WO2022138886A1 - Électrode de batterie entièrement solide et batterie entièrement solide - Google Patents

Électrode de batterie entièrement solide et batterie entièrement solide Download PDF

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WO2022138886A1
WO2022138886A1 PCT/JP2021/048075 JP2021048075W WO2022138886A1 WO 2022138886 A1 WO2022138886 A1 WO 2022138886A1 JP 2021048075 W JP2021048075 W JP 2021048075W WO 2022138886 A1 WO2022138886 A1 WO 2022138886A1
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electrode
solid
solid electrolyte
state battery
positive electrode
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PCT/JP2021/048075
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English (en)
Japanese (ja)
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金江達利
佐藤優太
上剃春樹
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マクセル株式会社
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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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers

Definitions

  • the present invention relates to an all-solid-state battery having excellent load characteristics and an electrode capable of forming the all-solid-state battery.
  • an organic electrolyte solution containing an organic solvent and a lithium salt is used as a non-aqueous electrolyte.
  • lithium-ion batteries With the further development of equipment to which lithium-ion batteries are applied, there is a demand for longer life, higher capacity, and higher energy density of lithium-ion batteries, as well as longer life, higher capacity, and higher energy density. The reliability of energy-dense lithium-ion batteries is also highly demanded.
  • the organic electrolyte used in the lithium-ion battery contains an organic solvent which is a flammable substance, the organic electrolyte may generate abnormal heat when an abnormal situation such as a short circuit occurs in the battery. There is. Further, with the recent increase in energy density of lithium ion batteries and the increasing tendency of the amount of organic solvent in organic electrolytic solutions, the reliability of lithium ion batteries is further required.
  • all-solid-state lithium batteries (all-solid-state batteries) that do not use organic solvents are attracting attention.
  • the all-solid-state battery uses a molded body of a solid electrolyte that does not use an organic solvent instead of the conventional organic solvent-based electrolyte, and has high safety without the risk of abnormal heat generation of the solid electrolyte.
  • all-solid-state batteries have not only high safety, but also high reliability, high environmental resistance, and long life, so they can contribute to the development of society and at the same time continue to contribute to safety and security. It is expected as a maintenance-free battery that can be used.
  • SDGs Sustainable Development Goals
  • Goal 12 to ensure sustainable production and consumption
  • Goal 3 for all ages
  • Patent Document 1 describes that the performance of an all-solid-state battery can be enhanced by using a material made of a mixed material obtained by granulating a sulfide-based inorganic solid electrolyte and an electrode active material.
  • Patent Document 1 the powder of the sulfide-based inorganic solid electrolyte and the powder of the electrode active material are mixed to form a mixed powder, which is pressure-molded to once form a molded body. Manufactures materials for solid cell batteries. Then, through this manufacturing method, in the all-solid-state battery material, a plurality of electrode active material particles are adjacent to each other to form an electron conduction path, and further, a sulfide system is formed between the electrode active material particles.
  • An ion conduction path is formed by arranging the inorganic solid electrolyte and forming a continuous phase by deforming the particles of the sulfide-based inorganic solid electrolyte by pressure molding and binding them to each other, and the particle shape disappears to form a continuous phase. It is supposed to be.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide an all-solid-state battery having excellent load characteristics and an electrode capable of forming the all-solid-state battery.
  • the electrode for an all-solid-state battery of the present invention contains a molded body of an electrode mixture, the electrode mixture contains an electrode material composite, and the electrode material composite contains granules containing an active material and a solid electrolyte. It is composed of a body, and the solid electrolyte is characterized by containing a granular argilodite-type sulfide-based solid electrolyte.
  • the all-solid-state battery of the present invention includes a positive electrode, a negative electrode, and a solid electrolyte layer interposed between the positive electrode and the negative electrode, and at least one of the positive electrode and the negative electrode is the all-solid state of the present invention. It is characterized by being a battery electrode.
  • the all-solid-state battery of the present invention includes a primary battery (all-solid-state primary battery) and a secondary battery (all-solid-state secondary battery).
  • an all-solid-state battery having excellent load characteristics and an electrode capable of forming the all-solid-state battery it is possible to provide an all-solid-state battery having excellent load characteristics and an electrode capable of forming the all-solid-state battery.
  • FIG. 1 is a plan view schematically showing an example of a part of a molded body of an electrode mixture contained in the electrode for an all-solid-state battery of the present invention.
  • FIG. 2 is an enlarged view of the area surrounded by the dotted line in FIG.
  • FIG. 3 is a plan view schematically showing another example of a part of the molded body of the electrode mixture contained in the electrode for an all-solid-state battery of the present invention.
  • FIG. 4 is a plan view schematically showing another example of a part of the molded body of the electrode mixture contained in the electrode for an all-solid-state battery of the present invention.
  • FIG. 5 is a cross-sectional view schematically showing an example of the all-solid-state battery of the present invention.
  • FIG. 6 is a plan view schematically showing another example of the all-solid-state battery of the present invention.
  • FIG. 7 is a cross-sectional view taken along the line II of FIG.
  • the electrode for an all-solid-state battery of the present invention is used for a positive electrode or a negative electrode of an all-solid-state battery, and has a molded body of an electrode mixture containing an electrode material composite.
  • the electrode material composite is composed of a granulated body containing an active material and a solid electrolyte, and contains a granular argilodite-type sulfide-based solid electrolyte as the solid electrolyte.
  • a molded body of an electrode mixture constituting an electrode for an all-solid-state battery is manufactured, for example, by simply mixing an active material and a solid electrolyte to form a mixed powder, which is subjected to a process such as pressure molding, the active material is generally active. Since the surface unevenness of the material particles is relatively large and the solid electrolyte particles cannot follow the uneven shape well, a relatively large gap is generated between the active material particles and the solid electrolyte particles. There is a certain limit to the improvement of ionic conductivity (lithium ionic conductivity) in. These points have been a factor that hinders the improvement of the load characteristics of the all-solid-state battery.
  • the electrode for an all-solid-state battery of the present invention it was decided to include an electrode material composite formed by pre-granulating an active material and an argylodite-type sulfide-based solid electrolyte in a molded body of an electrode mixture.
  • the active material and the argilodite-type sulfide-based solid electrolyte form the granules, the contact between the active material particles in the electrode material composite and the argilodite-type sulfide-based solid electrolyte particles is prevented. It is better than the case of a mixture in which the active material particles and the solid electrolyte particles are simply mixed.
  • the solid in the electrode material composite is also formed. Since the ionic conductivity in the molded body of the electrode mixture is improved by the action of the electrolyte, in the all-solid-state battery (all-solid-state battery of the present invention) using the electrode for the all-solid-state battery of the present invention having this molded body. Can ensure excellent load characteristics.
  • the algyrodite-type sulfide-based solid electrolyte contained in the electrode material composite contained in the electrode for an all-solid-state battery of the present invention is granular.
  • Patent Document 1 states that a good ionic conduction path is formed by the continuous phase of the sulfide-based inorganic solid electrolyte. Therefore, according to this description, the ionic conductivity inside the electrode is enhanced and the all-solid-state battery is used. It is expected that the solid electrolyte existing between the active materials forms a continuous phase instead of granules (particle shape) in order to improve the load characteristics of the active material.
  • the electrode material composite composed of a granulated body containing the active material contained in the electrode for an all-solid-state battery and the argylodite-type sulfide-based solid electrolyte
  • the electrode material composite is used. It was found that the presence of the solid electrolyte in the form of granules is advantageous in improving the load characteristics of the all-solid-state battery. The reason is not clear, but it is speculated that it may be as follows.
  • Algyrodite-type sulfide-based solid electrolytes are usually provided in the form of particles (particles), but such granular argilodite-type sulfide-based solid electrolytes are crystallized and are more than in the amorphous state. Also has high ionic conductivity.
  • the sulfide-based solid electrolyte existing between the active materials becomes a continuous phase in which the particles are bound to each other and the original shape (granular) is lost, it is considered amorphous. It is presumed that the solid electrolyte is not sufficiently exhibiting the ionic conductivity originally possessed by the solid electrolyte.
  • the electrode material composite contained in the all-solid-state battery electrode can exist in a state where the original granularity is maintained, the degree of crystallization is also compared. It is considered that the electrode material composite is maintained in a high target state, and as a result, the ionic conductivity of the electrode material composite, which is a granule, is increased. Therefore, the electrode for an all-solid-state battery of the present invention has high ionic conductivity. It is presumed that an all-solid-state battery with excellent load characteristics can be formed by using this.
  • the fact that the molded body of the electrode mixture contains an electrode material composite composed of a granule containing an active material and an argylodite-type sulfide-based solid electrolyte means that the electrode combination is used.
  • the image of the cross section of the molded body of the agent observed at 10000 times using a scanning electron microscope (SEM) 10 or more primary particles of the active material are aggregated, and the primary particles of the active material are between the primary particles of the active material.
  • the gap between the primary particles of the active material is preferably 4 ⁇ m or less, more preferably 3 ⁇ m or less, and is usually 0.5 ⁇ m or more, although it depends on the particle size of the solid electrolyte.
  • the solid electrolytes (aldirodite-type sulfide-based solid electrolytes and other solid electrolytes that may be contained in the electrode material composite) existing between the primary particles of the active material are granular. If it has the contour of, the solid electrolyte is considered to be granular. For example, when two solid electrolyte particles are in close contact with each other and the interface of each particle is ambiguous, when the shape of the particles is assumed to be a circle in a plan view, 60% or more of the circumference is assumed. If it can be confirmed, it is said that it has a granular contour.
  • FIG. 1 and 2 show a drawing schematically showing an example of a part of a molded body of an electrode mixture contained in the electrode for an all-solid-state battery of the present invention.
  • FIG. 1 is a plan view showing a part of a molded body of an electrode mixture
  • FIG. 2 is an enlarged view of a region surrounded by a dotted line in FIG.
  • the part surrounded by the ellipse in FIG. 1 is an electrode material composite 1 composed of a granulated product of an active material and an argylodite-type sulfide-based solid electrolyte (hereinafter, also simply referred to as argilodite-type solid electrolyte), and is an electrode material.
  • the composite 1 includes a solid electrolyte 2 added separately from the argylodite-type solid electrolyte constituting the electrode material composite 1 and an active material (active material) added separately from the active material constituting the electrode material composite 1. Together with the primary particles) 3, a molded body of the electrode mixture is formed. Then, in the electrode material complex 1, 10 or more primary particles 1a of the active material are aggregated.
  • the ellipse shown in FIG. 1 contains a part of the solid electrolyte 2 that exists around the electrode material composite 1 and does not constitute the electrode material composite 1, and also constitutes the electrode material composite 1. A part of the primary particles 1a of the active material to be formed protrudes from the ellipse shown in FIG. 1 (the same applies to FIGS. 3 and 4 described later). Further, in FIG. 1, the algyrodite type solid electrolyte constituting the electrode material complex 1 is not shown (the same applies to FIGS. 3 and 4 described later).
  • a granular argilodite-type sulfide-based solid electrolyte 1b is present in the gap between the primary particles 1a of the active material in the electrode material composite 1.
  • the molded body of the electrode mixture shown in FIG. 3 is formed of an electrode material composite 1 and a solid electrolyte 2 (separate from the argylodite-type solid electrolyte constituting the electrode material composite 1). That is, all of the active materials contained in the molded body of the electrode mixture shown in FIG. 3 constitute the electrode material complex 1.
  • the molded body of the electrode mixture shown in FIG. 4 includes an electrode material composite 1, a solid electrolyte 2 (added separately from the argylodite-type solid electrolyte constituting the electrode material composite 1), and an electrode material composite. It is formed of an active material (primary particles of the active material) 3 different from those constituting the body 1.
  • the electrode for an all-solid-state battery has a structure in which a molded body (pellet, etc.) formed by molding an electrode mixture or a layer (mixture layer) composed of a molded body of an electrode mixture is formed on a current collector. Things and so on.
  • the active material of the electrode material composite contained in the molded body of the electrode mixture is a conventionally known non-aqueous electrolyte.
  • the same positive electrode active material used for the primary battery can be used.
  • manganese dioxide; lithium-containing manganese oxide for example, LiMn 3 O6 or the same crystal structure as manganese dioxide ( ⁇ -type, ⁇ -type, or a structure in which ⁇ -type and ⁇ -type are mixed) is used.
  • Lithium-containing composite oxides such as 5/3 O4 ( 4/3 ⁇ a ⁇ 7/3); vanadium oxides; niobium oxides; titanium oxides; sulfides such as iron disulfide; graphite fluoride; Ag 2 Examples thereof include silver sulfides such as S; nickel oxides such as NiO 2 ; and the like.
  • the active material of the electrode material composite to be contained in the molded body of the electrode mixture has been conventionally known.
  • a positive electrode active material used in a non-aqueous electrolyte secondary battery that is, the same active material capable of storing and releasing Li (lithium) ions can be used.
  • Li 1-x M r Mn 2-r O 4 (where M is Li, Na, K, B, Mg, Ca, Sr, Ba, Ti, V, Cr, Zr, Fe, Co.
  • Li 1-x Ni 1-r Mr O 2 (where M is Al, Mg, Ti, Zr, Fe, Co, Cu, Zn, Ga, Ge, Nb). , Mo, Sn, Sb and Ba, at least one element selected from the group consisting of Li 1 + s- , a lithium nickel composite oxide represented by 0 ⁇ x ⁇ 1, 0 ⁇ r ⁇ 0.5).
  • x M 1-r N r PO 4 F s (where M is at least one element selected from the group consisting of Fe, Mn and Co, and N is Al, Mg, Ti, Zr, Ni, Cu.
  • N is at least one element selected from the group consisting of Al, Mg, Ti, Zr, Ni, Cu, Zn, Ga, Ge, Nb, Mo, Sn, Sb, V and Ba, and is 0. ⁇ x ⁇ 2, 0 ⁇ r ⁇ 0.5)
  • the represented pyrophosphoric acid compound and the like can be exemplified, and only one of these may be used, or two or more thereof may be used in combination.
  • the lithium cobalt composite oxide (A) represented by the following general formula (1) is preferably used among the above-exemplified positive electrode active materials.
  • M 1 is at least one element selected from the group consisting of Mg, Ni and Na
  • M 2 is Mn, Fe, Cu, Zr, Ti, Bi, Ca, F
  • It is at least one element selected from the group consisting of P, Sr, W, Ba, Nb, Si, Zn, Mo, V, Sn, Sb, Ta, Ge, Cr, K, S and Er, and is 0 ⁇ .
  • the lithium cobalt composite oxide (A) When the lithium cobalt composite oxide (A) is used as a positive electrode active material for a non-aqueous electrolyte secondary battery using an organic electrolytic solution, the inside of the battery is affected by the action of additive elements such as Al and M1 element contained therein. It is a material that increases resistance.
  • additive elements such as Al and M1 element contained therein. It is a material that increases resistance.
  • the electrolyte that transfers ions between the positive electrode and the negative electrode is a liquid (electrolyte)
  • the original internal resistance is small, so lithium.
  • the above-mentioned increase in internal resistance due to the cobalt composite oxide (A) has almost no effect on the battery characteristics.
  • the lithium cobalt composite oxide (A) is used as the positive electrode active material of the all-solid-state secondary battery, contrary to such an expectation, the internal resistance is lowered as compared with the case where LiCoO 2 is used as the positive electrode active material, for example. This is possible, and the load characteristics of the all-solid-state secondary battery can be further enhanced.
  • the electrolyte that transfers ions in the positive electrode is a solid (solid electrolyte), so the volume of the positive electrode active material changes due to the charging and discharging of the battery, so that the positive electrode active material and the solid electrolyte A gap is created between the two, and the internal resistance of the positive electrode, and eventually the internal resistance of the battery, increases.
  • the expansion of Co is suppressed by the action of Al and the element M1 even in the charged state, so that the positive electrode active material.
  • the total amount of expansion (volume change) becomes smaller. Therefore, by using a positive electrode for an all-solid-state battery using lithium cobalt composite oxide (A) as a positive electrode active material, contact between the lithium cobalt composite oxide (A) and the solid electrolyte in the positive electrode even when charged and discharged. Can be maintained well and the internal resistance can be kept low, so that an all-solid-state secondary battery having better load characteristics can be obtained.
  • Al is an element substituted with Co sites and M 1 is an element substituted with Li sites, both of which are the expansion amounts of Co during charging [lithium cobalt composite oxide (A). It has the effect of reducing the amount of expansion.
  • the lithium cobalt composite oxide (A) may contain at least one element of Mg, Ni and Na as the element M 1 , but has the same ionic radius as Li to be substituted and is further filled. Mg is preferable because it does not change the valence during discharge.
  • the amount a of Al is greater than 0 and less than 0.1, and the amount b of the element M1 is greater than 0 and less than 0.1 from the viewpoint of suppressing the amount of expansion during charging. And a + b is less than 0.1.
  • the amount a of Al is preferably 0.005 or more, and the amount b of the element M1 is preferably 0.005 or more. Further, the amount a of Al is preferably 0.08 or less , and the amount b of the element M1 is preferably 0.08 or less.
  • the lithium cobalt composite oxide (A) may or may not contain the element M 2 (the amount c may be 0), but if the amount of the element M 2 is too large, for example. As the amount of Co decreases, the capacity of the lithium cobalt composite oxide (A) may decrease. Therefore, the amount c of the element M 2 is preferably 0.05 or less.
  • the active material of the electrode material composite contained in the molded body of the electrode mixture includes metallic lithium and a lithium alloy (lithium-aluminum). Alloys, lithium-indium alloys, etc.) and the like.
  • the electrode for an all-solid-state battery is a negative electrode and is used for an all-solid-state secondary battery, it has been conventionally known as an active material of the electrode material composite to be contained in a molded body of an electrode mixture.
  • an active material that can store and release lithium ions used in a lithium secondary battery is an active material that can store and release lithium ions used in a lithium secondary battery.
  • carbon that can store and release lithium such as graphite, pyrolytic carbon, coke, glassy carbon, calcined organic polymer compound, mesocarbon microbeads (MCMB), and carbon fiber.
  • MCMB mesocarbon microbeads
  • One or a mixture of two or more of the system materials is used.
  • An oxide may be used as the negative electrode active material, for example, Li x Nby TiM 6 a O ⁇ 5y + 4/2 ⁇ + ⁇ (where M 6 is V, Cr, Mo, Ta, Zr, Mn, Fe, It is at least one selected from the group consisting of Mg, B, Al, Cu, and Si, and is 0 ⁇ x ⁇ 49, 0.5 ⁇ y ⁇ 24, -5 ⁇ ⁇ ⁇ 5, 0 ⁇ a ⁇ 0.
  • Examples thereof include a spinel-type lithium-titanium composite oxide represented by 12 , and one or more of these can be used.
  • Singles containing elements such as Si, Sn, Ge, Bi, Sb, In, compounds and alloys thereof; nitrides containing transition metals such as Co, Ni, Mn, Fe, Cr, Ti, and W and lithium.
  • a compound that can be charged and discharged at a low voltage close to that of a lithium metal such as an oxide; or a metallic lithium or a lithium alloy (lithium-aluminum alloy, lithium-indium alloy, etc.) can also be used as a negative electrode active material.
  • the active material of the electrode material composite can have a reaction suppressing layer for suppressing the reaction between the active material and the solid electrolyte on the surface thereof.
  • a reaction suppressing layer is provided on the surface of the active material (positive electrode active material).
  • the reaction suppressing layer may be made of a material having ionic conductivity and capable of suppressing the reaction between the active material and the solid electrolyte.
  • the material that can form the reaction suppression layer for example, an oxide containing Li and at least one element selected from the group consisting of Nb, P, B, Si, Ge, Ti and Zr, more specifically.
  • Examples include Nb-containing oxides such as LiNbO 3 , Li 3 PO 4 , Li 3 BO 3 , Li 4 SiO 4 , Li 4 GeO 4 , LiTIO 3 , LiZrO 3 , Li 2 WO 4 .
  • the reaction suppression layer may contain only one of these oxides, or may contain two or more of these oxides, and a plurality of these oxides may be a composite compound. May be formed. Among these oxides, it is preferable to use an Nb - containing oxide, and it is more preferable to use LiNbO3.
  • the reaction suppressing layer is preferably present on the surface in an amount of 0.1 to 1.0 part by mass with respect to 100 parts by mass of the active material (base material particles on which the reaction suppressing layer is formed). Within this range, the reaction between the active material and the solid electrolyte can be satisfactorily suppressed.
  • Examples of the method for forming the reaction suppression layer on the surface of the active material include a sol-gel method, a mechanofusion method, a CVD method, a PVD method, and an ALD method.
  • Algyrodite-type sulfide-based solid electrolytes are mainly used as the solid electrolytes of the electrode material composite contained in the molded body of the electrode mixture of the electrodes for all-solid-state batteries, but all the solid electrolytes used are argilodite-type sulfide-based electrolytes. It can also be a solid electrolyte.
  • Examples of the argilodite-type sulfide-based solid electrolyte include those represented by the following general formula (2) represented by Li 6 PS 5 Cl and those represented by the following general formula (3).
  • another solid electrolyte may be used together with the argylodite-type sulfide-based solid electrolyte.
  • examples of such other solid electrolytes include sulfide-based solid electrolytes other than argylodite-type sulfide-based solid electrolytes, hydride-based solid electrolytes, halide-based solid electrolytes, oxide-based solid electrolytes, and the like.
  • Examples of the sulfide-based solid electrolyte other than the algyrodite-type sulfide-based solid electrolyte include Li 2 SP 2 S 5, Li 2 S - SiS 2 , Li 2 SP 2 S 5 -GeS 2 , and Li 2 SB. 2 S 3 and the like glass-based particles; LGPS-based particles (Li 10 GeP 2 S 12 and the like);
  • Examples of the hydride-based solid electrolyte include a solid solution of LiBH 4 , LiBH 4 and the following alkali metal compound (for example, one having a molar ratio of LiBH 4 to the alkali metal compound of 1: 1 to 20: 1). Can be mentioned.
  • Examples of the alkali metal compound in the solid solution include lithium halide (LiI, LiBr, LiF, LiCl, etc.), rubidium halide (RbI, RbBr, RbF, RbCl, etc.), and cesium halide (CsI, CsBr, CsF, CsCl, etc.). , At least one selected from the group consisting of lithium amide, rubidium amide and cesium amide.
  • halide-based solid electrolyte examples include monoclinic type LiAlCl 4 , defective spinel type or layered structure LiInBr 4 , and monoclinic type Li 6-3m Ym X 6 (however, 0 ⁇ m ⁇ 2 and 0 ⁇ m ⁇ 2).
  • X Cl or Br
  • oxide-based solid electrolyte examples include garnet-type Li 7 La 3 Zr 2 O 12 , NASICON-type Li 1 + O Al 1 + O Ti 2-O (PO 4 ) 3 , Li 1 + p Al 1 + p Ge 2-p (PO 4 ). ) 3 , Perobskite type Li 3q La 2 / 3-q TiO 3 and the like can be mentioned.
  • the ratio of the argilodite-type sulfide-based solid electrolyte to the total amount of the solid electrolyte in the electrode material composite is 70. It is preferably mass% or more. Further, since it is preferable that all the solid electrolytes used in the electrode material composite are argylodite-type sulfide-based solid electrolytes, the ratio of the argilodite-type sulfide-based solid electrolytes to the total amount of the solid electrolytes in the electrode material composite. The preferable upper limit value of is 100% by mass.
  • the shape of the algyrodite-type sulfide-based solid electrolyte contained in the electrode material composite contained in the molded body of the electrode mixture is not particularly limited as long as it is granular, and the primary particle diameter is measured by, for example, the following method. As long as Rs satisfies the following values, it may have any shape such as a spherical shape, an ellipsoidal shape, and a plate shape. Further, when the electrode material composite also contains a solid electrolyte other than the argylodite-type sulfide-based solid electrolyte, it is preferable that the shape of the other solid electrolyte is also granular.
  • the average particle size of the primary particles of the active material contained in the electrode material composite is Ra
  • the solid electrolyte contained in the electrode material composite also contains other solid electrolytes other than the argylodite type solid electrolyte.
  • the ratio Ra / Rs thereof is preferably 2 or more, more preferably 4 or more. It is most preferably 6 or more, preferably 50 or less, more preferably 35 or less, and most preferably 18 or less.
  • Ra / Rs can be set in the range of 2 to 50, 2 to 35, 2 to 18, 4 to 50, 4 to 35, 4 to 18, 6 to 50, 6 to 35, and 6 to 18.
  • the average particle size Ra of the primary particles of the active material in the electrode material composite is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, most preferably 4 ⁇ m or more, and preferably 25 ⁇ m or less. , 15 ⁇ m or less is more preferable, and 10 ⁇ m or less is most preferable.
  • Ra can be set within the range of 1 to 25 ⁇ m, 1 to 15 ⁇ m, 1 to 10 ⁇ m, 3 to 25 ⁇ m, 3 to 15 ⁇ m, 3 to 10 ⁇ m, 4 to 25 ⁇ m, 4 to 15 ⁇ m, and 4 to 10 ⁇ m.
  • the average particle diameter Rs of the primary particles of the solid electrolyte in the electrode material composite is preferably 0.2 ⁇ m or more, more preferably 0.4 ⁇ m or more, and preferably 3 ⁇ m or less. It is more preferably 8.8 ⁇ m or less.
  • Rs can be set in the range of 0.2 to 3 ⁇ m, 0.2 to 1.8 ⁇ m, 0.4 to 3 ⁇ m, and 0.4 to 1.8 ⁇ m.
  • the average particle size of the primary particles of the active material contained in the electrode material composite is a value obtained as follows. Regarding the cross section of the molded body of the electrode mixture in the electrode for all-solid-state battery, 10 particles of the active material whose contour can be confirmed in the image observed at 2000 times using SEM were selected, and the two-point method was applied to the selected particles. Measure the longest diameter with. Then, the average value (number average) of the longest diameters of all the measured particles is taken as the average particle diameter of the primary particles of the active material.
  • the average particle size of the primary particles of the solid electrolyte contained in the electrode material composite is the average of the primary particle size of the active material contained in the electrode material composite, except that the magnification observed by SEM is changed to 30,000 times. It is a value obtained by the same method as the particle size.
  • the content of the argilodite type solid electrolyte is 2.5 parts by mass or more when the content of the active material is 100 parts by mass. It is preferably 8 parts by mass or more, more preferably 60 parts by mass or less, and even more preferably 40 parts by mass or less.
  • the content of the argilodite type solid electrolyte can be set within the range of 2.5 to 60 parts by mass, 2.5 to 40 parts by mass, 8 to 60 parts by mass, and 8 to 40 parts by mass.
  • the electrode material composite is produced by granulating particles of an active material and particles of an algyrodite-type sulfide-based solid electrolyte.
  • the granulation method is not particularly limited and a known method can be applied, but it is necessary to adjust the stress acting during granulation so that the argilodite-type sulfide-based solid electrolyte after granulation can maintain the granulation.
  • adjusting a known mixer so as to develop van der Waals force and electrostatic force due to collision / shearing action between materials is a desirable method for adjusting the stress acting during granulation.
  • the particles of the algyrodite-type sulfide-based solid electrolyte used for forming the electrode material composite are measured using a particle size distribution measuring device (such as a particle size distribution measuring device “MT-3300EXII” manufactured by Microtrac Bell Co., Ltd.).
  • the average particle size [value of 50% diameter (D 50 ) in the integrated fraction based on the volume when the integrated volume is obtained from particles having a small particle size] is usually about 0.2 to 3 ⁇ m. Therefore, an argilodite-type sulfide-based solid electrolyte having such a size is formed into the electrode material composite through granulation, and further, in the molding body of the electrode mixture formed by using the electrode material composite, the said.
  • the particles of the active material and the particles of the argylodite-type sulfide-based solid electrolyte may be granulated by selecting conditions that can satisfy the primary particle diameter Rs.
  • the molded body of the electrode mixture contained in the electrode for the all-solid-state battery may contain an active material in addition to the electrode material composite.
  • an active material the same ones as those of the various active materials exemplified above for forming the electrode material complex can be used.
  • the active material in the electrode material composite and the active material not constituting the electrode material composite are contained in the electrode material composite in a total of 100% by mass.
  • the ratio of the active material is preferably 60% by mass or more. It is not necessary to use an active material separately from the electrode material composite in the molded body of the electrode mixture, and the active material in the electrode material composite and the active material not constituting the electrode material composite are used.
  • the preferable upper limit of the ratio of the active material in the electrode material composite in the total of 100% by mass is 100% by mass.
  • the content of the active material (active material contained in the electrode material composite and, if necessary, an active material used separately from the electrode material composite) in the electrode mixture is 55 to 75% by mass. Is preferable.
  • the content of the active material referred to here includes the amount of the reaction suppressing layer when the active material has a reaction suppressing layer.
  • the molded body of the electrode mixture contained in the electrode for the all-solid-state battery may contain a solid electrolyte in addition to the solid electrolyte contained in the electrode material composite.
  • solid electrolytes include various sulfide-based solid electrolytes (aldylodite-type sulfide-based solid electrolytes and other sulfide-based solid electrolytes) exemplified above as those that can be used for the electrode material composite.
  • hydride-based solid electrolytes, halide-based solid electrolytes and oxide-based solid electrolytes can be mentioned.
  • the solid electrolyte used separately from the electrode material composite the same type as that contained in the electrode material composite may be used, or another type may be used, but the above-exemplified solid may be used.
  • the sulfide-based solid electrolyte is more preferable because it has high lithium ion conductivity, and the argylodite-type sulfide-based solid electrolyte has high chemical stability in addition to having particularly high lithium ion conductivity. Is more preferable.
  • the content of the solid electrolyte (the solid electrolyte contained in the electrode material composite and, if necessary, the solid electrolyte used separately from the electrode material composite) in the electrode mixture shall be 25 to 50% by mass. Is preferable.
  • a conductive auxiliary agent such as carbon black or graphene can be contained in the molded body of the electrode mixture contained in the electrode for the all-solid-state battery.
  • the content in the electrode mixture is preferably 2 to 10% by mass.
  • the resin binder may or may not be contained in the molded body of the electrode mixture contained in the electrode for the all-solid-state battery.
  • the resin binder include fluororesins such as polyvinylidene fluoride (PVDF).
  • PVDF polyvinylidene fluoride
  • the binder made of resin is not contained, or when it is contained, the content in the electrode mixture is 0.5% by mass or less.
  • the content of the resin binder in the electrode mixture is more preferably 0.3% by mass or less, and further preferably 0% by mass (that is, the resin binder is not contained).
  • a metal foil, punching metal, net, expanded metal, foamed metal; carbon sheet; or the like can be used as the current collector.
  • aluminum or stainless steel is preferable when the electrode for the all-solid-state battery is a positive electrode, and copper or nickel is preferable when the electrode for the all-solid-state battery is a negative electrode. Is preferable.
  • the molded body of the electrode mixture is, for example, an electrode mixture prepared by mixing the electrode material composite and the solid electrolyte with a conductive auxiliary agent or a binder added as needed, and compressed by pressure molding or the like. It can be formed by doing.
  • An electrode for an all-solid-state battery composed of only a molded body of an electrode mixture can be manufactured by such a method.
  • an electrode for an all-solid-state battery having a current collector it can be manufactured by bonding the molded body of the electrode mixture formed by the above method to the current collector by crimping it.
  • the electrode mixture and the solvent are mixed to prepare an electrode mixture-containing composition, which is applied onto a substrate such as a current collector or a solid electrolyte layer facing the electrode, dried, and then pressed.
  • a molded body of the electrode mixture may be formed.
  • a solvent for the electrode mixture-containing composition that does not easily deteriorate the solid electrolyte.
  • sulfide-based solid electrolytes and hydride-based solid electrolytes cause a chemical reaction with a very small amount of water, and are therefore represented by hydrocarbon solvents such as hexane, heptane, octane, nonane, decane, decalin, toluene, and xylene.
  • hydrocarbon solvents such as hexane, heptane, octane, nonane, decane, decalin, toluene, and xylene.
  • a non-polar aproton solvent it is more preferable to use a super dehydrating solvent having a water content of 0.001% by mass (10 ppm) or less.
  • fluorine-based solvents such as “Bertrel (registered trademark)” manufactured by Mitsui Dupont Fluorochemical, “Zeorolla (registered trademark)” manufactured by Zeon Corporation, and “Novec (registered trademark)” manufactured by Sumitomo 3M, as well as , Dichloromethane, diethyl ether and other non-aqueous organic solvents can also be used.
  • the thickness of the molded body of the electrode mixture (in the case of an electrode having a current collector, the thickness of the molded body of the electrode mixture per one side of the current collector; hereinafter the same) is usually 50 ⁇ m or more. From the viewpoint of increasing the capacity of the battery, it is preferably 200 ⁇ m or more. The thickness of the molded body of the electrode mixture is usually 3000 ⁇ m or less.
  • an electrode for an all-solid-state battery which is manufactured by forming an electrode mixture layer made of a molded body of the electrode mixture on a current collector using an electrode mixture-containing composition containing a solvent.
  • the thickness of the electrode mixture layer is preferably 50 to 1000 ⁇ m.
  • the all-solid-state battery of the present invention has a positive electrode, a negative electrode, and a solid electrolyte layer interposed between the positive electrode and the negative electrode, and at least one of the positive electrode and the negative electrode is the electrode for the all-solid-state battery of the present invention described above. be.
  • FIG. 5 shows a sectional view schematically showing an example of the all-solid-state battery of the present invention.
  • the all-solid-state battery 10 shown in FIG. 5 has a positive electrode 20, a negative electrode 30, and a positive electrode 20 and a negative electrode in an exterior body formed of an outer can 50, a sealing can 60, and a resin gasket 70 interposed between them.
  • a solid electrolyte layer 40 interposed between the 30 and 30 is enclosed.
  • the sealing can 60 is fitted to the opening of the outer can 50 via the gasket 70, and the opening end of the outer can 50 is tightened inward, whereby the gasket 70 comes into contact with the sealing can 60.
  • the opening of the outer can 50 is sealed and the inside of the battery has a sealed structure.
  • Stainless steel can be used for the outer can and the sealing can.
  • polypropylene, nylon, etc. can be used as the material of the gasket, and if heat resistance is required in relation to the use of the battery, tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), etc. can be used.
  • a glass hermetic seal can be used for the sealing.
  • FIGS. 6 and 7 show drawings schematically showing other examples of the all-solid-state battery of the present invention.
  • FIG. 6 is a plan view of the all-solid-state battery
  • FIG. 7 is a sectional view taken along line II of FIG.
  • an electrode body 200 composed of a positive electrode, a solid electrolyte layer, and a negative electrode is housed in a laminated film exterior body 500 composed of two metal laminated films, and the laminated film.
  • the exterior body 500 is sealed at the outer peripheral portion thereof by heat-sealing the upper and lower metal laminate films.
  • each layer constituting the laminated film exterior body 500, and the positive electrode, the negative electrode, and the solid electrolyte layer constituting the electrode body are not shown separately. ..
  • the positive electrode of the electrode body 200 is connected to the positive electrode external terminal 300 in the battery 100, and although not shown, the negative electrode of the electrode body 200 is also connected to the negative electrode external terminal 400 in the battery 100. There is.
  • the positive electrode external terminal 300 and the negative electrode external terminal 400 are drawn out on one end side to the outside of the laminated film exterior body 500 so that they can be connected to an external device or the like.
  • the negative electrode may be the all-solid-state battery electrode of the present invention or a negative electrode other than the all-solid-state battery electrode of the present invention.
  • the negative electrode other than the all-solid-state battery electrode of the present invention is the same as the all-solid-state battery electrode of the present invention except that the negative electrode active material that can be used for the electrode material composite is used in place of the electrode material composite.
  • Electrodes (negative electrodes) of the configuration consisting only of various alloys (lithium alloys such as lithium-aluminum alloys and lithium-indium alloys) that function as negative electrode active materials, metallic lithium foils, or the foils are placed on the current collector. Examples thereof include a negative electrode laminated as an active material layer; and the like.
  • the positive electrode may be the electrode for the all-solid-state battery of the present invention or a positive electrode other than the electrode for the all-solid-state battery of the present invention.
  • the positive electrode other than the electrode for the all-solid battery of the present invention is the same as the electrode for the all-solid battery of the present invention except that the positive electrode active material that can be used for the electrode material composite is used instead of the electrode material composite. Examples thereof include electrodes (positive electrodes) having a configuration.
  • the solid electrolytes constituting the solid electrolyte layer of the all-solid battery include various sulfide-based solid electrolytes (algirodite-type sulfide-based solid electrolytes and other sulfide-based solid electrolytes) exemplified above as those that can be used for the positive electrode.
  • sulfide-based solid electrolytes algirodite-type sulfide-based solid electrolytes and other sulfide-based solid electrolytes
  • hydride-based solid electrolytes, halide-based solid electrolytes and oxide-based solid electrolytes can be used.
  • it is preferable to contain a sulfide-based solid electrolyte it is more preferable to contain an algyrodite-type sulfide-based solid electrolyte.
  • the solid electrolyte layer may have a porous body such as a non-woven fabric made of resin as a support.
  • the solid electrolyte layer is a method of compressing the solid electrolyte by pressure molding or the like; a composition for forming a solid electrolyte layer prepared by dispersing the solid electrolyte in a solvent is applied onto a base material, a positive electrode, and a negative electrode, and dried. If necessary, it can be formed by a method of performing pressure molding such as press processing;
  • the thickness of the solid electrolyte layer is preferably 100 to 300 ⁇ m.
  • the positive electrode and the negative electrode can be used in a battery in the form of a laminated electrode body laminated via a solid electrolyte layer or a wound electrode body wound around the laminated electrode body.
  • the electrode body When forming the electrode body, it is preferable to perform pressure molding in a state where the positive electrode body, the negative electrode body and the solid electrolyte layer are laminated from the viewpoint of increasing the mechanical strength of the electrode body.
  • the all-solid-state battery of the present invention can be applied to the same applications as the conventionally known all-solid-state battery (all-solid-state primary battery or all-solid-state secondary battery).
  • Example 1 ⁇ Manufacturing of electrode material complex for positive electrode> Primary particles (positive electrode active material) of LiCo 0.98 Al 0.01 Mg 0.01 O 2 having an average particle size of 5 ⁇ m and a layer composed of LiNbO 3 on the surface, and argylodite-type sulfide having an average particle size of 0.6 ⁇ m. A solid electrolyte (Li 6 PS 5 Cl) was granulated to prepare an electrode material composite for a positive electrode. The composition of the component in the electrode material composite for the positive electrode was 20 parts by mass of the argilodite-type sulfide-based solid electrolyte with respect to 100 parts by mass of the positive electrode active material.
  • the amount of the layer composed of LiNbO 3 on the surface of LiCo 0.98 Al 0.01 Mg 0.01 O 2 is 1 with respect to 100 parts by mass of LiCo 0.98 Al 0.01 Mg 0.01 O 2 : It was a mass part. Furthermore, when granulating the positive electrode active material and the argilodite-type sulfide-based solid electrolyte, the mixing conditions in the mixer were adjusted so as to develop van der Waals force and electrostatic force due to the collision / shearing action between the materials.
  • the positive electrode material composite, the same argylodite-type sulfide-based solid electrolyte used for the positive electrode material composite, and acetylene black (conductive aid) are mixed in a mass ratio of 20: 5: 1.
  • the mixture was mixed and kneaded well to prepare a positive electrode mixture.
  • the positive electrode mixture 75 mg was placed in a powder molding die having a diameter of 7.5 mm, and pressure molding was performed using a press machine to prepare a positive electrode made of a cylindrical positive electrode mixture molded body.
  • Lithium titanate Li 4 Ti 5 O 12 , negative electrode active material, average particle size: 1.3 ⁇ m
  • argylodite-type sulfide-based solid electrolyte used for the electrode material composite of the positive electrode
  • graphene conductivity
  • Auxiliary agent was mixed at a mass ratio of 6: 5: 1 and kneaded well to prepare a negative electrode mixture.
  • the negative electrode mixture 100 mg was put onto the solid electrolyte layer in the powder molding mold, pressure molding was performed using a press machine, and the negative electrode mixture molded body was placed on the solid electrolyte layer.
  • a laminated electrode body in which a positive electrode, a solid electrolyte layer, and a negative electrode were laminated was produced.
  • the thicknesses of the positive electrode (positive electrode mixture molded body), the solid electrolyte layer, and the negative electrode (negative electrode mixture molded body) in the laminated electrode body were 750 ⁇ m, 100 ⁇ m, and 930 ⁇ m, respectively.
  • a plurality of laminated electrode bodies are produced, and for a part of them, the cross section of the positive electrode mixture molded body is observed by SEM, and the electrode material composite composed of the granulated body in the positive electrode mixture molded body by the above method.
  • the algyrodite-type sulfide-based solid electrolyte in the electrode material composite was confirmed to be granular.
  • the average particle size Ra of the primary particles of the positive electrode active material is 5 ⁇ m
  • the average particle size Rs of the primary particles of the argilodite-type sulfide-based solid electrolyte is 0.6 ⁇ m, which is Ra / Rs.
  • the value was 8.3.
  • a laminated electrode body consisting of a positive electrode, a solid electrolyte layer, and a negative electrode is stacked inside a stainless steel sealing can fitted with a polypropylene annular gasket so that the negative electrode side faces the inside of the sealing can, and then the stainless steel exterior. After covering the can, the open end of the outer can was caulked inward to seal the can, thereby producing an all-solid-state battery having a diameter of about 9 mm.
  • Example 2 Primary particles (negative electrode active material) of lithium titanate (Li 4 Ti 5 O 12 ) with an average particle size of 1.3 ⁇ m and an algyrodite-type sulfide-based solid electrolyte (Li 6 PS 5 Cl) with an average particle size of 0.6 ⁇ m. ) And granulated to prepare an electrode material composite for the negative electrode.
  • the composition of the component in the electrode material composite for the negative electrode was 40 parts by mass of the argilodite-type sulfide-based solid electrolyte with respect to 100 parts by mass of the negative electrode active material.
  • the mixing conditions in the mixer were adjusted so as to develop van der Waals force and electrostatic force due to the collision / shearing action between the materials.
  • the ratio of the electrode material composite for the negative electrode, the same argylodite-type sulfide-based solid electrolyte used for the electrode material composite for the negative electrode, and graphene (conducting aid) is 8: 2: 1 in mass ratio.
  • a laminated electrode body was prepared in the same manner as in Example 1 except that the negative electrode mixture prepared by mixing and kneading well was used.
  • a solid-state battery was manufactured.
  • a plurality of laminated electrode bodies are produced, and for some of them, the cross sections of the positive electrode mixture molded body and the negative electrode mixture molded body are observed by SEM, and the positive electrode mixture molded body and the negative electrode mixture are formed by the above method.
  • the average particle size Ra of the primary particles of the positive electrode active material is 5 ⁇ m
  • the average particle size Rs of the primary particles of the argylodite-type sulfide-based solid electrolyte is 0.6 ⁇ m. Yes, the value of Ra / Rs was 8.3.
  • the average particle size Ra of the primary particles of the negative electrode active material is 1.3 ⁇ m
  • the average particle size Rs of the primary particles of the algyrodite type sulfide-based solid electrolyte is 0. It was 6 ⁇ m, and the value of Ra / Rs was 2.2.
  • Example 3 An electrode material composite for a positive electrode was produced in the same manner as in Example 1 except that the amount of the argilodite-type sulfide-based solid electrolyte was changed to 48 parts by mass with respect to 100 parts by mass of the positive electrode active material. Then, except that the positive electrode material composite for the positive electrode and the acetylene black (conductive auxiliary agent) were mixed at a mass ratio of 26: 1 and kneaded well to prepare a positive electrode mixture, the same as in Example 1. A laminated electrode body was produced in the same manner, and an all-solid-state battery was produced in the same manner as in Example 1 except that the laminated electrode body was used.
  • a plurality of laminated electrode bodies are produced, and for a part of them, the cross section of the positive electrode mixture molded body is observed by SEM, and the electrode material composite composed of the granulated body in the positive electrode mixture molded body by the above method.
  • the algyrodite-type sulfide-based solid electrolyte in the electrode material composite was confirmed to be granular.
  • the average particle size Ra of the primary particles of the positive electrode active material is 5 ⁇ m
  • the average particle size Rs of the primary particles of the argilodite-type sulfide-based solid electrolyte is 0.6 ⁇ m, which is Ra / Rs.
  • the value was 8.3.
  • the positive electrode active material is a primary particle of LiCo 0.98 Al 0.01 Mg 0.01 O 2 (LiCo 0.98 Al 0.01 Mg 0.01 ) having an average particle diameter of 3 ⁇ m and a layer composed of LiNbO 3 on the surface. Same as Example 1 except that the amount of the layer composed of LiNbO 3 on the surface of O 2 was changed to LiCo 0.98 Al 0.01 Mg 0.01 O 2 : 1 part by mass with respect to 100 parts by mass).
  • the electrode material composite for the positive electrode was produced in the same manner as in Example 1 except that the electrode material composite for the positive electrode was used. An all-solid-state battery was produced in the same manner as in 1.
  • a plurality of laminated electrode bodies are produced, and for a part of them, the cross section of the positive electrode mixture molded body is observed by SEM, and the electrode material composite composed of the granulated body in the positive electrode mixture molded body by the above method.
  • the algyrodite-type sulfide-based solid electrolyte in the electrode material composite was confirmed to be granular.
  • the average particle size Ra of the primary particles of the positive electrode active material is 3 ⁇ m
  • the average particle size Rs of the primary particles of the argilodite-type sulfide-based solid electrolyte is 0.6 ⁇ m, which is Ra / Rs. The value was 5.
  • Example 5 An electrode material composite for a positive electrode was produced in the same manner as in Example 1 except that the amount of the argilodite-type sulfide-based solid electrolyte was changed to 37 parts by mass with respect to 100 parts by mass of the positive electrode active material. Then, the same argilodite-type sulfide-based solid electrolyte used for the positive electrode material composite and acetylene black (conductive aid) are mixed at a mass ratio of 24: 5: 1 and kneaded well. A laminated electrode body was produced in the same manner as in Example 1 except that the prepared positive electrode mixture was used, and an all-solid-state battery was produced in the same manner as in Example 1 except that this laminated electrode body was used.
  • a plurality of laminated electrode bodies are produced, and for a part of them, the cross section of the positive electrode mixture molded body is observed by SEM, and the electrode material composite composed of the granulated body in the positive electrode mixture molded body by the above method.
  • the algyrodite-type sulfide-based solid electrolyte in the electrode material composite was confirmed to be granular.
  • the average particle size Ra of the primary particles of the positive electrode active material is 5 ⁇ m
  • the average particle size Rs of the primary particles of the argilodite-type sulfide-based solid electrolyte is 0.6 ⁇ m, which is Ra / Rs.
  • the value was 8.3.
  • the positive electrode active material is obtained from the primary particles of LiCo 0.3 Ni 0.7 O 2 having an average particle diameter of 5 ⁇ m and having a layer composed of LiNbO 3 on the surface (from LiNbO 3 on the surface of LiCo 0.3 Ni 0.7 O 2 ).
  • An electrode material composite for a positive electrode was prepared in the same manner as in Example 1 except that the amount of the layer to be formed was changed to LiCo 0.3 Ni 0.7 O 2 : 1 part by mass with respect to 100 parts by mass).
  • a laminated electrode body was produced in the same manner as in Example 1 except that the positive electrode material composite was used, and an all-solid-state battery was produced in the same manner as in Example 1 except that this laminated electrode body was used.
  • a plurality of laminated electrode bodies are produced, and for a part of them, the cross section of the positive electrode mixture molded body is observed by SEM, and the electrode material composite composed of the granulated body in the positive electrode mixture molded body by the above method.
  • the algyrodite-type sulfide-based solid electrolyte in the electrode material composite was confirmed to be granular.
  • the average particle size Ra of the primary particles of the positive electrode active material is 5 ⁇ m
  • the average particle size Rs of the primary particles of the argilodite-type sulfide-based solid electrolyte is 0.6 ⁇ m, which is Ra / Rs.
  • the value was 8.3.
  • the positive electrode active material is a primary particle (LiNi 1/3 Co 1/3 Mn 1/3 ) of LiNi 1/3 Co 1/3 Mn 1/3 O2 having an average particle diameter of 5 ⁇ m and a layer composed of LiNbO 3 on the surface. Same as Example 1 except that the amount of the layer composed of LiNbO 3 on the surface of O 2 was changed to LiNi 1/3 Co 1/3 Mn 1/3 O 2 : 1 part by mass with respect to 100 parts by mass).
  • the electrode material composite for the positive electrode was produced in the same manner as in Example 1 except that the electrode material composite for the positive electrode was used.
  • An all-solid-state battery was produced in the same manner as in 1.
  • a plurality of laminated electrode bodies are produced, and for a part of them, the cross section of the positive electrode mixture molded body is observed by SEM, and the electrode material composite composed of the granulated body in the positive electrode mixture molded body by the above method.
  • the algyrodite-type sulfide-based solid electrolyte in the electrode material composite was confirmed to be granular.
  • the average particle size Ra of the primary particles of the positive electrode active material is 5 ⁇ m
  • the average particle size Rs of the primary particles of the argilodite-type sulfide-based solid electrolyte is 0.6 ⁇ m, which is Ra / Rs.
  • the value was 8.3.
  • Example 8 An electrode material composite for a positive electrode was prepared in the same manner as in Example 1 except that the argyrodite-type sulfide-based solid electrolyte was changed to Li 10 GeP 2 S 12 having an average particle diameter of 0.6 ⁇ m, and the electrode for the positive electrode was prepared.
  • Example 1 the solid electrolyte layer and the solid electrolyte used for the negative electrode mixture were changed to Li 10 GeP 2 S 12 having an average particle diameter of 0.6 ⁇ m, but the same as in Example 1 was applied.
  • a laminated electrode body was produced, and an all-solid-state battery was produced in the same manner as in Example 1 except that the laminated electrode body was used.
  • a plurality of laminated electrode bodies are produced, and for a part of them, the cross section of the positive electrode mixture molded body is observed by SEM, and the electrode material composite composed of the granulated body in the positive electrode mixture molded body by the above method.
  • the algyrodite-type sulfide-based solid electrolyte in the electrode material composite was confirmed to be granular.
  • the average particle size Ra of the primary particles of the positive electrode active material is 5 ⁇ m
  • the average particle size Rs of the primary particles of the argilodite-type sulfide-based solid electrolyte is 0.6 ⁇ m, which is Ra / Rs.
  • the value was 8.3.
  • Example 9 The electrode material for the positive electrode is the same as in Example 1 except that the argilodite type sulfide-based solid electrolyte is changed to Li 4.9 PS 4.2 Cl 0.9 Br 0.9 having an average particle diameter of 0.6 ⁇ m.
  • a positive electrode mixture was prepared in the same manner as in Example 1 except that it was changed to 9.9 Br 0.9 .
  • a plurality of laminated electrode bodies are produced, and for a part of them, the cross section of the positive electrode mixture molded body is observed by SEM, and the electrode material composite composed of the granulated body in the positive electrode mixture molded body by the above method.
  • the algyrodite-type sulfide-based solid electrolyte in the electrode material composite was confirmed to be granular.
  • the average particle size Ra of the primary particles of the positive electrode active material is 5 ⁇ m
  • the average particle size Rs of the primary particles of the argilodite-type sulfide-based solid electrolyte is 0.6 ⁇ m, which is Ra / Rs.
  • the value was 8.3.
  • Example 10 A laminated electrode body was produced in the same manner as in Example 1 except that the negative electrode active material was changed to graphite having an average particle size of 15 ⁇ m, and all solids were prepared in the same manner as in Example 1 except that this laminated electrode body was used. A battery was made.
  • a plurality of laminated electrode bodies are produced, and for a part of them, the cross section of the positive electrode mixture molded body is observed by SEM, and the electrode material composite composed of the granulated body in the positive electrode mixture molded body by the above method.
  • the algyrodite-type sulfide-based solid electrolyte in the electrode material composite was confirmed to be granular.
  • the average particle size Ra of the primary particles of the positive electrode active material is 5 ⁇ m
  • the average particle size Rs of the primary particles of the argilodite-type sulfide-based solid electrolyte is 0.6 ⁇ m, which is Ra / Rs.
  • the value was 8.3.
  • Comparative Example 1 The same primary particles (positive electrode active material) of LiCo 0.98 Al 0.01 Mg 0.01 O 2 having a layer made of LiNbO 3 on the surface, which is the same as that used in Example 1, and the one used in Example 1.
  • a positive electrode mixture was prepared by mixing the same argilodite-type sulfide-based solid electrolyte and acetylene black (conductive auxiliary) in a mass ratio of 17: 8: 1.
  • An all-solid-state battery was produced in the same manner as in Example 1 except that this positive electrode mixture was used.
  • the positive electrode active material and the solid electrolyte were not granulated.
  • the positive particle active material is LiCo 0.98 Al 0.01 Mg 0.01 O 2 primary particles (LiCo 0.98 Al 0.01 Mg 0.01 ) having an average particle size of 3 ⁇ m and a layer composed of LiNbO 3 on the surface. Same as Comparative Example 1 except that the amount of the layer composed of LiNbO 3 on the surface of O 2 was changed to LiCo 0.98 Al 0.01 Mg 0.01 O 2 : 1 part by mass with respect to 100 parts by mass). To make an all-solid-state battery.
  • the positive electrode active material is obtained from the primary particles of LiCo 0.3 Ni 0.7 O 2 (from LiNbO 3 on the surface of LiCo 0.3 Ni 0.7 O 2) having an average particle diameter of 5 ⁇ m and having a layer composed of LiNbO 3 on the surface .
  • An all-solid-state battery was produced in the same manner as in Comparative Example 1 except that the amount of the layer was changed to LiCo 0.3 Ni 0.7 O 2 : 1 part by mass with respect to 100 parts by mass).
  • Comparative Example 4 An all-solid-state battery was produced in the same manner as in Comparative Example 1 except that the negative electrode active material was changed to graphite having an average particle size of 15 ⁇ m.
  • An electrode material composite for a positive electrode was prepared in the same manner as in Example 1 except that the positive electrode active material and the argilodite-type sulfide-based solid electrolyte were mixed under conditions where a stress was applied to the extent that a mechanochemical reaction occurred.
  • a laminated electrode body was produced in the same manner as in Example 1 except that the positive electrode material composite was used, and an all-solid-state battery was produced in the same manner as in Example 1 except that this laminated electrode body was used.
  • a plurality of laminated electrode bodies were prepared, and for some of them, the cross section of the positive electrode mixture molded body was observed by SEM, and the algyrodite-type sulfide-based solid electrolyte in the electrode material composite could not maintain the granularity, and the solid electrolyte. It was confirmed that the phase was continuous. Further, in the electrode material composite, the average particle size Ra of the primary particles of the positive electrode active material was 5 ⁇ m.
  • the 1C discharge capacity was measured by charging and discharging under the same conditions as when the initial capacity was measured, except that the current value at the time of discharge was changed to 1C. Then, the value obtained by dividing the 1C discharge capacity of each battery by the initial capacity was expressed as a percentage to obtain the capacity retention rate, and the load characteristics of each battery were evaluated.
  • a molded body of an electrode mixture composed of a granulated body of an active material and an argilodite-type sulfide-based solid electrolyte and containing an electrode material composite in which the argilodite-type sulfide-based solid electrolyte is granular.
  • the all-solid-state batteries of Examples 1 to 10 using the electrodes having the above are the batteries of Comparative Examples 1 to 4 using the electrodes having the molded body of the electrode mixture not containing the electrode material composite, and the argyrodite type sulfide.
  • the molded body of the electrode mixture containing the electrode material composite is used.
  • the load characteristics were more excellent.
  • the present application can be implemented in a form other than the above as long as it does not deviate from the purpose.
  • the embodiments disclosed in the present application are examples, and the present invention is not limited thereto.
  • the scope of the present application shall be construed in preference to the description of the appended claims over the description of the specification described above, and all changes within the scope of the claims shall be included in the scope of the claims. It is something that can be done.
  • Electrode material composite 1a 3 Primary particles of active material 1b Algyrodite type sulfide-based solid electrolyte 2 Solid electrolyte 10,100 All-solid battery 20 Positive electrode 30 Negative electrode 40 Solid electrolyte layer 50 Exterior can 60 Sealed can 70 Gasket 200 Electrode body 300 Positive electrode external terminal 400 Negative electrode external terminal 500 Laminated film exterior

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  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Une électrode de batterie entièrement solide selon la présente invention comprend un corps moulé d'un mélange d'électrodes. Le mélange d'électrodes contient un complexe de matériau d'électrode. Le complexe de matériau d'électrode est formé d'un corps granulé contenant un matériau actif et un électrolyte solide. L'électrolyte solide contient un électrolyte solide à base de sulfure de type argyrodite granulaire. En outre, la batterie entièrement solide selon la présente invention comporte : une électrode positive, une électrode négative et une couche d'électrolyte solide interposée entre l'électrode positive et l'électrode négative. L'électrode positive et/ou l'électrode négative est l'électrode de batterie entièrement solide susmentionnée selon la présente invention.
PCT/JP2021/048075 2020-12-24 2021-12-24 Électrode de batterie entièrement solide et batterie entièrement solide WO2022138886A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016207418A (ja) * 2015-04-21 2016-12-08 トヨタ自動車株式会社 電極合材
JP2020021674A (ja) * 2018-08-02 2020-02-06 トヨタ自動車株式会社 全固体電池およびその製造方法
JP2020135948A (ja) * 2019-02-13 2020-08-31 三井金属鉱業株式会社 活物質、それを用いた正極合剤及び固体電池
JP2020161288A (ja) * 2019-03-26 2020-10-01 東京電力ホールディングス株式会社 硫黄正極合材およびその製造方法、硫黄正極、リチウム硫黄固体電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016207418A (ja) * 2015-04-21 2016-12-08 トヨタ自動車株式会社 電極合材
JP2020021674A (ja) * 2018-08-02 2020-02-06 トヨタ自動車株式会社 全固体電池およびその製造方法
JP2020135948A (ja) * 2019-02-13 2020-08-31 三井金属鉱業株式会社 活物質、それを用いた正極合剤及び固体電池
JP2020161288A (ja) * 2019-03-26 2020-10-01 東京電力ホールディングス株式会社 硫黄正極合材およびその製造方法、硫黄正極、リチウム硫黄固体電池

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