminum.
　従来のアルミニウム多孔体、例えば、特開２００２－３７１３２７号公報に記載のＡｌを溶融させた状態で発泡剤を加えて発泡させたアルミニウム多孔体には、閉気孔が多く存在する。また、前記した特開平８－１７０１２６号公報に記載のアルミニウム多孔体は、共晶金属であるためＢｉ、Ｃａその他のＡｌ以外の金属を含有する。このように、閉気孔が多く存在する場合には、充分な量のＬｉを充填することができないため、大きな容量密度が得られない。また、Ａｌ以外の金属を含有するため、Ｌｉ－Ａｌ合金の負極としての機能が低下する。 A conventional aluminum porous body, for example, an aluminum porous body which is foamed by adding a foaming agent in a molten state described in JP-A-2002-371327 has many closed pores. In addition, since the aluminum porous body described in JP-A-8-170126 is a eutectic metal, it contains Bi, Ca and other metals other than Al. Thus, when there are many closed pores, a sufficient amount of Li cannot be filled, so that a large capacity density cannot be obtained. In addition, since a metal other than Al is contained, the function of the Li—Al alloy as a negative electrode is lowered.
　一方、本発明のリチウム電池用合金負極においては、充分な量のＬｉ金属を充填できるため、一層容量密度が大きいリチウム電池用合金負極が得られる。また、アルミニウム多孔体がアルミニウムのみからなるため、負極としての機能を充分に発揮させることができる。 On the other hand, the alloy negative electrode for lithium batteries of the present invention can be filled with a sufficient amount of Li metal, so that an alloy negative electrode for lithium batteries having a higher capacity density can be obtained. Further, since the aluminum porous body is made of only aluminum, the function as the negative electrode can be sufficiently exhibited.
（７）本発明に係るリチウム電池は、
　前記（１）～（６）に記載のリチウム電池用合金負極を備えることを特徴とする。 (7) The lithium battery according to the present invention is
It is characterized by including the lithium battery alloy negative electrode described in (1) to (6) above.
　本発明のリチウム電池は、前記の特徴を備えるリチウム電池用合金を負極としているため、容量密度が大きく、充放電サイクル特性が優れたリチウム電池を提供することができる。 Since the lithium battery of the present invention uses the lithium battery alloy having the above characteristics as the negative electrode, it is possible to provide a lithium battery having a large capacity density and excellent charge / discharge cycle characteristics.
（８）本発明に係るリチウム電池用合金負極の製造方法は、
　連通孔を有する樹脂の表面にアルミニウム層を形成するアルミニウム層形成工程と、
　前記樹脂を溶融塩に浸漬した状態で、前記アルミニウム層をアルミニウムの標準電極電位より卑な電位に保ちながら前記樹脂をアルミニウムの融点以下の温度に加熱して、前記樹脂を加熱分解してアルミニウム多孔体を作製するアルミニウム多孔体作製工程と、
　前記アルミニウム多孔体にリチウム金属を充填するリチウム金属充填工程と
を有することを特徴とする。 (8) A method for producing an alloy negative electrode for a lithium battery according to the present invention comprises:
An aluminum layer forming step of forming an aluminum layer on the surface of the resin having communication holes;
While the resin layer is immersed in the molten salt, the resin layer is heated to a temperature below the melting point of aluminum while maintaining the aluminum layer at a potential lower than the standard electrode potential of aluminum, and the resin is thermally decomposed to form porous aluminum. An aluminum porous body manufacturing process for manufacturing a body;
A lithium metal filling step of filling the aluminum porous body with lithium metal.
　本発明のリチウム電池用合金負極の製造方法によれば、前記したようにアルミニウム層の表面の酸素量が３．１質量％以下であり、連通孔を有し、閉気孔を有さず、さらにアルミニウムのみからなるアルミニウム多孔体を用いた容量密度が大きく、微粉化とデンドライトショートの抑制効果の高いリチウム電池用合金負極を提供することができる。 According to the method for producing an alloy negative electrode for a lithium battery of the present invention, as described above, the amount of oxygen on the surface of the aluminum layer is 3.1% by mass or less, has communication holes, does not have closed pores, It is possible to provide an alloy negative electrode for a lithium battery having a large capacity density using an aluminum porous body made only of aluminum and having a high effect of suppressing pulverization and dendrite short.
（９）本発明に係るリチウム電池用合金負極の製造方法は、
　連通孔を有する樹脂の表面に銅、ニッケル、鉄のいずれかの金属からなる金属層を形成する金属層形成工程と、
　前記金属層の表面にアルミニウム層を形成するアルミニウム層形成工程と、
　前記樹脂を溶融塩に浸漬した状態で、前記アルミニウム層をアルミニウムの標準電極電位より卑な電位に保ちながら前記樹脂をアルミニウムの融点以下の温度に加熱して、前記樹脂を加熱分解してアルミニウム多孔体を作製するアルミニウム多孔体作製工程と、
　前記アルミニウム多孔体にリチウム金属を充填するリチウム金属充填工程と
を有することを特徴とする。 (9) A method for producing an alloy negative electrode for a lithium battery according to the present invention comprises:
A metal layer forming step of forming a metal layer made of one of copper, nickel, and iron on the surface of the resin having communication holes;
An aluminum layer forming step of forming an aluminum layer on the surface of the metal layer;
In a state where the resin is immersed in the molten salt, the resin is heated to a temperature below the melting point of aluminum while maintaining the aluminum layer at a potential lower than the standard electrode potential of aluminum, and the resin is thermally decomposed to form porous aluminum. An aluminum porous body manufacturing process for manufacturing a body;
A lithium metal filling step of filling the aluminum porous body with lithium metal.
　本発明のリチウム電池用合金負極の製造方法によれば、前記したようにアルミニウム層の表面の酸素量が３．１質量％以下であり、連通孔を有し、閉気孔を有さないアルミニウム多孔体を用いた容量密度が大きく、充放電サイクルに優れたリチウム電池用合金負極を提供することができ、さらに、アルミニウム多孔体に銅、ニッケル、鉄のいずれかの金属からなる金属を骨格としているため、強度に強いリチウム電池用合金負極を提供することができる。 According to the method for producing an alloy negative electrode for a lithium battery of the present invention, as described above, the amount of oxygen on the surface of the aluminum layer is 3.1% by mass or less, and has an open pore and no closed pores. A lithium battery alloy negative electrode with a large capacity density using a body and an excellent charge / discharge cycle can be provided. Further, the porous aluminum body has a skeleton made of a metal made of copper, nickel, or iron. Therefore, it is possible to provide a lithium battery alloy negative electrode having high strength.
（１０）また、前記のリチウム電池用合金負極の製造方法は、
　前記アルミニウム層の形成方法が、真空蒸着法、スパッタリング法、レーザアブレーション法又はプラズマＣＶＤ法であることを特徴とする。 (10) Moreover, the manufacturing method of the said alloy negative electrode for lithium batteries is as follows.
The method for forming the aluminum layer is a vacuum deposition method, a sputtering method, a laser ablation method, or a plasma CVD method.
　真空蒸着法では、例えば、原料のアルミニウム金属に電子ビームを照射してアルミニウム金属を溶融・蒸発させ、連通孔を有する樹脂体の樹脂表面にアルミニウム金属を付着させることにより、アルミニウム金属層を形成することができる。スパッタリング法では、例えば、アルミニウム金属のターゲットにプラズマ照射してアルミニウム金属を気化させ、連通孔を有する樹脂体の樹脂表面にアルミニウム合金を付着させることにより、アルミニウム金属層を形成することができる。レーザアブレーション法では、例えば、レーザ照射によりアルミニウム金属を溶融・蒸発させ、連通孔を有する樹脂体の樹脂表面にアルミニウム金属を付着させることにより、アルミニウム金属層を形成することができる。プラズマＣＶＤ法では、原料であるアルミニウム化合物に高周波を印加することによってプラズマ化させ、連通孔を有する樹脂の表面に付着させることにより、アルミニウム金属層を形成することができる。 In the vacuum deposition method, for example, an aluminum metal layer is formed by irradiating an aluminum beam as a raw material with an electron beam to melt and evaporate the aluminum metal and adhere the aluminum metal to the resin surface of the resin body having communication holes. be able to. In the sputtering method, for example, an aluminum metal target can be vaporized by plasma irradiation on an aluminum metal target, and an aluminum alloy is adhered to the resin surface of a resin body having communication holes, whereby an aluminum metal layer can be formed. In the laser ablation method, for example, an aluminum metal layer can be formed by melting and evaporating aluminum metal by laser irradiation and attaching the aluminum metal to the resin surface of the resin body having the communication holes. In the plasma CVD method, an aluminum metal layer can be formed by applying a high frequency to an aluminum compound as a raw material to form a plasma and attaching it to the surface of a resin having communication holes.
（１１）また、前記のリチウム電池用合金負極の製造方法は、
　前記アルミニウム層の形成方法が、前記樹脂の表面を導電化処理した後、アルミニウムをめっきするめっき法であることを特徴とする。 (11) Moreover, the manufacturing method of the said alloy negative electrode for lithium batteries is as follows.
The method for forming the aluminum layer is a plating method in which aluminum is plated after the surface of the resin is subjected to a conductive treatment.
（１２）また、本発明のリチウム電池用合金負極の製造方法は、
　前記アルミニウム層の形成方法が、前記金属層の表面にアルミニウムをめっきするめっき法であることを特徴とする。 (12) Moreover, the manufacturing method of the alloy negative electrode for lithium batteries of this invention,
The method for forming the aluminum layer is a plating method for plating aluminum on the surface of the metal layer.
　水溶液中でアルミニウムをめっきすることは、実用上ほとんど不可能であるため、溶融塩中でアルミニウムをめっきする溶融塩電解めっきが行われる。この場合において、予め樹脂の表面を導電化処理した後に、溶融塩中でアルミニウムをめっきすることが好ましい。 Since it is practically impossible to plate aluminum in an aqueous solution, molten salt electroplating in which aluminum is plated in molten salt is performed. In this case, it is preferable to plate aluminum in a molten salt after conducting a conductive treatment on the surface of the resin in advance.
　ここで用いる溶融塩は、樹脂を加熱分解する工程で用いられることになる溶融塩と同じであっても、異なっていてもよい。具体的には、塩化カリウム、塩化アルミニウム、塩化ナトリウム等の溶融塩が使用される。また、２成分以上の塩を使用し、共晶溶融塩として使用してもよい。共晶溶融塩にした場合、溶融温度が低下するので好ましい。この溶融塩中には、少なくともアルミニウムイオンが含まれている必要がある。 The molten salt used here may be the same as or different from the molten salt to be used in the step of thermally decomposing the resin. Specifically, molten salts such as potassium chloride, aluminum chloride, and sodium chloride are used. Further, a salt of two or more components may be used and used as a eutectic molten salt. The eutectic molten salt is preferable because the melting temperature is lowered. This molten salt needs to contain at least aluminum ions.
（１３）また、前記のリチウム電池用合金負極の製造方法は、
　前記アルミニウム層の形成方法が、前記樹脂の表面または前記金属層の表面にアルミニウムペーストを塗布する塗布法であることを特徴とする。 (13) Moreover, the manufacturing method of the said alloy negative electrode for lithium batteries is as follows.
The method for forming the aluminum layer is a coating method in which an aluminum paste is applied to the surface of the resin or the surface of the metal layer.
　樹脂の表面にアルミニウムペーストを塗布する場合において、そのアルミニウムペーストは、たとえば、アルミニウム粉末、結着剤（バインダー樹脂）及び有機溶剤が混合されたものである。具体的には、アルミニウムペーストを樹脂の表面に塗布した後、加熱して有機溶剤及びバインダー樹脂を消失させるとともに、アルミニウムペーストを焼結させる。焼結時の加熱は、一段階でおこなっても複数回に分けておこなっても良い。例えば、アルミニウムペーストを塗布した後に低温で加熱して有機溶剤を消失させた後、溶融塩中に浸漬して加熱することにより、樹脂の分解と同時にアルミニウムペーストの焼結を行っても良い。 When the aluminum paste is applied to the resin surface, the aluminum paste is a mixture of, for example, aluminum powder, a binder (binder resin) and an organic solvent. Specifically, after the aluminum paste is applied to the surface of the resin, it is heated to eliminate the organic solvent and the binder resin, and the aluminum paste is sintered. Heating at the time of sintering may be performed in one step or in multiple steps. For example, the aluminum paste may be sintered at the same time as the resin decomposition by applying aluminum paste and heating at a low temperature to eliminate the organic solvent and then immersing in molten salt and heating.
　本発明によれば、容量密度が大きく、充放電サイクルに優れたリチウム電池用合金負極とその製造方法およびリチウム電池を提供することができる。 According to the present invention, it is possible to provide a lithium battery alloy negative electrode having a large capacity density and excellent charge / discharge cycle, a method for producing the same, and a lithium battery.
図１Ａは、アルミニウム多孔体の製造工程における、連通孔を有する樹脂の断面の一部を示す模式図である。FIG. 1A is a schematic view showing a part of a cross section of a resin having a communication hole in a manufacturing process of an aluminum porous body. 図１Ｂは、アルミニウム多孔体の製造工程における、連通孔を有する樹脂の表面にアルミニウム層が形成された様子（アルミニウム層被膜樹脂）を示す模式図である。FIG. 1B is a schematic view showing a state (aluminum layer coating resin) in which an aluminum layer is formed on the surface of a resin having communication holes in the manufacturing process of the aluminum porous body. 図１Ｃは、アルミニウム多孔体の製造工程における、アルミニウム層被膜樹脂から樹脂を熱分解させて消失させた後の様子（アルミニウム多孔体）を示す模式図である。FIG. 1C is a schematic diagram illustrating a state (aluminum porous body) after the resin is thermally decomposed and disappeared from the aluminum layer coating resin in the manufacturing process of the aluminum porous body. 図２は、溶融塩の中での樹脂の分解工程を説明するための模式図である。FIG. 2 is a schematic view for explaining a decomposition process of the resin in the molten salt. 図３は、本発明のアルミニウム多孔体のＳＥＭ写真である。FIG. 3 is a SEM photograph of the porous aluminum body of the present invention. 図４は、本発明によるアルミニウム多孔体のＥＤＸ分析結果を示す図である。FIG. 4 is a view showing an EDX analysis result of the aluminum porous body according to the present invention. 図５は、本発明のリチウム電池を説明する図である。FIG. 5 is a diagram illustrating a lithium battery according to the present invention.
　以下、図面に基づいて本発明の実施の形態を説明する。なお、以下の図面において同一または相当する部分には、同一の参照符号を付し、その説明は、繰り返さない。また、図面の寸法比率は、説明のものと必ずしも一致していない。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the following drawings, the same or corresponding parts are denoted by the same reference numerals, and description thereof will not be repeated. Further, the dimensional ratios in the drawings do not necessarily match those described.
（実施の形態１）
Ａ．リチウム電池用合金負極
　本実施の形態におけるリチウム電池用合金負極は、アルミニウム多孔体中にリチウム金属が充填されており、アルミニウム多孔体の骨格は、アルミニウムによって形成されている。そして、本実施の形態におけるリチウム電池用合金負極は、下記の製造方法により製造される（図１Ａ～図１Ｃを参照）。 (Embodiment 1)
A. Lithium battery alloy negative electrode In the lithium battery alloy negative electrode in the present embodiment, an aluminum porous body is filled with lithium metal, and the skeleton of the aluminum porous body is formed of aluminum. Then, the lithium battery alloy negative electrode in the present embodiment is manufactured by the following manufacturing method (see FIGS. 1A to 1C).
Ｂ．リチウム電池用合金負極の製造方法
　多孔性の樹脂１には、連通孔を有する発泡樹脂や不織布が用いられ、特に気孔率が８０％～９８％、気孔径が５０μｍ～５００μｍ程度の樹脂が好ましく、発泡ウレタンが好ましく用いられる。 B. Method for Producing Lithium Battery Alloy Negative Electrode For porous resin 1, a foamed resin or nonwoven fabric having communication holes is used, and a resin having a porosity of 80% to 98% and a pore diameter of about 50 μm to 500 μm is particularly preferable. Foam urethane is preferably used.
　以下、リチウム電池用合金負極の製造方法を、アルミニウム層形成工程、アルミニウム多孔体作製工程、およびリチウム金属含入（充填）工程の順に説明する。
（１）アルミニウム層形成工程
　真空蒸着、スパッタリング法、レーザアブレーション法若しくはプラズマＣＶＤ等の気相法、めっき法、アルミニウムペースト塗布法等により、樹脂１の表面に、アルミニウム層２を、直に形成してアルミニウム層被覆樹脂３を作製する。 Hereinafter, the manufacturing method of the alloy negative electrode for lithium batteries is demonstrated in order of an aluminum layer formation process, an aluminum porous body preparation process, and a lithium metal containing (filling) process.
(1) Aluminum layer forming step An aluminum layer 2 is directly formed on the surface of the resin 1 by a vapor deposition method such as vacuum deposition, sputtering, laser ablation or plasma CVD, plating, aluminum paste coating, or the like. Thus, the aluminum layer coating resin 3 is produced.
　電解めっきを行うためには、予め樹脂１の表面を導電化処理する。導電化処理には、ニッケル等の導電性金属の無電解めっき、アルミニウム等の蒸着若しくはスパッタリング、又はカーボン等の導電性粒子を含有した導電性塗料の塗布などの任意の方法が選択される。アルミニウムめっきするためのめっき浴には、例えばＡｌＣｌ3－ＸＣｌ（Ｘ：アルカリ金属）－ＭＣｌX（Ｍは、Ｃｒ、Ｍｎ、及び遷移金属元素から選択される添加元素）の多成分系の溶融塩が使用される。溶融塩の中に樹脂１を浸漬し、導電化処理をした樹脂を負極にして電解めっきを行う。 In order to perform electroplating, the surface of the resin 1 is subjected to a conductive treatment in advance. For the conductive treatment, an arbitrary method such as electroless plating of a conductive metal such as nickel, vapor deposition or sputtering of aluminum or the like, or application of a conductive paint containing conductive particles such as carbon is selected. As a plating bath for aluminum plating, for example, a multi-component molten salt of AlCl 3 —XCl (X: alkali metal) -MCl X (M is an additive element selected from Cr, Mn, and a transition metal element) Is used. Resin 1 is immersed in the molten salt, and electroplating is performed using the conductive resin as the negative electrode.
　アルミニウム層の形成は、前記の通り、アルミニウムペーストの塗布によっても行うことができる。アルミニウムペーストは、アルミニウム粉末と結着剤（バインダー樹脂）及び有機溶剤を混合したものであり、樹脂１の表面に所定量のアルミニウムペーストを塗布後、非酸化性雰囲気下で焼結する。 The formation of the aluminum layer can also be performed by applying an aluminum paste as described above. The aluminum paste is a mixture of aluminum powder, a binder (binder resin), and an organic solvent. After applying a predetermined amount of aluminum paste to the surface of the resin 1, it is sintered in a non-oxidizing atmosphere.
（２）アルミニウム多孔体作製工程
　次に、樹脂１を熱分解させて除去する。図２は、溶融塩６の中での多孔性樹脂の分解工程を説明するための模式図である。表面にアルミニウム層を形成した樹脂（すなわち、アルミニウム層被膜樹脂３）をＬｉＣｌ、ＫＣｌ、ＮａＣｌ、ＡｌＣｌ３からなる群より選択される１種以上を含む塩の中で、アルミニウムの融点以下の、好ましくは５００℃～６００℃の温度にて加熱して、白金またはチタン製の正極５との間に所定の電圧を印加してアルミニウム層被膜樹脂３のアルミニウム層をアルミニウムの標準電極電位より卑な電位（Ｌｉ、Ｋ、Ｎａの還元電位より貴な電位）で保って多孔性樹脂１を熱分解させて除去し、図１Ｃのアルミニウム多孔体４を作製する。 (2) Aluminum porous body preparation process Next, the resin 1 is thermally decomposed and removed. FIG. 2 is a schematic diagram for explaining a decomposition process of the porous resin in the molten salt 6. Resin (i.e., the aluminum layer coating resin 3) forming an aluminum layer on the surface of LiCl, KCl, NaCl, in a salt containing one or more selected from the group consisting of AlCl 3, aluminum below the melting point, preferably Is heated at a temperature of 500 ° C. to 600 ° C., and a predetermined voltage is applied between the positive electrode 5 made of platinum or titanium, so that the aluminum layer of the aluminum layer coating resin 3 has a lower potential than the standard electrode potential of aluminum. The porous resin 1 is thermally decomposed and removed while maintaining at (a potential nobler than the reduction potential of Li, K, Na), and the porous aluminum body 4 of FIG. 1C is produced.
（３）リチウム金属含入（充填）工程
　次に、作製したアルミニウム多孔体に所定量のリチウム金属を含入し、リチウムとアルミニウムの合金（Ｌｉ－Ａｌ合金）を生成させてリチウム電池用合金負極を作製する。具体的には、例えばアルミニウム多孔体と所定の厚さのリチウム箔を貼り合わせた後、１８０℃以上に加熱し、リチウム箔を溶融させてアルミニウム多孔体の空孔に浸透させる。また、１８０℃以上に加熱したリチウムの溶融浴にアルミニウム多孔体を浸漬させてもよい。なお、含入するリチウム量は、アルミニウム多孔体の空孔に占めるリチウム金属の体積の比率が５０％以上１００％未満となるように調整される。例えば気孔率が９７％のアルミニウム多孔体と厚さがアルミニウム多孔体の１／２のリチウム箔を貼り合わせた場合、空孔に占めるリチウム金属の体積の比率は、５１．５％になる。 (3) Lithium Metal Inclusion (Filling) Step Next, a predetermined amount of lithium metal is contained in the produced porous aluminum body to produce an alloy of lithium and aluminum (Li—Al alloy) to form an alloy negative electrode for a lithium battery. Is made. Specifically, for example, an aluminum porous body and a lithium foil having a predetermined thickness are bonded together, and then heated to 180 ° C. or higher to melt the lithium foil and permeate the pores of the aluminum porous body. Alternatively, the aluminum porous body may be immersed in a molten lithium bath heated to 180 ° C. or higher. The amount of lithium to be included is adjusted so that the ratio of the volume of lithium metal in the pores of the aluminum porous body is 50% or more and less than 100%. For example, when an aluminum porous body having a porosity of 97% and a lithium foil having a thickness of ½ of an aluminum porous body are bonded together, the ratio of the volume of lithium metal in the pores is 51.5%.
Ｃ．リチウム電池
　このようにして作製されたリチウム電池用合金負極においては、生成させたＬｉ－Ａｌ合金にアルミニウムの濃度が骨格の近傍で高く、骨格から離れるに従って低い濃度勾配が生じる。このため、充放電を行った際にＬｉ－Ａｌ合金が膨張収縮しても応力緩和がされ易く、微粉化が抑制される。 C. Lithium Battery In the lithium battery alloy negative electrode thus produced, the resulting Li—Al alloy has a high aluminum concentration near the skeleton and a lower concentration gradient as the distance from the skeleton increases. For this reason, even when the Li—Al alloy expands and contracts during charge / discharge, the stress is easily relaxed, and pulverization is suppressed.
　また、アルミニウム多孔体の空孔に占めるリチウム金属の体積の比率が５０％以上であるため、充分に高い容量密度が確保される一方、１００％未満とすることによりＬｉ充填後のアルミニウム多孔体中に空孔が残されているため、リチウムデンドライトが生成した場合でもデンドライトショートが抑制される。 In addition, since the ratio of the volume of lithium metal in the pores of the aluminum porous body is 50% or more, a sufficiently high capacity density is ensured, while in the aluminum porous body after filling Li by setting it to less than 100% As a result, the dendrite short circuit is suppressed even when lithium dendrite is generated.
（実施の形態２）
　実施の形態２では、アルミニウム多孔体の骨格は、芯材の表面にアルミニウム層が形成されたアルミニウム被覆材である。また、芯材は、銅、ニッケル、鉄のいずれかの金属からなり、連通孔を有する樹脂の表面に炭素粉末を塗布して導電処理をした後、所定の厚さでめっきを施すことにより形成される。 (Embodiment 2)
In Embodiment 2, the skeleton of the aluminum porous body is an aluminum covering material in which an aluminum layer is formed on the surface of the core material. The core is made of copper, nickel, or iron, and is formed by applying carbon powder to the surface of the resin having the communication holes and conducting a conductive treatment, followed by plating with a predetermined thickness. Is done.
　実施の形態２は、アルミニウム多孔体の骨格がアルミニウム被覆材である点を除いて、実施の形態１と同じ要領でリチウム電池用合金負極およびリチウム電池を製造する。 Embodiment 2 manufactures an alloy negative electrode for lithium batteries and a lithium battery in the same manner as Embodiment 1, except that the skeleton of the porous aluminum body is an aluminum coating material.
（実施の形態３）
　前記した各実施の形態において、リチウム金属の含入は、アルミニウム多孔体の空孔への浸透に限定されず、アルミニウム多孔体の表面に形成する形態であってもよい。 (Embodiment 3)
In each of the above-described embodiments, the lithium metal inclusion is not limited to the penetration of the porous aluminum body into the pores, but may be formed on the surface of the porous aluminum body.
　また、リチウム金属は、単体である必要はなく、他の金属との合金であってもよく、特に、Ｌｉ－Ｓｉ（ケイ素）、Ｌｉ－Ｓｎ（スズ）は、合金負極として好適である。 Further, the lithium metal does not have to be a single element, and may be an alloy with another metal. In particular, Li—Si (silicon) and Li—Sn (tin) are suitable as an alloy negative electrode.
　このようなＬｉ－ＳｉあるいはＬｉ－Ｓｎの合金負極をアルミニウム多孔体に形成する場合、ＬｉとＳｉまたはＳｎとの合金層をアルミニウム多孔体の表面に形成してもよく、あるいは、「アルミニウム骨格」や「銅などの芯材の表面に形成されたアルミニウム層」の上に、ＳｉまたはＳｎ金属層を設け、さらに、Ｌｉ金属層を積層して形成してもよい。 When such a Li—Si or Li—Sn alloy negative electrode is formed in an aluminum porous body, an alloy layer of Li and Si or Sn may be formed on the surface of the aluminum porous body, or “aluminum skeleton” Alternatively, a Si or Sn metal layer may be provided on an “aluminum layer formed on the surface of a core material such as copper”, and a Li metal layer may be further stacked.
（実施例１、２）
　実施例１は、骨格がアルミニウムにより形成されたアルミニウム多孔体に、リチウム金属を含入して形成される負極を有するリチウム二次電池である。 (Examples 1 and 2)
Example 1 is a lithium secondary battery having a negative electrode formed by including lithium metal in an aluminum porous body having a skeleton formed of aluminum.
　実施例２は、骨格がＣｕ製の芯材の表面にアルミニウム層が形成されアルミニウム被覆材であるアルミニウム多孔体に、リチウム金属を含入して形成される負極を有するリチウム二次電池である。 Example 2 is a lithium secondary battery having a negative electrode formed by including lithium metal in an aluminum porous body that is an aluminum coating material in which an aluminum layer is formed on the surface of a core material having a skeleton made of Cu.
（１）アルミニウム多孔体の作製
　実施例１では、気孔率９７％、気孔径約３００μｍのポリウレタンフォームを準備した。このポリウレタンフォームの表面に真空蒸着法により、厚さ約５０μｍのアルミニウム層を形成した後、温度５００℃のＬｉＣｌ－ＫＣｌ共晶溶融塩に浸漬し、アルミニウム層をアルミニウムの標準電極電位より卑な電位で３０分間保持した。その後大気中で室温まで冷却し、水洗して溶融塩を除去してアルミニウム層を骨格とする厚さ０．５ｍｍ、気孔率９７％のアルミニウム多孔体を作製した。 (1) Production of porous aluminum body In Example 1, a polyurethane foam having a porosity of 97% and a pore diameter of about 300 μm was prepared. An aluminum layer having a thickness of about 50 μm is formed on the surface of the polyurethane foam by a vacuum deposition method, and then immersed in a LiCl—KCl eutectic molten salt at a temperature of 500 ° C., so that the aluminum layer has a lower potential than the standard electrode potential of aluminum. For 30 minutes. Thereafter, it was cooled to room temperature in the atmosphere, washed with water to remove the molten salt, and a porous aluminum body having a thickness of 0.5 mm and a porosity of 97% having an aluminum layer as a skeleton was produced.
　実施例２では、気孔率９７％、気孔径約３００μｍのポリウレタンフォームを準備した。このポリウレタンフォームの表面に炭素粉末を塗布して導電処理をした後、厚さ２０μｍの銅メッキを施し、芯材を形成した。その上に真空蒸着法により、厚さ約５０μｍのアルミニウムの表層を形成した後、温度５００℃のＬｉＣｌ－ＫＣｌ共晶溶融塩に浸漬し、アルミニウム層をアルミニウムの標準電極電位より卑な電位で３０分間保持した。その後大気中で室温まで冷却し、水洗して溶融塩を除去してＣｕの芯材の表面にアルミニウムの表層を形成したアルミニウム被覆材を骨格とする厚さ０．５ｍｍ、気孔率９６％のアルミニウム多孔体を作製した。 In Example 2, a polyurethane foam having a porosity of 97% and a pore diameter of about 300 μm was prepared. After applying carbon powder on the surface of this polyurethane foam and conducting a conductive treatment, copper plating with a thickness of 20 μm was applied to form a core material. A surface layer of aluminum having a thickness of about 50 μm is formed thereon by vacuum deposition, and then immersed in a LiCl—KCl eutectic molten salt at a temperature of 500 ° C., and the aluminum layer is 30 bases lower than the standard electrode potential of aluminum. Hold for a minute. Thereafter, it is cooled to room temperature in the atmosphere, washed with water to remove the molten salt, and an aluminum covering material having a surface layer of aluminum formed on the surface of the Cu core material, having a thickness of 0.5 mm and a porosity of 96%. A porous body was produced.
　参考例では、孔径が２００μｍ～５００μｍであり、気孔率が９７％で、厚みが１．０ｍｍの発泡ウレタンフォームを準備した。この発泡ウレタンフォームを、真空蒸着装置内に配置した。アルミニウム金属を溶融・蒸発させる真空蒸着法により、発泡ウレタン樹脂の表面にアルミニウム膜を蒸着させた。その後、大気中で、５５０℃の熱処理をすることにより、発泡ウレタンフォームを除去した。これにより、参考例であるアルミニウム多孔体を得た。 In the reference example, a foamed urethane foam having a pore diameter of 200 μm to 500 μm, a porosity of 97%, and a thickness of 1.0 mm was prepared. This foamed urethane foam was placed in a vacuum deposition apparatus. An aluminum film was deposited on the surface of the foamed urethane resin by a vacuum deposition method in which aluminum metal was melted and evaporated. Thereafter, the foamed urethane foam was removed by heat treatment at 550 ° C. in the atmosphere. This obtained the aluminum porous body which is a reference example.
（２）アルミニウム多孔体の構造の確認と酸素量の測定
　実施例１のアルミニウム多孔体のＳＥＭ写真を図３に示す。図３より、アルミニウム多孔体を構成する孔が連通していることが分かった。また、実施例１のアルミニウム多孔体は、閉気孔を有しないことが分かった。 (2) Confirmation of structure of porous aluminum body and measurement of oxygen content An SEM photograph of the porous aluminum body of Example 1 is shown in FIG. From FIG. 3, it was found that the pores constituting the aluminum porous body communicated. Moreover, it turned out that the aluminum porous body of Example 1 does not have a closed pore.
　実施例１のアルミニウム多孔体の表面について、１５ｋＶの加速電圧でＥＤＸ分析した。その結果を図４に示す。酸素のピークは、観測されなかった。したがって、アルミニウム多孔体の酸素量は、ＥＤＸの検出限界以下であることが分かった。ここで、ＥＤＸによる検出限界は、酸素量３．１質量％であるので、実施例１のアルミニウム多孔体の表面の酸素量は、３．１質量％以下であるといえる。 The surface of the aluminum porous body of Example 1 was subjected to EDX analysis at an acceleration voltage of 15 kV. The result is shown in FIG. No oxygen peak was observed. Therefore, it was found that the oxygen content of the aluminum porous body was below the detection limit of EDX. Here, since the detection limit by EDX is an oxygen content of 3.1% by mass, it can be said that the oxygen content on the surface of the porous aluminum body of Example 1 is 3.1% by mass or less.
　実施例２についても、ＳＥＭ写真の撮影とＥＤＸ分析を行ったが、実施例１と同様の結果であることを確認した。 Also for Example 2, SEM photography and EDX analysis were performed, and it was confirmed that the result was the same as Example 1.
　参考例のアルミニウム多孔体の表面についても、同様な条件でＥＤＸ分析した。その結果、酸素のピークが観測され、アルミニウム多孔体の酸素量は、少なくとも３．１質量％を超えることが分かった。熱処理する際に、アルミニウム多孔体の表面が酸化したためである。 The surface of the aluminum porous body of the reference example was also subjected to EDX analysis under the same conditions. As a result, an oxygen peak was observed, and it was found that the oxygen content of the aluminum porous body exceeded at least 3.1 mass%. This is because the surface of the aluminum porous body was oxidized during the heat treatment.
　なお、この分析で用いた装置は、ＥＤＡＸ社製の「ＥＤＡＸ　Ｐｈｏｎｅｎｉｘ」であり、その型式は、ＨＩＴ２２　１３６－２．５である。 The apparatus used in this analysis is “EDAX Phonenix” manufactured by EDAX, and its model is HIT22 136-2.5.
（３）負極の作製
　アルミニウム多孔体に、厚さ３５０μｍのリチウム箔を貼り合わせた後、２５０℃に加熱してＬｉを溶融させ、Ｌｉを空孔に浸透させた。なお、空孔に占めるリチウム金属の体積の比率は、７５％である。 (3) Production of negative electrode After a 350 μm-thick lithium foil was bonded to an aluminum porous body, it was heated to 250 ° C. to melt Li, and Li was permeated into the pores. In addition, the ratio of the volume of lithium metal in the vacancies is 75%.
　リチウム金属を空孔に浸透させたアルミニウム多孔体を直径１５ｍｍの円形に成形してリチウム電池用合金負極を作製した。 An aluminum porous body in which lithium metal was infiltrated into pores was formed into a circle having a diameter of 15 mm to produce an alloy negative electrode for a lithium battery.
（４）リチウム電池用正極の作製
　ＭｎＯ２（活物質）、アセチレンブラック（導電助剤）、ＰＶＤＦ（バインダー）を所定の比率で混合し、直径が１５ｍｍ、容量密度が１０ｍＡｈ／ｃｍ２のリチウム電池用正極を作製した。 (4) Production of positive electrode for lithium battery MnO2 (active material), acetylene black (conductive aid), PVDF (binder) are mixed at a predetermined ratio, and the positive electrode for lithium battery has a diameter of 15 mm and a capacity density of 10 mAh / cm2. Was made.
（５）リチウム二次電池の作製
　次に、負極および正極に用いてリチウム二次電池を作製した。図５は、本実施例のリチウム電池の構成を説明するための図である。図５において、１１はリチウム二次電池、１２はリチウム電池用正極、１３はセパレーター、１４はリチウム電池用合金負極である。 (5) Production of lithium secondary battery Next, a lithium secondary battery was produced using the negative electrode and the positive electrode. FIG. 5 is a diagram for explaining the configuration of the lithium battery of this embodiment. In FIG. 5, 11 is a lithium secondary battery, 12 is a positive electrode for a lithium battery, 13 is a separator, and 14 is an alloy negative electrode for a lithium battery.
　具体的には、正極１２と負極１４との間にポリプロピレン製のセパレーター１３を挟んで積層し、ＬｉＣｌＯ４を１モル％溶解させた（１Ｍ）プロピレンカーボネート／エチレンカーボネート／ジメトキシエタンの混合液からなる電解液を用いて組立てた。 Specifically, an electrolyte made of a mixed solution of propylene carbonate / ethylene carbonate / dimethoxyethane in which 1 mol% of LiClO 4 was dissolved by laminating a polypropylene separator 13 between the positive electrode 12 and the negative electrode 14. It assembled using the liquid.
（比較例）
　比較例は、Ａｌ－Ｌｉ合金箔の負極を有するリチウム二次電池である。 (Comparative example)
A comparative example is a lithium secondary battery having a negative electrode of an Al—Li alloy foil.
　アルミニウムの比率が５０原子％、直径が１５ｍｍのＡｌ－Ｌｉ合金箔を作製してリチウム電池用合金負極とし、この負極と、実施例と同様にして作成されるリチウム電池用正極に用いて、実施例と同様にしてリチウム二次電池を作製した。 An Al—Li alloy foil having an aluminum ratio of 50 atomic% and a diameter of 15 mm was prepared as an alloy negative electrode for a lithium battery, and this negative electrode and a positive electrode for a lithium battery prepared in the same manner as in the examples were used. A lithium secondary battery was produced in the same manner as in the example.
（実施例１、２および比較例のリチウム二次電池の特性評価）
（１）歩留り
　実施例１、２の場合、電池の組立における歩留りが１００％であるのに対して、比較例の歩留りは、約５０％と低かった。比較例の場合、このように歩留りが低いのは、リチウム電池用合金負極が脆弱で、ハンドリング時に割れや欠けが生じるためである。 (Characteristic evaluation of lithium secondary batteries of Examples 1 and 2 and Comparative Example)
(1) Yield In the case of Examples 1 and 2, the yield in battery assembly was 100%, whereas the yield in the comparative example was as low as about 50%. In the case of the comparative example, the reason for the low yield is that the lithium battery alloy negative electrode is brittle and cracks and chips occur during handling.
（２）充放電サイクル特性
　イ．試験方法
　カットオフ電圧を２．０－３．３Ｖとし、６ｍＡ／ｈと１８ｍＡ／ｈの２種類の放電深度で充放電サイクル試験を行い、放電容量が初期の５０％以下となるサイクル数を調べた。 (2) Charging / discharging cycle characteristics a. Test method The cut-off voltage is set to 2.0-3.3V, charge / discharge cycle tests are conducted at two discharge depths of 6 mA / h and 18 mA / h, and the number of cycles at which the discharge capacity is 50% or less of the initial value is investigated. It was.
　ロ．試験結果
　実施例１、２および比較例の試験結果を表１に示す。 B. Test results Table 1 shows the test results of Examples 1 and 2 and the comparative example.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１より実施例１、２は、サイクル特性が優れていることが分かる。実施例のサイクル特性がこのように優れているのは、微粉化とデンドライトショートの抑制効果の高いリチウム電池用合金負極を用いているためである。 Table 1 shows that Examples 1 and 2 have excellent cycle characteristics. The reason why the cycle characteristics of the examples are excellent in this way is that an alloy negative electrode for a lithium battery having a high effect of suppressing pulverization and dendrite short is used.
　また、前記したように、実施例は、閉気孔がなく酸素量が少ないアルミニウム多孔体にＬｉを含入させているため、容量密度が高いリチウム電池用合金負極を有するリチウム二次電池である。 Also, as described above, the example is a lithium secondary battery having a lithium battery alloy negative electrode having a high capacity density because Li is contained in an aluminum porous body having no closed pores and a small amount of oxygen.
　以上、本発明の実施の形態について説明したが、本発明は、上記の実施の形態に限定されるものではない。本発明と同一および均等の範囲内において、上記の実施の形態に対して種々の変更を加えることが可能である。 As mentioned above, although embodiment of this invention was described, this invention is not limited to said embodiment. Various modifications can be made to the above-described embodiment within the same and equivalent scope as the present invention.
　以上の如く本発明によれば、閉気孔がなく酸素量が少ないアルミニウム多孔体にリチウムを含入させているため、容量密度が大きく、充放電サイクルに優れたリチウム電池用合金負極とその製造方法およびリチウム電池を提供することができる。 As described above, according to the present invention, lithium is contained in an aluminum porous body having no closed pores and a small amount of oxygen, and therefore, an alloy negative electrode for a lithium battery having a large capacity density and an excellent charge / discharge cycle and a method for producing the same And a lithium battery can be provided.
　１　　　　　樹脂
　２　　　　　アルミニウム層　
　３　　　　　アルミニウム層被覆樹脂
　４　　　　　アルミニウム多孔体
　５　　　　　正極
　６　　　　　溶融塩
１１　　　　　リチウム二次電池
１２　　　　　リチウム電池用正極
１３　　　　　セパレーター
１４　　　　　リチウム電池用合金負極　　 1 Resin 2 Aluminum layer
DESCRIPTION OF SYMBOLS 3 Aluminum layer coating resin 4 Aluminum porous body 5 Positive electrode 6 Molten salt 11 Lithium secondary battery 12 Positive electrode for lithium batteries 13 Separator 14 Alloy negative electrode for lithium batteries

Claims (13)

  1. 　非水電解液を用いるリチウム電池用合金負極であって、
    　アルミニウム多孔体中にリチウム金属が充填されていることを特徴とするリチウム電池用合金負極。     An alloy negative electrode for a lithium battery using a non-aqueous electrolyte,
    An alloy negative electrode for a lithium battery, wherein a porous aluminum body is filled with lithium metal.
  2. 　前記アルミニウム多孔体の骨格が、アルミニウムによって形成されていることを特徴とする請求項１に記載のリチウム電池用合金負極。 The alloy negative electrode for a lithium battery according to claim 1, wherein the skeleton of the aluminum porous body is formed of aluminum.
  3. 　前記アルミニウム多孔体の骨格が、銅、ニッケル、鉄のいずれかの金属からなる芯材の表面にアルミニウム層が形成されたアルミニウム被覆材によって形成されていることを特徴とする請求項１に記載のリチウム電池用合金負極。 The skeleton of the porous aluminum body is formed of an aluminum coating material in which an aluminum layer is formed on the surface of a core material made of any metal of copper, nickel, and iron. Alloy negative electrode for lithium batteries.
  4. 　前記アルミニウム多孔体の空孔に占める前記リチウム金属の体積の比率が、５０％以上１００％未満であることを特徴とする請求項１ないし請求項３のいずれか１項に記載のリチウム電池用合金負極。 The lithium battery alloy according to any one of claims 1 to 3, wherein a volume ratio of the lithium metal occupying the pores of the aluminum porous body is 50% or more and less than 100%. Negative electrode.
  5. 　前記アルミニウム多孔体の骨格を形成するアルミニウム、または前記アルミニウム被覆材のアルミニウム層の表面の酸素量が、３．１質量％以下であることを特徴とする請求項１ないし請求項４のいずれか１項に記載のリチウム電池用合金負極。 The amount of oxygen on the surface of aluminum forming the skeleton of the aluminum porous body or the aluminum layer of the aluminum covering material is 3.1% by mass or less. The alloy negative electrode for lithium batteries as described in the item.
  6. 　前記アルミニウム多孔体が、連通孔を有し、閉気孔を有さず、
    　さらにアルミニウムのみからなることを特徴とする請求項１ないし請求項５のいずれか１項に記載のリチウム電池用合金負極。     The aluminum porous body has communication holes, no closed pores,
    The alloy negative electrode for a lithium battery according to any one of claims 1 to 5, further comprising only aluminum.
  7. 　請求項１ないし請求項６のいずれか1項に記載のリチウム電池用合金負極を備えることを特徴とするリチウム電池。 A lithium battery comprising the alloy negative electrode for a lithium battery according to any one of claims 1 to 6.
  8. 　連通孔を有する樹脂の表面にアルミニウム層を形成するアルミニウム層形成工程と、
    　前記樹脂を溶融塩に浸漬した状態で、前記アルミニウム層をアルミニウムの標準電極電位より卑な電位に保ちながら前記樹脂をアルミニウムの融点以下の温度に加熱して、前記樹脂を加熱分解してアルミニウム多孔体を作製するアルミニウム多孔体作製工程と、
    　前記アルミニウム多孔体にリチウム金属を充填するリチウム金属充填工程と
    を有することを特徴とするリチウム電池用合金負極の製造方法。     An aluminum layer forming step of forming an aluminum layer on the surface of the resin having communication holes;
    While the resin layer is immersed in the molten salt, the resin layer is heated to a temperature below the melting point of aluminum while maintaining the aluminum layer at a potential lower than the standard electrode potential of aluminum, and the resin is thermally decomposed to form porous aluminum. An aluminum porous body manufacturing process for manufacturing a body;
    A method for producing an alloy negative electrode for a lithium battery, comprising: a lithium metal filling step of filling the aluminum porous body with lithium metal.
  9. 　連通孔を有する樹脂の表面に銅、ニッケル、鉄のいずれかの金属からなる金属層を形成する金属層形成工程と、
    　前記金属層の表面にアルミニウム層を形成するアルミニウム層形成工程と、
    　前記樹脂を溶融塩に浸漬した状態で、前記アルミニウム層をアルミニウムの標準電極電位より卑な電位に保ちながら前記樹脂をアルミニウムの融点以下の温度に加熱して、前記樹脂を加熱分解してアルミニウム多孔体を作製するアルミニウム多孔体作製工程と、
    　前記アルミニウム多孔体にリチウム金属を充填するリチウム金属充填工程と
    を有することを特徴とするリチウム電池用合金負極の製造方法。     A metal layer forming step of forming a metal layer made of one of copper, nickel, and iron on the surface of the resin having communication holes;
    An aluminum layer forming step of forming an aluminum layer on the surface of the metal layer;
    In a state where the resin is immersed in the molten salt, the resin is heated to a temperature below the melting point of aluminum while maintaining the aluminum layer at a potential lower than the standard electrode potential of aluminum, and the resin is thermally decomposed to form porous aluminum. An aluminum porous body manufacturing process for manufacturing a body;
    A method for producing an alloy negative electrode for a lithium battery, comprising: a lithium metal filling step of filling the aluminum porous body with lithium metal.
  10. 　前記アルミニウム層の形成方法が、真空蒸着法、スパッタリング法、レーザアブレーション法又はプラズマＣＶＤ法であることを特徴とする請求項８または請求項９に記載のリチウム電池用合金負極の製造方法。 The method for producing an alloy negative electrode for a lithium battery according to claim 8 or 9, wherein the aluminum layer is formed by a vacuum deposition method, a sputtering method, a laser ablation method, or a plasma CVD method.
  11. 　前記アルミニウム層の形成方法が、前記樹脂の表面を導電化処理した後、アルミニウムをめっきするめっき法であることを特徴とする請求項８に記載のリチウム電池用合金負極の製造方法。 The method for producing an alloy negative electrode for a lithium battery according to claim 8, wherein the method for forming the aluminum layer is a plating method in which the surface of the resin is subjected to a conductive treatment and then aluminum is plated.
  12. 　前記アルミニウム層の形成方法が、前記金属層の表面にアルミニウムをめっきするめっき法であることを特徴とする請求項９に記載のリチウム電池用合金負極の製造方法。 The method for producing an alloy negative electrode for a lithium battery according to claim 9, wherein the method for forming the aluminum layer is a plating method in which aluminum is plated on the surface of the metal layer.
  13. 　前記アルミニウム層の形成方法が、前記樹脂の表面または前記金属層の表面にアルミニウムペーストを塗布する塗布法であることを特徴とする請求項８または請求項９に記載のリチウム電池用合金負極の製造方法。 10. The method for producing an alloy negative electrode for a lithium battery according to claim 8, wherein the aluminum layer is formed by a coating method in which an aluminum paste is applied to the surface of the resin or the surface of the metal layer. Method.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3276709A1 (en) * 2016-07-25 2018-01-31 LG Chem, Ltd. Negative electrode comprising mesh-type current collector, lithium secondary battery comprising the same, and manufacturing method thereof
US10468665B2 (en) 2015-01-29 2019-11-05 Sigma Lithium Limited Composite materials
CN114270575A (en) * 2021-03-31 2022-04-01 宁德新能源科技有限公司 Electrochemical device and electronic device
CN114421029A (en) * 2021-12-29 2022-04-29 华中科技大学 Construction method and application of in-situ alloy-SEI layer on surface of metal lithium

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013161652A (en) * 2012-02-06 2013-08-19 Toyota Industries Corp Secondary battery
KR101621410B1 (en) * 2013-09-11 2016-05-16 주식회사 엘지화학 Lithium electrode and lithium secondary battery including the same
KR101621412B1 (en) 2013-09-11 2016-05-16 주식회사 엘지화학 Lithium electrode and lithium secondary battery including the same
CN105529453B (en) * 2015-11-22 2018-03-30 天津赫维科技有限公司 A kind of 3V can fill the preparation method of button lithium battery lithium-aluminium alloy negative pole
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KR102142552B1 (en) * 2016-10-05 2020-08-10 주식회사 엘지화학 Negative electrode for lithium metal secondary battery and lithium metal secondary battery comprising the same
CN110462106A (en) * 2017-04-05 2019-11-15 住友电气工业株式会社 Aluminium porous body and method for producing aluminium porous body
CN108063222B (en) * 2017-08-31 2024-04-02 广东猛狮新能源科技股份有限公司 Lithium ion battery negative electrode material, preparation method thereof and lithium ion battery
CN108134049B (en) * 2017-12-19 2023-06-30 成都大超科技有限公司 Negative electrode layer, preparation method thereof, lithium battery cell and lithium battery
CN108281611A (en) * 2017-12-19 2018-07-13 成都亦道科技合伙企业（有限合伙） Negative electrode layer and preparation method thereof, lithium battery electric core and lithium battery
CN108598365B (en) * 2018-05-25 2020-11-03 哈尔滨工业大学 Negative electrode for lithium secondary battery, preparation method thereof and lithium secondary battery
WO2021079784A1 (en) * 2019-10-25 2021-04-29 パナソニックＩｐマネジメント株式会社 Aluminum foil, lithium secondary battery negative electrode, lithium secondary battery separator, and lithium secondary battery
CN111434609B (en) * 2019-12-27 2022-09-20 蜂巢能源科技有限公司 Pre-lithiated negative electrode active material, preparation method thereof, negative plate and lithium ion battery

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6342819B2 (en) * 1981-08-29 1988-08-25 Nippon Telegraph & Telephone
JPS6463268A (en) * 1987-09-02 1989-03-09 Kanebo Ltd Organic electrolytic battery using aluminum-lithium alloyed porous body for negative electrode
JPH0454352B2 (en) * 1983-01-18 1992-08-31 Sanyo Electric Co
JP2005294013A (en) * 2004-03-31 2005-10-20 Sanyo Electric Co Ltd Precursor battery and nonaqueous electrolyte secondary battery
JP2008016329A (en) * 2006-07-06 2008-01-24 Sumitomo Electric Ind Ltd Negative electrode material for lithium secondary battery

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02309558A (en) * 1989-05-24 1990-12-25 Sumitomo Electric Ind Ltd Negative electrode for lithium secondary battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6342819B2 (en) * 1981-08-29 1988-08-25 Nippon Telegraph & Telephone
JPH0454352B2 (en) * 1983-01-18 1992-08-31 Sanyo Electric Co
JPS6463268A (en) * 1987-09-02 1989-03-09 Kanebo Ltd Organic electrolytic battery using aluminum-lithium alloyed porous body for negative electrode
JP2005294013A (en) * 2004-03-31 2005-10-20 Sanyo Electric Co Ltd Precursor battery and nonaqueous electrolyte secondary battery
JP2008016329A (en) * 2006-07-06 2008-01-24 Sumitomo Electric Ind Ltd Negative electrode material for lithium secondary battery

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10468665B2 (en) 2015-01-29 2019-11-05 Sigma Lithium Limited Composite materials
EP3276709A1 (en) * 2016-07-25 2018-01-31 LG Chem, Ltd. Negative electrode comprising mesh-type current collector, lithium secondary battery comprising the same, and manufacturing method thereof
JP2018018821A (en) * 2016-07-25 2018-02-01 エルジー・ケム・リミテッド Negative electrode comprising mesh-type current collector, lithium secondary battery comprising the same, and manufacturing method thereof
US10686193B2 (en) 2016-07-25 2020-06-16 Lg Chem, Ltd. Negative electrode comprising mesh-type current collector, lithium secondary battery comprising the same, and manufacturing method thereof
CN114270575A (en) * 2021-03-31 2022-04-01 宁德新能源科技有限公司 Electrochemical device and electronic device
CN114421029A (en) * 2021-12-29 2022-04-29 华中科技大学 Construction method and application of in-situ alloy-SEI layer on surface of metal lithium
CN114421029B (en) * 2021-12-29 2023-09-01 华中科技大学 Construction method and application of in-situ alloy-SEI layer on surface of metallic lithium

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