WO2024048102A1 - 電極、それを用いた電池及び電極の製造方法 - Google Patents

電極、それを用いた電池及び電極の製造方法 Download PDF

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WO2024048102A1
WO2024048102A1 PCT/JP2023/026326 JP2023026326W WO2024048102A1 WO 2024048102 A1 WO2024048102 A1 WO 2024048102A1 JP 2023026326 W JP2023026326 W JP 2023026326W WO 2024048102 A1 WO2024048102 A1 WO 2024048102A1
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electrode
particles
oxide
solid electrolyte
active material
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French (fr)
Japanese (ja)
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健二 松原
秀治 武澤
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to EP23859872.6A priority Critical patent/EP4583180A4/en
Priority to JP2024544016A priority patent/JPWO2024048102A1/ja
Priority to CN202380062020.9A priority patent/CN119768927A/zh
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid 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
    • 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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 disclosure relates to an electrode, a battery using the same, and a method for manufacturing the electrode.
  • Patent Document 1 discloses that an electrode sintered body containing a solid electrolyte material and an electrode active material at high density is obtained by setting the ratio of the average particle size of the electrode active material to the average particle size of the solid electrolyte material from 12 times to 79 times. Disclose what you get.
  • electrode active material a solid electrolyte in contact with the electrode active material; Equipped with The electrode active material contains an oxide containing titanium and not containing lithium, The oxide is present in the form of particles having a median diameter of more than 2 ⁇ m and less than 7 ⁇ m, Provide electrodes.
  • FIG. 1 is a cross-sectional view showing a schematic configuration of an electrode in the first embodiment.
  • FIG. 2 is a process diagram showing a method for manufacturing an electrode.
  • FIG. 3 is a sectional view showing a schematic configuration of a battery in the second embodiment.
  • FIG. 4 is a process diagram showing a method for manufacturing a battery.
  • FIG. 5 is a graph showing the charge/discharge curve of the first cycle of a half cell using the electrode of Example 1.
  • FIG. 6 is a graph showing the particle size distribution of TiO 2 particles.
  • FIG. 7A is a SEM image (3000x magnification) of the cross section of the electrode of Example 1.
  • FIG. 7B is a SEM image (10,000 times) of the cross section of the electrode of Example 1.
  • FIG. 7A is a SEM image (3000x magnification) of the cross section of the electrode of Example 1.
  • FIG. 7B is a SEM image (10,000 times) of the cross section of the electrode of Example 1.
  • FIG. 8 is a SEM image (10,000 times magnification) of the cross section of the electrode of Example 2.
  • FIG. 9A is a SEM image (3000x magnification) of the cross section of the electrode of Comparative Example 2.
  • FIG. 9B is a SEM image (10,000 times magnification) of the cross section of the electrode of Comparative Example 2.
  • FIG. 10 is a SEM image (10,000 times) of the cross section of the electrode of Comparative Example 4.
  • FIG. 11A is a SEM image (3000x magnification) of the cross section of the electrode of Example 3.
  • FIG. 11B is a SEM image (10,000 times magnification) of the cross section of the electrode of Example 3.
  • Oxides containing titanium have advantages such as being able to be mass-produced at low cost, having excellent charge/discharge characteristics, and being highly safe, and are therefore considered promising as electrode active materials for solid-state batteries.
  • Oxides containing titanium are known to be used in pigments, cosmetics, catalysts, etc. Oxides for these applications typically have the shape of particles on the nano-order.
  • titanium-containing oxide nanoparticles tend to exist in the gaps between particles of the solid electrolyte at the stage of molding the electrode material. In this case, the total contact area between the oxide nanoparticles and the solid electrolyte particles becomes large. Therefore, the oxide nanoparticles become a factor that inhibits the sinterability between particles of the solid electrolyte, worsening the sinterability of the electrode, and ultimately deteriorating the ionic conductivity within the electrode.
  • oxide nanoparticles tend to exist in gaps between particles of the conductive additive, and become a factor that inhibits the electron path, thereby deteriorating the electrical conductivity within the electrode. That is, oxide nanoparticles are not necessarily suitable for producing electrodes with practical electrical conductivity and practical ionic conductivity. Therefore, when using an oxide containing titanium as an electrode active material, it is important to note that sintering between particles of the solid electrolyte and the formation of electron paths between particles of the conductive additive are inhibited. There is a need for a technology to improve the sinterability of electrodes while suppressing the sinterability.
  • FIG. 1 is a cross-sectional view showing a schematic configuration of an electrode 10 in the first embodiment.
  • Electrode 10 includes an electrode active material and a solid electrolyte.
  • the electrode 10 is an electrode manufactured by firing a molded body of a powder material containing powder of an electrode active material and powder of a solid electrolyte.
  • the electrode 10 is used, for example, as a positive electrode or a negative electrode of a solid-state battery.
  • sintering refers to a phenomenon in which bonding occurs between particles when a molded body of powder material is heated, and the molded body becomes dense with volumetric contraction. "Calcination” means heat treatment for sintering.
  • the electrode active material is a material that has the ability to absorb and release metal ions such as lithium ions.
  • the electrode active material includes an oxide that contains titanium and does not contain lithium.
  • the oxide as the electrode active material exists in the form of particles having a median diameter of more than 2 ⁇ m and less than 7 ⁇ m. The oxide particles are bound together by a sintered phase of solid electrolyte. The median diameter of the oxide particles may be more than 3 ⁇ m and less than 7 ⁇ m, or more than 3.4 ⁇ m and less than 6 ⁇ m.
  • the electrode 10 has oxide particles on the order of micrometers as an electrode active material. Oxide particles of such size may exist between solid electrolyte particles during molding of powder materials, but compared to the case where oxide particles of nanometer order size are used, oxidation The total contact area between particles of the object and particles of the solid electrolyte can be reduced. Therefore, the influence of the oxide particles on the order of micrometers as a sintering inhibiting factor can be reduced, and the sinterability of the electrode 10 can be improved. That is, it becomes possible to form a good contact interface between the oxide and the solid electrolyte. This reduces the resistance of the electrode 10. The quality of the sinterability of the electrode 10 can be determined based on the porosity of the electrode 10, for example.
  • the median diameter of the oxide particles as the electrode active material may be a value calculated from an electron microscope image of the cross section of the electrode 10. Specifically, a cross section of the electrode 10 is observed using a scanning electron microscope. The magnification is, for example, 3000 times. Image analysis software is used to measure the Feret diameter of oxide particles present in two different observation fields. "Ferret diameter" is the length of a perpendicular line formed by sandwiching a particle between two parallel lines in a fixed direction. The number of particles to be measured is, for example, 185 or more. That is, the width of the observation fields is adjusted so that 185 or more particles are included in two different observation fields.
  • the coarse particles are, for example, particles having a Feret diameter of 16.5 ⁇ m or more.
  • the volume of each particle is calculated assuming that it is a sphere having the measured Feret diameter.
  • the above median diameter may be the median diameter of secondary particles.
  • Secondary particles may be produced by granulating primary particles with a size on the order of nanometers.
  • primary particles on the order of micrometers can be produced by hydrothermal synthesis.
  • oxides containing titanium include titanium (IV) oxide and composite oxides containing titanium and transition metals other than titanium. These materials have the ability to insert and release metal ions such as lithium ions, and are therefore suitable for the electrode 10 of this embodiment.
  • the oxide as the electrode active material can be co-sintered with the solid electrolyte. Specifically, it is desirable that it is difficult to react with the solid electrolyte and that the crystal structure of the oxide is maintained even after sintering.
  • titanium (IV) oxide is suitable for the electrode 10 of this embodiment because it hardly reacts with a NASICON type oxide solid electrolyte, which is a typical oxide solid electrolyte.
  • titanium (IV) oxide examples include anatase-type (tetragonal) titanium oxide, rutile-type (tetragonal) titanium oxide, and brookite-type (rectangular) titanium oxide.
  • the titanium oxide may include anatase type titanium oxide.
  • the main component of the titanium oxide may be anatase type titanium oxide.
  • Anatase-type titanium oxide is suitable, for example, as an active material for lithium ion secondary batteries. Further, by using anatase-type titanium oxide, the sinterability of the electrode 10 is improved.
  • "Main component" means the component contained in the largest amount in terms of mass ratio. 90% by mass or more of the titanium oxide may be anatase type titanium oxide.
  • the titanium oxide may include substantially only anatase-type titanium oxide.
  • titanium oxide can be investigated by X-ray diffraction measurement or Raman spectroscopy.
  • the ratio of components contained in titanium oxide can be confirmed by analyzing the results of X-ray diffraction measurement using the Rietveld method.
  • composite oxides suitable for electrode active materials include composite oxides containing titanium and niobium.
  • a composite oxide containing titanium and niobium also has the ability to insert and release metal ions such as lithium ions, and is therefore suitable for the electrode 10 of this embodiment.
  • the composite oxide containing titanium and niobium has a composition of, for example, TiNb 2 O 7 .
  • the oxide particles as the electrode active material may contain secondary particles.
  • the secondary particles have a plurality of voids inside them.
  • the voids absorb changes in the volume of the particles.
  • one of the causes of deterioration of sintered oxide all-solid-state batteries is that cracks occur in the electrodes during charging and discharging, resulting in poor contact between the active material and the solid electrolyte. If secondary particles are used as the active material, it is possible to reduce such deterioration.
  • a solid electrolyte may be an electrolyte suitable for forming the electrode 10.
  • Such electrolytes include oxide solid electrolytes.
  • the oxide solid electrolyte include a solid electrolyte having a NASICON type structure, a solid electrolyte having a perovskite type structure, a solid electrolyte having a LISICON type structure, a solid electrolyte having a garnet type structure, and the like.
  • a lithium-containing phosphoric acid compound having a NASICON type structure is suitable for the electrode 10.
  • the NASICON type solid electrolyte is a material that can be sintered at a lower temperature than other oxide solid electrolytes such as a solid electrolyte with a perovskite structure and a solid electrolyte with a garnet structure. Being able to sinter at low temperatures means that it is advantageous for suppressing the reaction between the electrode active material and the solid electrolyte. Furthermore, if sintering is possible at low temperatures, the transition from anatase-type titanium oxide to rutile-type titanium oxide can also be avoided.
  • the lithium-containing phosphoric acid compound may have a composition of Li 1+x Al x Ge 2-x (PO 4 ) 3 (0 ⁇ x ⁇ 2).
  • LAGP a compound having the above composition
  • lithium-containing phosphate compounds include Li 1+x Al x Ti 2-x (PO 4 ) 3 (0 ⁇ x ⁇ 2). This compound may be referred to herein as "LATP.”
  • LAGP is more suitable for the electrode 10 of the present disclosure. That is, since LAGP does not contain Ti, it has a wider potential window on the base side (minus side) than LATP. In this case, it is possible to select a negative electrode active material with a lower potential. This is advantageous in providing high voltage and high capacity batteries.
  • An example of such an effect is a combination of LAGP and titanium (IV) oxide.
  • LAGP is an electrolyte that can be sintered at a lower temperature than LATP. Being able to sinter at low temperatures means that it is advantageous for suppressing the reaction between the electrode active material and the solid electrolyte.
  • the solid electrolyte constitutes a network-like sintered phase.
  • the length of the interface where the particles of the electrode active material and the sintered phase of the solid electrolyte are in contact with each other without a gap is on the order of micrometers, and the sintered phase of the solid electrolyte is in contact with the sintered phase of the electrode active material. forms a good interface with the particles. The presence of such a contact interface contributes to reducing the resistance of the electrode 10.
  • the sintered phase of the solid electrolyte may be a phase in which particles of the solid electrolyte are bonded to each other and grain boundaries are lost.
  • a sintered phase without grain boundaries exhibits excellent ionic conductivity and can form a good contact interface with particles of the electrode active material.
  • Such a structure can be formed by using an amorphous solid electrolyte as a raw material for the electrode 10.
  • the structure of the sintered phase can be confirmed by observing the cross section of the electrode 10 at a magnification of 10,000 times using a scanning electron microscope.
  • the sintered phase of the solid electrolyte includes a crystalline phase and an amorphous phase. It is desirable when the sintered phase of the solid electrolyte includes a crystalline phase because the electrode 10 exhibits higher ionic conductivity.
  • a crystalline phase can be formed by appropriately adjusting the calcination temperature. For example, if firing is performed at a temperature equal to or higher than the crystallization temperature of the solid electrolyte, an electrode 10 containing a crystalline solid electrolyte can be obtained.
  • an amorphous phase may be included in the solid electrolyte. When an amorphous phase is included, the flexibility of the solid electrolyte increases, so volume changes due to expansion and contraction of the electrode active material are easily absorbed by the solid electrolyte.
  • the crystallinity of the solid electrolyte can be examined by X-ray diffraction measurement or a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the electrode 10 may further contain a conductive aid.
  • the conductive aid include carbon materials such as graphite, carbon black, carbon fiber, and carbon nanotubes.
  • Graphite may be natural graphite or artificial graphite.
  • Examples of carbon black include acetylene black and Ketjen black.
  • the carbon material may be crystalline or amorphous.
  • the conductive aid typically has a particle shape on the order of nanometers or micrometers. Examples of the shape of the particles include spherical, ellipsoidal, scaly, and fibrous shapes.
  • the porosity of the electrode 10 is, for example, 30% or less.
  • the lower limit of the porosity is not particularly limited, and is, for example, 5%.
  • the porosity can be calculated from the true density of each material included in the electrode 10, the content of each material, the mass of the electrode 10, and the dimensions of the electrode 10.
  • the content of the electrode active material in the electrode 10 is, for example, 15% by mass or more and 60% by mass or less.
  • the content of the solid electrolyte in the electrode 10 is, for example, 30% by mass or more and 80% by mass or less.
  • the content of the conductive aid in the electrode 10 is, for example, 0.1% by mass or more and 10% by mass or less.
  • FIG. 2 is a process diagram showing a method for manufacturing the electrode 10.
  • the electrode 10 is manufactured by firing a molded body of a mixture of an electrode active material and a solid electrolyte.
  • raw materials are mixed to prepare a slurry.
  • Raw materials for the slurry include, for example, an electrode active material, a solid electrolyte, a conductive aid, a binder, and a solvent.
  • a binder solution may be prepared by mixing a binder and a solvent in advance, and a slurry may be prepared by mixing an electrode active material, a solid electrolyte, and a conductive aid with the binder solution.
  • the oxide particles as the electrode active material have a median diameter of more than 3 ⁇ m and less than 10 ⁇ m, for example, as measured by a laser diffraction particle size distribution analyzer. With such a configuration, the sinterability of the electrode 10 can be improved.
  • the median diameter measured by a laser diffraction particle size distribution analyzer is usually larger than the median diameter determined from a cross-sectional SEM image.
  • the electrode active material, solid electrolyte, and conductive aid may each be powder materials.
  • the median diameter of the solid electrolyte particles is desirably smaller than the median diameter of the electrode active material particles.
  • the ratio of the median diameter of the electrode active material particles to the median diameter of the solid electrolyte particles is, for example, 2 or more and 30 or less.
  • the ratio of the median diameter of the electrode active material particles to the median diameter of the solid electrolyte particles may be 4 or more and 30 or less, or 4 or more and 20 or less.
  • the oxide particles as the electrode active material may have a particle diameter (D90) in a range of more than 6 ⁇ m and less than 15 ⁇ m.
  • D90 is a particle diameter when the cumulative volume is 90% in a volume-based particle size distribution, and can be measured by a laser diffraction particle size distribution measuring device.
  • the BET specific surface area of the oxide particles as the electrode active material may be 1 m 2 /g or more and 7 m 2 /g or less.
  • the BET specific surface area of the oxide particles is appropriately adjusted, side reactions between the oxide particles and the solid electrolyte particles during firing are suppressed.
  • the electrode 10 can have high ionic conductivity. If a side reaction occurs between the oxide particles and the solid electrolyte particles, an interfacial resistance layer will be formed, and such side reactions should be suppressed.
  • the oxide particles as the electrode active material may include primary particles and secondary particles.
  • the ratio (Dp/D50) of the average particle diameter (Dp) of the primary particles to the median diameter (D50) of the particles of the electrode active material is, for example, 0.6 or less.
  • the ratio (Dp/D50) is preferably 0.16 or less.
  • the average particle diameter (Dp) of the primary particles of the oxide can be determined by the following method. Observe the oxide particles with a scanning electron microscope (30,000x magnification). Fifty primary particles whose contours can be confirmed in the obtained image are selected. Measure the particle diameter on the long axis side of the selected primary particle. The average particle diameter of 50 primary particles is calculated. The calculated value is regarded as the average particle diameter (Dp) of the primary particles.
  • the oxide particles serving as the electrode active material may have a bimodal particle size distribution.
  • the sinterability of the electrode 10 can be improved.
  • the resistance of the electrode 10 can be lowered.
  • a first peak exists in the range of 0.5 ⁇ m or more and 2.5 ⁇ m or less, and a second peak exists in the range of 3 ⁇ m or more and 9 ⁇ m or less. sell.
  • the second peak is larger than the first peak.
  • a peak may exist in the range of 0.2 ⁇ m or more and 2 ⁇ m or less.
  • the solid electrolyte particles have a median diameter of, for example, 100 nm or more and 2000 nm or less.
  • the solid electrolyte particles as a raw material may be amorphous.
  • the amorphous solid electrolyte can form a good interface with particles of the electrode active material at low temperatures by performing pre-calcination in a temperature range above the glass transition temperature and below the crystallization temperature. This is because the solid electrolyte has good flexibility in a temperature range above the glass transition temperature and below the crystallization temperature. Thereafter, the ionic conductivity of the electrode 10 is improved by increasing the crystallinity of the solid electrolyte by firing at an appropriate temperature range above the crystallization temperature and below the melting point. Furthermore, an amorphous solid electrolyte can be sintered at a lower temperature than a crystalline solid electrolyte. The fact that it can be sintered at a low temperature means that it is advantageous in terms of suppressing the reaction between the electrode active material and the solid electrolyte.
  • the solid electrolyte is amorphous using a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the degree of crystallinity is determined by the following formula.
  • the measured heat of crystallization means the amount of heat generated during crystallization of the solid electrolyte that is the sample to be measured.
  • Completely amorphous crystallization heat amount means the heat amount associated with crystallization in an amorphous solid electrolyte in which only a halo pattern is observed in the X-ray diffraction pattern.
  • Crystallinity (%) 100 x (Qa-Qs)/Qa Qs: Measured crystallization heat (J/g) Qa: Completely amorphous crystallization heat (J/g)
  • volume diameter means the particle diameter when the cumulative volume in the volume-based particle size distribution is 50%.
  • the volume-based particle size distribution is measured at the raw material stage using a laser diffraction particle size distribution measuring device. At the electrode 10 stage, measurement is performed by cross-sectional image analysis.
  • the binder is decomposed and removed by firing.
  • thermoplastic resins such as polyvinyl butyral, polyvinylidene fluoride, cellulose, acrylic, urethane, and polyvinyl alcohol can be used.
  • the solvent is typically an organic solvent such as absolute alcohol (eg, absolute ethanol), toluene, butyl acetate, NMP, and the like.
  • the slurry may contain a plasticizer.
  • the type of plasticizer is not particularly limited, and phthalate esters such as dioctyl phthalate and diisononyl phthalate can be used.
  • the conductive aid may be a carbon material.
  • the carbon material may include amorphous carbon.
  • the carbon material particles may have a median diameter of 70 nm or less and a BET specific surface area of 60 m 2 /g or less. By using such a carbon material, the sinterability of the electrode 10 can be improved.
  • the lower limit of the median diameter of the carbon material particles is not particularly limited, and is, for example, 10 nm.
  • the lower limit of the BET specific surface area of the carbon material particles is not particularly limited, and is, for example, 10 m 2 /g.
  • step S2 the slurry is applied to the base material to form a coating film.
  • the substrate can be a resin substrate, a glass substrate, a ceramic substrate or a metal substrate.
  • the solvent is removed from the coating film. Thereby, a molded body for an electrode is obtained.
  • the coating film may be heated or the coating film may be naturally dried. If necessary, the coating film may be subjected to press processing or hot press processing.
  • the slurry may be shaped and dried without the use of a substrate.
  • the coating film After applying the slurry to a base material to form a coating film, the coating film may be pulverized, and the raw material powder obtained by the pulverization may be pressed or hot-pressed to produce an electrode molded body.
  • step S3 the electrode molded body is pre-fired.
  • Temporary firing is performed, for example, in the air or in an inert atmosphere.
  • the inert atmosphere is, for example, a nitrogen gas atmosphere or a rare gas atmosphere. It is also possible to mix small amounts of oxygen into the inert atmosphere.
  • the temperature for pre-firing is, for example, from 250°C to 600°C.
  • the firing time for the temporary firing is, for example, 1 hour to 60 hours.
  • the pre-calcination be performed in a temperature range where the binder is sufficiently removed, the solid electrolyte is softened above the glass transition temperature, and where crystallization of the solid electrolyte does not proceed. In this way, a good interface is formed between the electrode active material and the solid electrolyte as the binder is removed.
  • step S4 the electrode molded body is fired.
  • the main firing is performed, for example, in the air or in an inert atmosphere.
  • the inert atmosphere is, for example, a nitrogen gas atmosphere or a rare gas atmosphere. It is also possible to mix small amounts of oxygen into the inert atmosphere.
  • the main firing temperature (ambient temperature) is, for example, 550°C to 900°C.
  • the firing time for the main firing is, for example, 1 hour to 15 hours.
  • the main firing particles of the solid electrolyte are bonded to each other to form a sintered phase without grain boundaries.
  • the main firing is desirably carried out in a temperature range where crystallization of the solid electrolyte progresses appropriately. As the crystallinity of the solid electrolyte improves, the ionic conductivity of the electrode 10 improves.
  • the electrode 10 can be manufactured through the above steps.
  • FIG. 3 is a cross-sectional view showing a schematic configuration of a battery 100 in the second embodiment.
  • the battery 100 includes a positive electrode 20, a negative electrode 30, and an electrolyte layer 40. Electrolyte layer 40 is arranged between positive electrode 20 and negative electrode 30.
  • the electrode 10 described in the first embodiment is used as the positive electrode 20 or the negative electrode 30.
  • the effect of lowering the resistance can be obtained in the positive electrode 20 or the negative electrode 30.
  • the electrode 10 described in the first embodiment is preferably used as the negative electrode 30.
  • an oxide containing titanium acts as a negative electrode active material.
  • Electrode 10 is suitable for negative electrode 30 because titanium-containing oxides are suitable for negative electrode active materials.
  • the titanium-containing oxide does not contain lithium in a state where the battery 100 is not charged or discharged after assembly. In other words, the battery 100 is in a fully discharged state.
  • the electrode 10 is also possible to use the electrode 10 as a positive electrode.
  • a material less noble than the titanium-containing oxide, such as lithium metal, is used for the negative electrode active material.
  • the positive electrode 20 includes a positive electrode active material.
  • the positive electrode active material is a material that has the ability to absorb and release metal ions such as lithium ions.
  • Examples of the positive electrode active material include lithium-containing transition metal oxides, lithium-containing transition metal phosphates, and the like. Among these, lithium-containing transition metal phosphates are suitable for electrode 10. Examples of lithium-containing transition metal phosphates include lithium iron phosphate, lithium vanadium phosphate, lithium cobalt phosphate, and lithium nickel phosphate.
  • the positive electrode 20 may contain a solid electrolyte, a conductive additive, and the like.
  • the electrolyte layer 40 includes a solid electrolyte.
  • the solid electrolyte include a sulfide solid electrolyte, a halide solid electrolyte, a complex hydride solid electrolyte, a porous oxide solid electrolyte impregnated with an electrolytic solution, and an oxide solid electrolyte.
  • the composition of the solid electrolyte included in the electrolyte layer 40 may be the same as or different from the composition of the solid electrolyte included in the positive electrode 20.
  • the composition of the solid electrolyte included in the electrolyte layer 40 may be the same as or different from the composition of the solid electrolyte included in the negative electrode 30.
  • the positive electrode 20, the electrolyte layer 40, and the negative electrode 30 may contain solid electrolytes of the same composition.
  • the positive electrode 20, the negative electrode 30, and the electrolyte layer 40 may be made of a sintered body.
  • the positive electrode 20, negative electrode 30, and electrolyte layer 40 can be integrally formed by co-firing.
  • the positive electrode 20, negative electrode 30, and electrolyte layer 40 are integrated by simultaneous firing, mutual contact between the positive electrode 20, negative electrode 30, and electrolyte layer 40 can be ensured, which improves the conductivity of metal ions such as lithium ions. can be improved.
  • FIG. 4 is a process diagram showing a method for manufacturing the battery 100.
  • a slurry is prepared. Specifically, a positive electrode slurry, an electrolyte layer slurry, and a negative electrode slurry are prepared. These slurries can be prepared following the method described in step S1 of FIG. Note that the electrolyte slurry does not contain an electrode active material or a conductive aid.
  • a green sheet is produced. Specifically, a positive electrode green sheet, an electrolyte layer green sheet, and a negative electrode green sheet are produced using a positive electrode slurry, an electrolyte layer slurry, and a negative electrode slurry.
  • a green sheet can be produced by applying the slurry to a base material to form a coating film, and drying the coating film. The green sheet is peeled off from the base material at an appropriate timing.
  • step ST3 green sheets are stacked. Specifically, a positive electrode green sheet, an electrolyte layer green sheet, and a negative electrode green sheet are laminated in this order and pressed together. As a result, a laminate including a positive electrode green sheet, an electrolyte layer green sheet, and a negative electrode green sheet is obtained.
  • step ST4 and step ST5 the steps of preliminary firing and main firing are performed.
  • the preliminary firing and main firing are as explained in step S3 and step S4 of FIG.
  • a sintered battery 100 is obtained through the above steps.
  • Electrode active material a solid electrolyte in contact with the electrode active material; Equipped with The electrode active material contains an oxide containing titanium and not containing lithium, The oxide is present in the form of particles having a median diameter of more than 2 ⁇ m and less than 7 ⁇ m, electrode.
  • Titanium oxide has the ability to absorb and release metal ions such as lithium ions, so it is suitable for the electrode of the present disclosure.
  • a composite oxide containing titanium and niobium also has the same ability and is therefore suitable for the electrode of the present disclosure.
  • the resistance of the battery can be lowered.
  • the electrode active material includes oxide particles containing titanium and not containing lithium, The oxide particles have a median diameter of more than 3 ⁇ m and less than 10 ⁇ m, Method of manufacturing electrodes.
  • the positive electrode green sheet or the negative electrode green sheet is a molded body of a mixture containing an electrode active material and a solid electrolyte,
  • the electrode active material includes oxide particles containing titanium and not containing lithium, The oxide particles have a median diameter of more than 3 ⁇ m and less than 10 ⁇ m, How to manufacture batteries.
  • Example 1 20 parts by mass of TiO 2 (anatase type), 75 parts by mass of LAGP (amorphous), 5 parts by mass of acetylene black (manufactured by Denka, Li-400), 38.75 parts by mass of binder solution, and 116 parts by mass
  • a slurry was prepared by mixing .25 parts by mass of super dehydrated ethanol. These raw materials were mixed using a rotation and revolution mixer (manufactured by Shinky Co., Ltd., Rentaro) at 2000 rpm for 30 minutes.
  • a binder solution was prepared by mixing 15 parts by mass of polyvinyl butyral (BM-1, manufactured by Sekisui Chemical Co., Ltd.) and 140 parts by mass of super-dehydrated ethanol.
  • the TiO 2 particles used were secondary particles.
  • the particle size distribution of TiO 2 , the BET specific surface area of TiO 2 , and the particle size distribution of LAGP were measured in advance.
  • the particle size distribution of TiO 2 and the particle size distribution of LAGP were measured using a laser diffraction particle size distribution analyzer (Mastersizer 3000, manufactured by Malvern Panalytical). D10, D50, and D90 were calculated from the particle size distribution. The results are shown in Table 1.
  • the median diameter of TiO 2 was 4.180 ⁇ m.
  • the median diameter of LAGP was 0.888 ⁇ m.
  • D10 is the particle diameter when the cumulative volume is 10% in the volume-based particle size distribution.
  • Mastersizer is a registered trademark of Malvern Panalytical.
  • the average particle diameter (Dp) of the primary particles of TiO 2 was calculated by the method described above using a scanning electron microscope.
  • the BET specific surface area of TiO 2 was measured by the following method. A predetermined amount of TiO 2 was placed in a measurement test tube, and the measurement test tube was connected to a specific surface area/pore distribution measuring device (Autosorb iQ-MP, manufactured by Quantachrome). Thereafter, a nitrogen gas adsorption test was conducted under the conditions of an adsorption temperature of 77 K and an upper limit of adsorption relative pressure of 0.99 (P/P0). Analysis software ASiQWin was used to perform analysis using the BET method in the linear region of the adsorption isotherm, and the BET specific surface area was calculated. "Autosorb” is a registered trademark of Sysmex Corporation.
  • the slurry was dried on a hot plate with a set temperature of 80°C. After confirming that ethanol had been sufficiently removed from the slurry, the dried membrane was coarsely ground and subjected to vacuum drying treatment (80° C., 2 hours). The coarsely ground product after vacuum drying was placed in a mortar and manually ground for 15 minutes to obtain a raw material powder.
  • the raw material powder was molded by a uniaxial pressing method to obtain a molded body for an electrode.
  • the pressurizing conditions were 276 MPa and 1 minute.
  • the electrode molded body was pre-fired to remove the binder.
  • the conditions for pre-firing were 530° C. (ambient temperature) in the atmosphere for 2 hours.
  • the electrode molded body was subjected to main firing to obtain the electrode of Example 1.
  • the main firing conditions were 700° C. (ambient temperature) for 2 hours under a nitrogen atmosphere.
  • the dimensions of the electrode of Example 1 were 9.53 mm in diameter and 0.6471 mm in thickness. The mass was 115.0 mg.
  • Example 2 As shown in Table 1, the electrode of Example 2 was produced in the same manner as Example 1 except that LAGP (amorphous) having a median diameter of 0.300 ⁇ m was used. The dimensions of the electrode of Example 2 were 9.26 mm in diameter and 0.6363 mm in thickness. The mass was 111.5 mg.
  • LAGP amorphous
  • Comparative Example 1 As shown in Table 1, an electrode of Comparative Example 1 was produced in the same manner as in Example 1, except that titanium oxide (anatase type) having a median diameter of 0.491 ⁇ m was used. The dimensions of the electrode of Comparative Example 1 were 9.96 mm in diameter and 0.6528 mm in thickness. The mass was 114.9 mg. The titanium oxide particles used were secondary particles.
  • Comparative Example 2 As shown in Table 1, an electrode of Comparative Example 2 was produced in the same manner as in Example 1, except that titanium oxide (anatase type) having a median diameter of 1.540 ⁇ m was used. The dimensions of the electrode of Comparative Example 2 were 9.96 mm in diameter and 0.6380 mm in thickness. The mass was 114.4 mg. The titanium oxide particles used were secondary particles.
  • Example 3 As shown in Table 1, Example 1 except that titanium oxide (anatase type) with a median diameter of 1.540 ⁇ m was used and LAGP (amorphous) with a median diameter of 0.300 ⁇ m was used.
  • An electrode of Comparative Example 3 was produced in the same manner as described above. The dimensions of the electrode of Comparative Example 3 were 9.80 mm in diameter and 0.6457 mm in thickness. The mass was 112.6 mg.
  • the titanium oxide particles used were secondary particles.
  • Comparative example 4 As shown in Table 1, an electrode of Comparative Example 4 was produced in the same manner as in Example 1, except that titanium oxide (anatase type) having a median diameter of 0.675 ⁇ m was used. The dimensions of the electrode of Comparative Example 4 were 9.91 mm in diameter and 0.6410 ⁇ m in thickness. The mass was 114.6 mg. The titanium oxide particles used were secondary particles.
  • the true density of each material used for making the electrode was measured in advance.
  • the porosity of the electrode was calculated using the dimensions of the electrode, the measured true density, and the content of each material.
  • the electrode was assumed to contain only TiO 2 , LAGP and conductive aid.
  • the true density was measured by the He substitution method using a pycnometer (Ultrapyc 5000, manufactured by Anton Paar).
  • LAGP while an amorphous material is used as a starting material, it is difficult to evaluate the density after sintering. Therefore, the theoretical density was used as the true density of LAGP. The results are shown in Table 2.
  • the electrical conductivity of the electrode was measured by the following method. First, the electrode was placed in a vacuum dryer and dried at 80° C. for 1 hour. Next, the Li metal foil, the solid polymer electrolyte membrane, the electrode, the solid polymer electrolyte membrane, and the Li metal foil were laminated in this order, and these were placed in a closed bipolar cell (manufactured by Hosensha). A LiTFSI-PEO membrane was used as the solid polymer electrolyte membrane. The weight average molecular weight Mw of PEO contained in the LiTFSI-PEO film was 600,000.
  • chronoamperometry measurements were performed at measurement voltages of 0.1V, 0.25V, 0.5V, and 0.75V.
  • the current value the value 70 seconds after the voltage was applied was used.
  • the ambient temperature during the measurement was 60°C.
  • the resistance value was calculated from the relationship between voltage and current. Ionic conductivity was calculated using the electrode dimensions. The results are shown in Table 2.
  • the electrical conductivity of the electrode was measured by the following method. First, the electrode was placed in a vacuum dryer and dried at 80° C. for 1 hour. Next, a 290 nm thick Au thin film was formed on both sides of the electrode by sputtering. The electrodes were placed in a closed bipolar cell (manufactured by Hosensha). Thereafter, chronoamperometry measurements were performed at measurement voltages of 0.1V, 0.25V, 0.5V, and 0.75V. As the current value, the value 70 seconds after the voltage was applied was used. The ambient temperature during the measurement was 25°C. The resistance value was calculated from the relationship between voltage and current. Electrical conductivity was calculated using the dimensions of the electrode. The results are shown in Table 2.
  • the amount of interfacial side reaction of the electrode was measured by the following method. First, the electrode was placed in a vacuum dryer and dried at 80° C. for 1 hour. Next, a 290 nm thick Au thin film was formed on one side of the electrode by sputtering. Next, the Au thin film, electrode, solid polymer electrolyte membrane, and Li metal foil were laminated in this order, and these were placed in a closed bipolar cell (manufactured by Hosensha) to obtain a half cell. A LiTFSI-PEO membrane was used as the solid polymer electrolyte membrane.
  • a half cell charge/discharge test was conducted in constant current/constant voltage (CCCV) mode at 60° C., and a first cycle charge/discharge curve was obtained.
  • the battery was discharged at a constant current of 0.01C until the voltage reached 1.5V, and then discharged at a constant voltage of 1.5V for 5 hours.
  • the battery was charged at a constant current of 0.01C until the voltage reached 3V, and then charged at a constant voltage of 3V for 5 hours.
  • FIG. 5 is a graph showing a charge/discharge curve of a half cell using the electrode of Example 1.
  • the vertical axis represents the potential (unit: V) relative to the dissolution deposition potential of lithium metal.
  • the horizontal axis represents the ratio (%) of the capacity at each point on the graph when the discharge capacity in the first cycle is assumed to be 100.
  • TiO 2 has a plateau region at a potential lower than 2V. Therefore, the drive potential range of TiO 2 is less than 2V.
  • the capacitance value during discharge is defined as the "interfacial side reaction amount Ci.”
  • the redox capacitance observed outside the drive potential region of TiO 2 captures charging and discharging originating from a diffusion layer (reaction layer) formed when Ti contained in TiO 2 diffuses into LAGP during sintering.
  • a small amount of interfacial side reaction means that the side reaction between LAGP and TiO 2 during sintering is suppressed, and also means that the formation of a reaction layer due to the side reaction is suppressed. do. Suppression of the formation of a reaction layer due to side reactions is desirable because the resistance of the electrode is reduced.
  • the porosity of the electrodes of Examples 1 and 2 was 26.86% and 24.82%, respectively, which was significantly lower than the porosity of the electrodes of Comparative Examples 1 to 4.
  • the electrodes of Examples 1 and 2 exhibited high electrical conductivity that significantly exceeded the electrical conductivity of the electrodes of Comparative Examples 1 to 4.
  • the ionic conductivities of the electrodes of Examples 1 and 2 were higher than those of the electrodes of Comparative Examples 1 to 4. It is presumed that this result was brought about by the low porosity of the electrode of the example and the characteristic structure of the electrode of the example.
  • the influence of the characteristic structure of the electrode in the example was also noticeable in the amount of interfacial side reactions. That is, the amount of interfacial side reactions in Example 1 was about 50% of the amount of interfacial side reactions in Comparative Example 4.
  • FIG. 6 is a graph showing the particle size distribution of TiO 2 particles used in Examples and Comparative Examples.
  • the horizontal axis shows the particle diameter on a logarithmic scale.
  • the vertical axis indicates the ratio of the total volume of the particles having the particle diameter shown on the horizontal axis to the volume of the entire particle.
  • the TiO 2 particles used in Examples 1 and 2 had a bimodal particle size distribution, ie, two peaks.
  • a first peak existed in the range of 0.5 ⁇ m or more and 2.5 ⁇ m or less
  • a second peak existed in the range of 3 ⁇ m or more and 9 ⁇ m or less.
  • the second peak was larger than the first peak.
  • the TiO 2 particles used in the comparative example also exhibited a bimodal particle size distribution and contained relatively large particles.
  • the porosity of the electrode of the comparative example was low. It is presumed that the large particles contained in the TiO 2 particles of the comparative example were only weakly agglomerated primary particles, and were separated into nano-order primary particles during processes such as slurry preparation and coating film pulverization. This is supported by the absence of large particles of TiO 2 in the SEM images of FIGS. 9A, 9B and 10.
  • FIG. 7A and 7B are SEM images (3000x or 10000x) of the cross section of the electrode of Example 1.
  • FIG. 8 is a SEM image (10,000 times magnification) of the cross section of the electrode of Example 2.
  • 9A and 9B are SEM images (3000x or 10000x) of the cross section of the electrode of Comparative Example 2.
  • FIG. 10 is a SEM image (10,000 times) of the cross section of the electrode of Comparative Example 4.
  • the electrode active material 12 (TiO 2 ) maintained the state of particles with a large diameter.
  • the large diameter particles of the electrode active material 12 were secondary particles having a plurality of pores inside. Grain boundaries with lengths on the order of micrometers were formed along the outer edges of the sintered phase of the solid electrolyte 14 (LAGP) and the particles of the electrode active material 12. Due to the progress of sintering, grain boundaries between particles of the solid electrolyte 14 were not observed.
  • the conductive aid 16 was uniformly dispersed throughout the electrode.
  • the median diameter (D50) of the electrode active material 12 was calculated by the method described above. As a result, in the electrode of Example 1, the median diameter of the electrode active material 12 was 3.5 ⁇ m. Secondary particles having a plurality of pores were regarded as the electrode active material 12.
  • the electrode of Example 2 using a solid electrolyte with a median diameter of 0.300 ⁇ m also had the same structure as the electrode of Example 1 shown in FIGS. 7A and 7B.
  • the median diameter of the electrode active material 12 was calculated using a SEM image (3000x magnification) of the cross section of the electrode of Example 2. As a result, in the electrode of Example 2, the median diameter of the electrode active material 12 was 3.6 ⁇ m.
  • the particles of the electrode active material 12a were dispersed while maintaining nano-order size. While some particles of the electrode active material 12a are completely surrounded by the sintered phase of the solid electrolyte 14a, they do not have sufficient contact with the solid electrolyte 14a facing the void of the electrode. Many particles were also present.
  • the conductive aid 16a was uniformly dispersed throughout the electrode.
  • oxide (TiO 2 ) particles having a maximum Feret diameter of more than 5 ⁇ m appeared in the cross-sectional SEM images. Specifically, oxide (TiO 2 ) particles having a maximum Feret diameter of approximately 7 ⁇ m appeared in the cross-sectional SEM image. This also applies to Example 3, which will be described later. As shown in FIGS. 9A, 9B, and 10, no such large-sized oxides were observed in the cross section of the electrode of the comparative example.
  • the "maximum Feret diameter" is the maximum length of a perpendicular line formed by sandwiching a particle between two parallel lines.
  • Example 3 An electrode of Example 3 was produced in the same manner as Example 1 except that TiNb 2 O 7 (D50 ⁇ 5 ⁇ m) was used instead of titanium oxide.
  • the dimensions of the electrode of Example 3 were 9.44 mm in diameter and 0.6497 mm in thickness, and the mass was 115.1 mg.
  • the porosity of the electrode of Example 3 was 26.7%. Similar to the electrodes of Examples 1 and 2, the porosity of the electrode of Example 3 was also sufficiently low.
  • the electrode of Example 3 Similar to the electrodes of Examples 1 and 2, the electrode of Example 3 also showed good electrical and ionic conductivity.
  • the cross section of the electrode of Example 3 was observed using a scanning electron microscope using the method described above.
  • 11A and 11B are SEM images (3000x or 10000x) of the cross section of the electrode of Example 3.
  • the electrode of Example 3 also had the same structure as the electrodes of Example 1 and Example 2 (FIGS. 7A, 7B, and 8).
  • the median diameter of the electrode active material 12 was calculated. As a result, in the electrode of Example 3, the median diameter of the electrode active material 12 was 2.5 ⁇ m.
  • the electrode of the present disclosure is suitable as an electrode for a solid-state battery.

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JP2017157305A (ja) * 2016-02-29 2017-09-07 Fdk株式会社 全固体電池の製造方法および全固体電池
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