WO2014050569A1 - Électrode positive pour batteries secondaires au lithium-ion et batterie secondaire au lithium-ion l'utilisant - Google Patents

Électrode positive pour batteries secondaires au lithium-ion et batterie secondaire au lithium-ion l'utilisant Download PDF

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WO2014050569A1
WO2014050569A1 PCT/JP2013/074566 JP2013074566W WO2014050569A1 WO 2014050569 A1 WO2014050569 A1 WO 2014050569A1 JP 2013074566 W JP2013074566 W JP 2013074566W WO 2014050569 A1 WO2014050569 A1 WO 2014050569A1
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positive electrode
active material
electrode active
lithium
current collector
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PCT/JP2013/074566
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English (en)
Japanese (ja)
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木村　浩二
小林　伸行
武内　幸久
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日本碍子株式会社
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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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a positive electrode for a lithium ion secondary battery and a lithium ion secondary battery using the same.
  • lithium ion secondary batteries have attracted attention from the viewpoint of high energy density.
  • a lithium-containing compound such as a lithium composite oxide is used as a positive electrode active material of a lithium ion secondary battery, and positive electrodes having various configurations have been proposed in order to improve battery characteristics.
  • Patent Document 1 Japanese Patent Laid-Open No. 8-180904
  • the positive electrode is composed of a sintered body of a lithium composite oxide, whereby the conductivity, active material filling property, and reaction area at the positive electrode are increased. It is disclosed that charge / discharge efficiency and energy density are improved.
  • this sintered body positive electrode high conductivity can be obtained without containing a conductive agent, and since the conductive agent and binder are not included, the packing density of the active material is increased and the reaction area is also increased. ing.
  • this positive electrode is produced by press-molding powder or its raw material powder with a mold, and only a thick positive electrode active material layer can be obtained. As a result, the rate characteristics of the lithium ion battery are not practical. It was insufficient. Further, the electrode disclosed in this document has a high internal resistance and an output surface is not sufficient.
  • Patent Document 2 International Publication No. 2011/132627 discloses a configuration of an all-solid-state secondary battery and a manufacturing method thereof. According to this configuration, since each constituent layer is formed by the green sheet method, the positive electrode active material layer can be made thinner than that in Patent Document 1 (Japanese Patent Laid-Open No. 8-180904). An improvement in rate characteristics can be expected.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 8-180904
  • the positive electrode in the battery has a configuration in which an active material is provided only on one side with respect to the current collecting layer. I must.
  • the electrode structure disclosed in this document is a structure conscious of the internal resistance of the electrode, and there is no suggestion of output characteristics.
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2-297860 describes that an active material is formed on both sides of a current collector.
  • the active material disclosed in this document is obtained by drying a paste made of an organic binder, a conductive additive, and an organic solvent on an active material powder, the amount of the active material that functions effectively is small. The discharge capacity, the charge / discharge rate, and the output were not compatible.
  • the electrode structure disclosed in this document is a structure that functions only in a structure in which unit cells are stacked.
  • JP-A-8-180904 International Publication No. 2011/132627 JP-A-2-297860 JP 2011-051800 A JP 2011-073962 A JP 2011-073963 A
  • the inventors of the present invention have been able to charge and discharge as a positive electrode of a lithium ion battery by embedding an internal current collector in the positive electrode active material plate and making lithium ions movable between both surfaces.
  • capacitance, a charging / discharging rate, an output, and mechanical strength are compatible also in a unit battery was acquired.
  • an object of the present invention is to provide a positive electrode for a lithium ion secondary battery that can achieve high charge / discharge capacity, charge / discharge rate, output and mechanical strength even in a unit battery.
  • a positive electrode active material plate comprising a positive electrode active material comprising a lithium composite oxide;
  • a positive electrode for a secondary battery is provided.
  • a lithium ion secondary battery comprising the positive electrode, a negative electrode, and an electrolyte provided between the positive electrode and the negative electrode.
  • At least one comprising the positive electrode, two negative electrodes provided on both sides of the positive electrode, and an electrolyte provided between the positive electrode and the negative electrode.
  • a lithium ion secondary battery having two stacked structures is provided.
  • the positive electrode Figure 1 for a lithium ion secondary battery a configuration of a positive electrode for a lithium ion secondary battery according to the present invention is shown schematically.
  • a positive electrode 10 shown in FIG. 1 is formed of an integrated sintered body including a positive electrode active material plate 12 and an internal current collector 14.
  • the positive electrode active material plate 12 includes a positive electrode active material made of a lithium composite oxide.
  • the internal current collector 14 is embedded in the positive electrode active material plate 12, has at least one opening 14a, and the opening is filled with the positive electrode active material so that lithium ions can move.
  • the side end portion of the internal current collector 14 may extend from the side end portion of the positive electrode active material plate 12 so as to be easily connected to the external terminal.
  • the positive electrode of the present invention has a very characteristic layer structure in which the current collector is provided inside the positive electrode, contrary to the conventional positive electrode in which the current collector is provided outside.
  • This layer configuration can be said to be a configuration in which the positive electrode active material layers 12a and 12b are provided on both sides of the current collector 14, but the positive electrode active material 12c is also present in the opening 14a of the internal current collector. Therefore, when configured as a lithium ion secondary battery as shown in FIG. 2, lithium ions that have reached the positive electrode active material layer 12 b from the negative electrode 22 through the electrolyte 28 are in the opening 14 a of the internal current collector 14.
  • the positive electrode 10 having such a characteristic layer structure is integrated by firing. According to such a positive electrode of the present invention, a high charge / discharge capacity, charge / discharge rate, output and mechanical strength can be achieved in a unit battery as a positive electrode of a lithium ion battery.
  • the positive electrode of the present invention since the positive electrode active material plate containing the positive electrode active material is baked and integrated and reinforced with the internal current collector embedded therein, the active material layer It is possible to effectively suppress problems such as cracks associated with the thinning of the sheet.
  • the positive electrode of the present invention has a structure in which a positive electrode active material is disposed on both sides of a current collector and integrated with sintering.
  • a positive electrode active material is disposed on both sides of a current collector and integrated with sintering.
  • the internal current collector is provided with an opening for allowing lithium ions to move, so that the unit battery is used and the unit battery is stacked and operated.
  • the active material existing on both sides of the internal current collector can be utilized to the maximum regardless of the presence of the internal current collector.
  • the unit battery as shown in FIG. 2 will be described as an example. If a solid battery is configured by electrically joining the internal current collector 14 to an external terminal, the positive electrode disposed on both surfaces of the internal current collector 14.
  • the active material layers 12a and 12b can function as a positive electrode because lithium ions can move through the internal current collector 14, and include a conventional positive electrode in which a positive electrode active material layer is disposed only on one side of the current collector. In comparison, battery characteristics are dramatically improved. Therefore, in the positive electrode of the present invention, even if the positive electrode active material layer provided on each surface is thin, by providing them on both surfaces, both rate characteristics and capacity characteristics can be realized.
  • the positive electrode active material plate containing the positive electrode active material is provided with a current collector and integrated by firing, it becomes a conventionally used resistance component.
  • the use of a conductive bonding material that can be avoided can be avoided.
  • the positive electrode of the present invention is advantageous in increasing the output because the internal resistance is reduced.
  • the positive electrode active material plate 12 is made of a ceramic sintered body containing a positive electrode active material made of a lithium composite oxide.
  • the positive electrode active material is not particularly limited as long as it can function as an active material in the positive electrode of the lithium ion secondary battery, but is preferably a lithium-transition metal composite oxide.
  • the positive electrode active material, particularly the lithium-transition metal composite oxide preferably has a layered rock salt structure or a spinel structure, and more preferably has a layered rock salt structure.
  • the layered rock salt structure has the property that the redox potential decreases due to occlusion of lithium ions, and the redox potential increases due to elimination of lithium ions.
  • the layered rock salt structure is a crystal structure in which transition metal layers other than lithium and lithium layers are alternately stacked with an oxygen atom layer interposed therebetween, that is, an ion layer and lithium ions of transition metals other than lithium.
  • Crystal structure in which layers are alternately stacked with oxide ions typically ⁇ -NaFeO 2 type structure: a structure in which transition metal and lithium are regularly arranged in the [111] axis direction of cubic rock salt type structure ).
  • lithium-transition metal composite oxides having a layered rock salt structure include lithium nickelate, lithium manganate, nickel / lithium manganate, nickel / lithium cobaltate, cobalt / nickel / lithium manganate, cobalt / manganese
  • these materials include Mg, Al, Si, Ca, Ti, V, Cr, Fe, Cu, Zn, Ga, Ge, Sr, Y, Zr, Nb, Mo, Ag, Sn, and the like.
  • One or more elements such as Sb, Te, Ba, Bi and the like may be further included.
  • the lithium-transition metal composite oxide is Li x M1O 2 or Li x (M1, M2) O 2 (where 0.5 ⁇ x ⁇ 1.10, M1 is a group consisting of Ni, Mn, and Co)
  • M1 is a group consisting of Ni, Mn, and Co
  • M2 is at least one composition selected from the group consisting of Mg, Al and Zr, more preferably Li x (M1, M2) O 2 , where M1 is Ni and Co And M2 is Al.
  • the proportion of Ni in the total amount of M1 and M2 is preferably 0.6 or more in atomic ratio.
  • Any of such compositions can take a layered rock salt structure.
  • the positive electrode active material is a polycrystal composed of a plurality of crystal particles, and the plurality of crystal particles are preferably oriented. That is, it is effective to orient the crystal faces of the crystal particles constituting the positive electrode active material plate that is a sintered body so that lithium ions are easily diffused. That is, this orientation facilitates the movement of lithium ions, further enhancing the effect of the internal current collecting structure and improving the rate characteristics.
  • This orientation is preferably oriented so that the (003) plane of the layered rock salt structure intersects the plate surface (principal surface) of the positive electrode active material plate, more preferably a plane other than (003). (For example, (104) plane) is preferably oriented parallel to the plate surface of the positive electrode active material plate.
  • the degree of orientation in such a positive electrode active material plate is the ratio of the diffraction intensity (peak intensity) due to the (003) plane to the diffraction intensity due to the (104) plane in the X-ray diffraction from the plate surface of the positive electrode active material plate [003].
  • / [104] and a preferable [003] / [104] ratio is 2 or less, more preferably 1 or less, and still more preferably 0.5 or less.
  • a low [003] / [104] ratio means that the ratio of the appearance of the (003) plane parallel to the plate surface in the plate surface or inside of the positive electrode active material plate is reduced.
  • the positive electrode active material plate 12 is made of a ceramic sintered body containing a positive electrode active material.
  • this ceramic sintered body may contain arbitrary components, such as a conductive support agent, besides a positive electrode active material, it is also possible to set it as the structure which does not contain such arbitrary components substantially.
  • the positive electrode active material plate is preferably made of only the positive electrode active material (consisting essentially of), more preferably made of only the positive electrode active material (consisting of).
  • the positive electrode active material plate 12 and the positive electrode active material constituting the positive electrode active material plate 12 preferably have pores.
  • the presence of pores in the positive electrode active material plate can relieve stress that may be caused by expansion or contraction associated with insertion / extraction of lithium ions due to charge / discharge. Furthermore, it is possible to significantly relieve internal stress that is likely to occur during simultaneous firing with the internal current collector, and to improve reliability. As a result, it is possible to effectively prevent peeling at the interface that may occur when the dense plates are joined together.
  • the positive electrode active material preferably has a porosity of 3 to 30%, more preferably 5 to 25%, and still more preferably 10 to 20%.
  • the voidage is a volume ratio of pores (including open pores and closed pores) in the positive electrode active material plate, and is sometimes referred to as porosity. It can be calculated from the density.
  • the dimensions of the positive electrode active material plate 12 are not particularly limited, but the thickness is preferably 1 to 300 ⁇ m, more preferably 3 to 100 ⁇ m, and still more preferably 3 to 50 ⁇ m from the viewpoint of the active material capacity per unit area.
  • the size of the surface is preferably 0.2 mm ⁇ 0.2 mm to 10 mm ⁇ 10 mm, more preferably 0.5 mm ⁇ 0.5 mm to 2 mm ⁇ 2 mm, from the viewpoint of suppressing warpage of the plate surface and ease of electrode production. .
  • the internal current collector 14 is a current collector mainly composed of a conductor embedded in the positive electrode active material plate 12 and may be in the form of a plate, foil, or film.
  • the material of the internal current collector 14 is not particularly limited as long as it is a conductor such as stainless steel, gold, platinum, palladium, copper, nickel, silver, etc., and can be fired and integrated simultaneously with the lithium composite oxide. A metal foil may be processed.
  • the internal current collector 14 is not limited to a metal, and may be a composite of a lithium ion conductor and an electron conductor.
  • the thickness of the internal current collector 14 is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 10 ⁇ m, still more preferably 1 to 10 ⁇ m.
  • the internal current collector 14 has at least one opening 14a, and the opening 14a is filled with the positive electrode active material 12c so that lithium ions can move. It is preferable that a plurality of openings 14a exist innumerably.
  • the shape of the opening 14a is not particularly limited as long as lithium ion permeability can be ensured, and may be a lattice shape, a mesh shape, a structure having innumerable fine holes, or the like, but is preferably a lattice shape.
  • the opening 14a needs to be filled with an active material. If a grid is used, the active material can be easily filled, and the flatness of the current collector can be easily secured, and the distance between the electrodes is constant. Electric field concentration is less likely to occur. In addition, the influence on the diffusion of lithium ions is suppressed, and the active material on the side not in direct contact with the electrolyte can function as effectively as possible.
  • an external current collector 16 is further provided on one surface of the positive electrode active material plate 12, and the external current collector 16 is electrically connected to the internal current collector 14. Good. Thereby, the function as a current collector can be further improved without impairing various advantages obtained as the positive electrode of the present invention.
  • a plurality of internal current collectors 14 may be embedded in the positive electrode active material plate 12 so as to be separated from each other and in parallel.
  • battery capacity can be further improved without impairing various advantages obtained as the positive electrode of the present invention.
  • An example of the positive electrode according to this embodiment is shown in FIG. In the positive electrode 100 shown in FIG. 4, two internal current collectors 114 a and 114 b are embedded in a positive electrode active material plate 112 so as to be separated from each other and in parallel.
  • the electrolyte batteries 128a and 128b and the negative electrodes 122a and 122b are sequentially formed on both sides of the positive electrode 100, so that the unit cells are arranged in parallel.
  • a stacked battery can be configured.
  • the positive electrode according to the present invention comprises an integrated sintered body provided with a positive electrode active material plate and an internal current collector.
  • the positive electrode can be manufactured by a method including a sintering step in which a material to be a positive electrode active material plate containing a positive electrode active material and a material to be an internal current collector are integrated by firing. desired.
  • a green sheet of a positive electrode active material is prepared by a tape molding method, a printing method, etc., and a conductor paste is printed in a desired pattern on one side of the active material green sheet.
  • the green body of the current collector After forming the green body of the current collector, a method of laminating green sheets of active material so as to sandwich the conductor pattern, and pressing and integrating them, (2) producing a green sheet of the conductor, as described above (3) Laminate and press and sinter so that the conductive foil is sandwiched between green sheets of active material as described above. And (4) a method in which active material particles are directly applied to a conductor foil by aerosol deposition, powder jet deposition, thermal spraying, and the like, and then integrated by sintering. In any of the above methods, the external current collector may be formed simultaneously.
  • the green sheet of the positive electrode active material used in the manufacturing method described above may be made of a positive electrode active material precursor that gives a positive electrode active material made of lithium composite oxide through sintering, and may be manufactured by any method. Good. Therefore, a green sheet may be formed using a molding slurry containing a compound of a constituent element other than lithium in the lithium composite oxide in the form of particles, and a lithium compound such as lithium carbonate may be applied to the green sheet. Alternatively, a green sheet containing a compound containing all the constituent elements of the lithium composite oxide may be formed at a time. That is, the lithium compound can be added at the time of molding or before firing after molding.
  • the lithium compound can be added to the molding slurry described above together with the positive electrode active material precursor particles during molding.
  • a compact that does not contain a lithium compound is temporarily calcined (molded calcined), and then a mixture of the calcined compact and the lithium compound is calcined (main calcining) in two stages (lithium
  • the molded body to be preliminarily fired sandwiches a conductor pattern to be an internal current collector.
  • any lithium-containing compound that can finally give the composition of the positive electrode active material preferably Li x M1O 2 or Li x (M1, M2) O 2
  • examples include lithium oxide and lithium carbonate.
  • the lithium amount may be excessive by about 0.5 to 40 mol%.
  • the green sheet can be produced by forming the raw slurry into a sheet and drying it. Thereby, a green sheet in which a large number of primary particles are oriented can be obtained.
  • the thickness of the green sheet is preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less. In addition, the thickness of the green sheet is preferably 0.5 ⁇ m or more.
  • the molding method is not particularly limited as long as the raw material powder is filled in the molded body with the same crystal orientation. For example, a green sheet filled with the raw material powder with the same crystal orientation can be obtained by forming (forming) a slurry containing the raw material powder using a doctor blade method.
  • a slurry containing raw material powder is applied to a flexible substrate (for example, an organic polymer plate such as a PET film), and the applied slurry is dried and solidified.
  • a dry film is used.
  • the dry film is peeled from the above-described substrate to obtain a green sheet in which the raw material powder is oriented (filled with the same crystal orientation).
  • the obtained green sheet is preferably dried and then processed into a desired size by punching or the like.
  • a binder, a plasticizer, or the like may be appropriately added to the raw material powder dispersed in an appropriate dispersion medium.
  • the type and amount of the additive such as a binder are appropriately adjusted so that the packing density and orientation degree of the raw material powder at the time of molding can be controlled to a desired state.
  • a slurry containing raw material powder it is preferable to adjust the viscosity to 0.5 to 20 Pa ⁇ s or to defoam under reduced pressure. Further, when another compound is present in the pores, it is preferable to prepare a slurry containing this compound and the raw material powder.
  • Lithium ion secondary battery A lithium ion secondary battery can be constructed using the positive electrode of the present invention.
  • FIG. 2 conceptually shows an example of such a lithium ion secondary battery.
  • a lithium ion secondary battery positive electrode 10 shown in FIG. 2 a negative electrode 22, and an electrolyte 28 provided between the positive electrode 10 and the negative electrode 22 are provided, and a separator is appropriately provided as necessary.
  • Portions other than the positive electrode 10 in the lithium ion secondary battery 20 can be formed using various conventionally known materials.
  • the negative electrode active material constituting the negative electrode layer 24 amorphous carbonaceous materials such as soft carbon and hard carbon, highly graphitized carbon materials such as artificial graphite and natural graphite, acetylene black, lithium metal, and the like are used. it can.
  • the negative electrode 22 is formed by applying a negative electrode material prepared using these negative electrode active materials onto the negative electrode current collector 26 made of a metal foil or the like, or using metallic lithium as it is.
  • the electrolyte 28 may be either an electrolytic solution or a solid electrolyte.
  • Organic solvents used for non-aqueous electrolytes include carbonate solvents such as ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), propylene carbonate (PC), ⁇ -butyrolactone, tetrahydrofuran A single solvent such as acetonitrile or a mixed solvent thereof is preferred.
  • Examples of the electrolyte contained in the electrolytic solution include lithium complex fluorine compounds such as lithium hexafluorophosphate (LiPF 6 ) and lithium borofluoride (LiBF 4 ); lithium halides such as lithium perchlorate (LiClO 4 ); Can be used.
  • electrolyte solution is prepared by melt
  • LiPF 6 that hardly causes oxidative decomposition and has high conductivity of the nonaqueous electrolytic solution.
  • an inorganic solid electrolyte having lithium ion conductivity is preferable.
  • the lithium ion conductive inorganic solid electrolyte include at least one selected from the group consisting of garnet-based ceramic materials, nitride-based ceramic materials, perovskite-based ceramic materials, and phosphate-based ceramic materials.
  • garnet based ceramic materials include Li—La—Zr—O based materials (specifically, Li 7 La 3 Zr 2 O 12 etc.), Li—La—Ta—O based materials (specifically, Li 7 La 3 Ta 2 O 12 ) and the like described in Patent Documents 4 to 6 (Japanese Patent Laid-Open Nos.
  • nitride ceramic materials include Li 3 N, LiPON, and the like.
  • perovskite ceramic materials include Li—La—Ti—O materials (specifically, LiLa 1-x Ti x O 3 (0.04 ⁇ x ⁇ 0.14), etc.).
  • phosphoric acid based ceramic materials include Li—Al—Ti—PO, Li—Al—Ge—PO, and Li—Al—Ti—Si—PO (specifically, Li 1 + x + y Al x Ti 2-x Si y P 3-y O 12 (0 ⁇ x ⁇ 0.4, 0 ⁇ y ⁇ 0.6) and the like.
  • a particularly preferred lithium ion conductive inorganic solid electrolyte is a garnet-based ceramic material in that no reaction occurs even when it is in direct contact with negative electrode lithium.
  • an oxide sintered body having a garnet type or a garnet type-like crystal structure containing Li, La, Zr and O is excellent in sinterability and easily densified, and has high ionic conductivity. This is preferable.
  • a garnet-type or garnet-like crystal structure of this type of composition is called an LLZ crystal structure, and is referred to as an X-ray diffraction file No. of CSD (Cambridge Structural Database). It has an XRD pattern similar to 422259 (Li 7 La 3 Zr 2 O 12 ). In addition, No.
  • the constituent elements are different and the Li concentration in the ceramics may be different, so the diffraction angle and the diffraction intensity ratio may be different.
  • the molar ratio Li / La of Li to La is preferably 2.0 or more and 2.5 or less, and the molar ratio Zr / La to La is preferably 0.5 or more and 0.67 or less.
  • This garnet-type or garnet-like crystal structure may further comprise Nb and / or Ta. That is, by replacing a part of Zr of LLZ with one or both of Nb and Ta, the conductivity can be improved as compared with that before the substitution.
  • the substitution amount (molar ratio) of Zr with Nb and / or Ta is preferably set such that the molar ratio of (Nb + Ta) / La is 0.03 or more and 0.20 or less.
  • the garnet-based oxide sintered body preferably further contains Al and / or Mg, and these elements may exist in the crystal lattice or may exist in other than the crystal lattice.
  • the amount of Al added is preferably 0.01 to 1% by mass of the sintered body, and the molar ratio Al / La to La is preferably 0.008 to 0.12.
  • the amount of Mg added is preferably 0.01 to 1% by mass or more, more preferably 0.05 to 0.30% by mass.
  • the molar ratio of Mg to La, Mg / La, is preferably 0.0016 to 0.07.
  • Such LLZ ceramics are manufactured according to a known method as described in Patent Documents 4 to 6 (Japanese Patent Application Laid-Open Nos. 2011-051800, 2011-073962, and 2011-073963). Or it can carry out by correcting it suitably.
  • a positive electrode 100 in which two internal current collectors 114a and 114b are embedded in a positive electrode active material plate 112 apart from each other and in parallel is used.
  • the lithium ion secondary battery includes a positive electrode 100, two negative electrodes 114a and 114b provided on both sides of the positive electrode 100, and electrolytes 128a and 128b provided between the positive electrode 100 and the negative electrodes 114a and 114b. It can be set as the structure provided with the at least 1 laminated structure provided.
  • the negative electrodes 114a and 114b may be composed of negative electrode layers 124a and 124b made of a negative electrode active material and negative electrode current collectors 126a and 126b made of metal foil or the like, respectively. According to this configuration, since the unit battery is a stacked battery that is stacked in parallel, a higher battery capacity can be realized. Moreover, you may comprise the laminated battery which stacked this laminated structure in multiple numbers.
  • a plurality of plate-like positive electrodes are prepared, and the plurality of plate-like positive electrodes are arranged in a tile shape on the plate-like solid electrolyte. Accordingly, there is an advantage that the active material can be filled in the electrode with higher density.
  • Example 1 A positive electrode for a lithium ion secondary battery was produced as follows. First, 100 parts by weight of cobalt oxide particles, 50 parts by weight of dispersion soot (containing xylene and butanol at a weight ratio of 1: 1), polyvinyl butyral as a binder (product number BM-2) 10 Part by weight, 4.5 parts by weight of DOP (Di (2-ethylhexyl) phthalate: manufactured by Kurokin Kasei Co., Ltd.) as a plasticizer, and 3 parts by weight of a dispersant (Kao Co., Ltd., Rheodor SPO-30) were weighed. .
  • DOP Di (2-ethylhexyl) phthalate: manufactured by Kurokin Kasei Co., Ltd.
  • a gold foil to be an internal current collector was laminated so as to be sandwiched between the two upper and lower green sheets.
  • As the gold foil one having a thickness of 5 ⁇ m in which 0.2 mm square holes are arranged in a staggered pattern so that lithium ions can diffuse is used.
  • This green sheet / current collector / green sheet laminate was simultaneously fired at 1000 ° C. to obtain an intermediate product.
  • Lithium carbonate was applied to the obtained intermediate product and fired at 750 ° C. to obtain an integrated sintered body.
  • the positive electrode thus obtained was formed by aligning a plurality of crystal particles made of LiCoO 2 having a layered rock salt structure as a positive electrode active material, and had pores. Further, in the positive electrode after firing, the positive electrode active material was also filled in the grid-like holes of the internal current collector.
  • the obtained positive electrode had an area of 5 mm ⁇ 5 mm and a thickness of 20 ⁇ m.
  • a coin-type unit cell battery was manufactured using the obtained positive electrode, an electrolyte solution, a negative electrode, and the like.
  • the electrolytic solution a solution obtained by dissolving LiPF 6 in an organic solvent in which ethylene carbonate (EC) and diethyl carbonate (DEC) were mixed at an equal volume ratio to a concentration of 1 mol / L was used. Li metal was used as the negative electrode.
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • discharge capacity at 1C rate A value obtained by dividing “discharge capacity at 1 C rate” by “discharge capacity at 0.1 C rate” (actually, the value expressed as a percentage) was defined as “rate capacity maintenance rate”.
  • the volume-converted discharge capacity (mAh / cc) was calculated as the capacity obtained by multiplying the discharge capacity (mAh / g) at 0.1 C described above by the bulk density (g / cc) of the positive electrode.
  • the density of the positive electrode required at that time was calculated using the Archimedes method or the like.
  • the positive electrode of this invention since the positive electrode of this invention has a collector inside, the mass and volume of the collector were measured in advance, and the volume conversion discharge capacity was computed as the positive electrode active material net.
  • the rate characteristic of the sample of the present invention obtained by integrally firing the 10 ⁇ m active material on both main surfaces of the internal current collector was 92% and the volume conversion discharge capacity was 580 mAh / cc.
  • Example 2 (Comparison) Instead of the positive electrode produced in Example 1, for the purpose of comparison, the unit cell battery was produced in the same manner as described above, except that a positive electrode that was integrally fired with an active material of 20 ⁇ m disposed only on one side of the current collector was used. Evaluation was performed. As a result, the rate characteristic of this comparative sample was 78% and the volume conversion discharge capacity was 590 mAh / cc. This rate characteristic was considerably lower than the rate characteristic of Example 1 of 92%.
  • the positive electrode having active material layers on both sides according to the present invention can achieve both high rate characteristics and high battery capacity.
  • a liquid electrolyte was used. From these results, it can be seen that superior battery characteristics can be expected in combination with solid electrolytes such as polymers, gels, and ceramics.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne une électrode positive pour batteries secondaires au lithium-ion, qui est apte à réaliser un bon équilibre entre une capacité de charge/décharge élevée, un débit de charge/décharge élevée, une sortie élevée et une résistance mécanique élevée même dans une cellule d'unité. Cette électrode positive pour batteries secondaires au lithium-ion est composée d'un corps fritté intégré qui comprend une plaque de matériau actif d'électrode positive, qui contient un matériau actif d'électrode positive qui est composé d'un oxyde de composite de lithium, et un collecteur interne qui est intégré dans la plaque de matériau actif d'électrode positive. Le collecteur interne comprend au moins une ouverture, et l'ouverture est remplie avec le matériau actif d'électrode positive de façon à rendre mobiles des ions de lithium.
PCT/JP2013/074566 2012-09-26 2013-09-11 Électrode positive pour batteries secondaires au lithium-ion et batterie secondaire au lithium-ion l'utilisant WO2014050569A1 (fr)

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WO2019187917A1 (fr) * 2018-03-28 2019-10-03 日本碍子株式会社 Batterie rechargeable au lithium et carte ayant une batterie intégrée
WO2019220985A1 (fr) * 2018-05-17 2019-11-21 本田技研工業株式会社 Électrode de batterie secondaire au lithium-ion
CN111919327A (zh) * 2018-03-27 2020-11-10 日本碍子株式会社 锂二次电池
CN112088458A (zh) * 2018-05-17 2020-12-15 日本碍子株式会社 锂二次电池
CN112088458B (zh) * 2018-05-17 2024-06-04 日本碍子株式会社 锂二次电池

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CN111919327B (zh) * 2018-03-27 2023-10-17 日本碍子株式会社 锂二次电池
CN111919327A (zh) * 2018-03-27 2020-11-10 日本碍子株式会社 锂二次电池
WO2019187917A1 (fr) * 2018-03-28 2019-10-03 日本碍子株式会社 Batterie rechargeable au lithium et carte ayant une batterie intégrée
CN111886741B (zh) * 2018-03-28 2024-05-28 日本碍子株式会社 锂二次电池及电池内置卡
CN111868992A (zh) * 2018-03-28 2020-10-30 日本碍子株式会社 锂二次电池及内置电池的卡片
CN111886741A (zh) * 2018-03-28 2020-11-03 日本碍子株式会社 锂二次电池及电池内置卡
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TWI755585B (zh) * 2018-03-28 2022-02-21 日商日本碍子股份有限公司 鋰二次電池及內建電池的卡片
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CN112088458A (zh) * 2018-05-17 2020-12-15 日本碍子株式会社 锂二次电池
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JPWO2019220985A1 (ja) * 2018-05-17 2021-05-27 本田技研工業株式会社 リチウムイオン二次電池用電極
WO2019220985A1 (fr) * 2018-05-17 2019-11-21 本田技研工業株式会社 Électrode de batterie secondaire au lithium-ion
CN112088458B (zh) * 2018-05-17 2024-06-04 日本碍子株式会社 锂二次电池

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