WO2011152244A1 - 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 - Google Patents
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 Download PDFInfo
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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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- 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
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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
- H01M4/13—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
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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
- H01M4/13—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—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
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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
- H01M4/66—Selection of materials
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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
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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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
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- 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.
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Abstract
Description
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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)。
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。
(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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
(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。
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。
実施例1、2および比較例の試験結果を表1に示す。
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
Claims (13)
- 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。 - 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。
- 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。
- 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。
- 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。
- 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。 - 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。
- 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。 - 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。 - 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。
- 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。
- 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。
- 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。
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CN114270575A (zh) * | 2021-03-31 | 2022-04-01 | 宁德新能源科技有限公司 | 电化学装置和电子装置 |
CN114421029A (zh) * | 2021-12-29 | 2022-04-29 | 华中科技大学 | 一种金属锂表面原位合金-sei层的筑构方法与应用 |
CN114421029B (zh) * | 2021-12-29 | 2023-09-01 | 华中科技大学 | 一种金属锂表面原位合金-sei层的筑构方法与应用 |
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JP2011249286A (ja) | 2011-12-08 |
TW201201440A (en) | 2012-01-01 |
JP5605749B2 (ja) | 2014-10-15 |
KR20130042487A (ko) | 2013-04-26 |
CN102906906A (zh) | 2013-01-30 |
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