WO2014038521A1 - Matériau céramique électrolytique solide - Google Patents

Matériau céramique électrolytique solide Download PDF

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WO2014038521A1
WO2014038521A1 PCT/JP2013/073575 JP2013073575W WO2014038521A1 WO 2014038521 A1 WO2014038521 A1 WO 2014038521A1 JP 2013073575 W JP2013073575 W JP 2013073575W WO 2014038521 A1 WO2014038521 A1 WO 2014038521A1
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ceramic material
component
firing
garnet
material according
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PCT/JP2013/073575
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English (en)
Japanese (ja)
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直仁 山田
一博 山本
昭彦 本多
直美 齊藤
将伸 中山
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日本碍子株式会社
国立大学法人名古屋工業大学
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Priority to JP2014534352A priority Critical patent/JP6272229B2/ja
Publication of WO2014038521A1 publication Critical patent/WO2014038521A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G29/00—Compounds of bismuth
    • C01G29/006—Compounds containing, besides bismuth, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G35/00—Compounds of tantalum
    • C01G35/006—Compounds containing, besides tantalum, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/486—Fine ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C04B2235/3203—Lithium oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
    • C04B2235/762—Cubic symmetry, e.g. beta-SiC
    • C04B2235/764—Garnet structure A3B2(CO4)3
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a solid electrolyte ceramic material having lithium ion conductivity.
  • the lithium-air battery is a battery that can be expected to have a theoretical maximum capacity by using atmospheric oxygen as a positive electrode active material and lithium metal as a negative electrode active material.
  • such an air battery also has the problem of the dendrite, and as described above, the solution is strongly desired.
  • Non-Patent Document 1 Li 7 La 3 Zr 2 O 12 (hereinafter referred to as LLZ) is lithium-resistant. It has been reported that it can be used as a solid electrolyte of an all-solid lithium secondary battery.
  • Patent Document 1 Japanese Patent Publication No. 2007-528108 discloses a garnet-type solid ion conductor having a composition of L 5 + x A y G z M 2 O 12 .
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2011-051800 discloses that the addition of Al in addition to Li, La and Zr, which are basic elements of LLZ, can improve the density and lithium ion conductivity.
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2011-073962 discloses that lithium ion conductivity can be further improved by adding Nb and / or Ta in addition to Li, La and Zr which are basic elements of LLZ. ing.
  • Patent Document 4 Japanese Patent Laid-Open No. 2011-073963
  • Patent Document 5 Japanese Patent Laid-Open No.
  • Li x Ln 3 (M 1 y M 2 z ) O t (where Ln is La, Pr, Nd, Sm, Lu, Y, K, mg, Ba, Ca, 1 or more elements selected from the group consisting of Sr, M 1 is, Si, Sc, Ti, V , Ga, Ge, Y, Zr, Nb, in, Sb, Te, Hf,
  • M 1 is, Si, Sc, Ti, V , Ga, Ge, Y, Zr, Nb, in, Sb, Te, Hf
  • One or more elements selected from the group consisting of Ta, W, Bi, M 2 is an element different from M 1, and is Sc, Ti, V, Y, Nb, Hf, Ta, Si, Ga, and
  • a garnet-type lithium ion conductive oxide containing Al in a skeleton represented by one or more elements selected from the group consisting of Ge is disclosed.
  • Non-Patent Document 2 (Materials Science and Engineering B 143 (2007) 14-20) discloses Li 5 La 3 Bi 2 O 12 and reports a value of 0.04 mS / cm for the ionic conductivity in the grains. Has been. However, these solid electrolytes cannot be said to have sufficiently high conductivity, and further higher conductivity is desired.
  • the present inventors have recently found that in a garnet-type or garnet-like LLZ-based solid electrolyte ceramic material, a higher conductivity can be realized by using a composition in which a substitution element containing at least Bi coexists. Got.
  • an object of the present invention is to realize further higher conductivity in a garnet-type or garnet-type-like LLZ-based solid electrolyte ceramic material.
  • a solid electrolyte ceramic material having lithium ion conductivity comprising the ceramic material comprising an oxide sintered body having a garnet-type or garnet-type similar crystal structure containing a main constituent element of Li, La, Zr and O and a substitution element containing at least Bi Material is provided.
  • the ceramic material according to the present invention is a solid electrolyte ceramic material having lithium ion conductivity.
  • This ceramic material is made of an oxide sintered body having a garnet-type or garnet-type crystal structure containing a main constituent element such as Li, La, Zr, and O and a substitution element containing at least Bi.
  • the substitution element preferably further contains Ta or Nb.
  • this crystal structure is a garnet-type or garnet-type crystal structure composed of at least Li, La, Zr and O (hereinafter referred to as LLZ crystal structure), and a part of the Zr site is Bi and It is optionally substituted with a substitution element containing Ta or Nb.
  • the Zr site in the LLZ crystal structure is composed of a plurality of predetermined elements.
  • the ionic conductivity can be improved because the Zr site is composed of a plurality of predetermined elements.
  • the partial substitution amount of Zr by the substitution element is preferably 5 to 30 mol%, more preferably 5 to 20 mol%, and still more preferably 10 to 10 mol% with respect to the total number of moles of elements constituting the Zr site. 20 mol%.
  • Such a ceramic material of the present invention can be said to be a garnet-type or garnet-type-like LLZ-based solid electrolyte ceramic material, but other elements other than Li, La, Zr, Bi, Ta, Nb and O (for example, Al) may be included in the crystal lattice or other portions (for example, grain boundaries).
  • Ta and Nb which may exist if desired are substituted into the Zr site as the same pentavalent element, since the ionic radii are equivalent, the same effect is brought about in the change of the crystal structure and hence the ionic conductivity. . Therefore, even if the Zr site is replaced with any of the combination of Bi and Ta, the combination of Bi and Nb, or the combination of Bi, Ta and Nb, the same effect can be obtained.
  • the ceramic material of the present invention is a garnet-type or garnet-type similar LLZ-based solid electrolyte ceramic material.
  • an X-ray diffraction file No. of CSD Cambridge Structural Database
  • 422259 Li 7 La 3 Zr 2 O 12
  • the constituent elements are different and the Li concentration in the ceramics may be different, so the diffraction angle and the diffraction intensity ratio may be different.
  • the garnet-type or garnet-like crystal structure in the ceramic material of the present invention has the general formula: Li 7-xy La 3 (Zr 2-xy , M x , Bi y ) O 12- ⁇ (Where 0 ⁇ x ⁇ 0.6, 0.03 ⁇ y ⁇ 0.6 (eg, 0.05 ⁇ y ⁇ 0.6), 0.1 ⁇ x + y ⁇ 0.6, and M is Ta or Nb is included, and ⁇ represents the amount of oxygen deficiency but may be 0) Is preferably included, more preferably 0 ⁇ x ⁇ 0.4, 0.05 ⁇ y ⁇ 0.4, 0.1 ⁇ x + y ⁇ 0.4, and further preferably 0 ⁇ x.
  • the above general formula is conventionally Li 7-xy La 3 (Zr 2-xy , M x , Bi is abbreviated y) O 12 it is permissible. In any case, it is considered that there is no problem if 0 ⁇ ⁇ ⁇ 1. Further, the above general formula defines the composition ratio of the main constituent element and the substitution element, and the crystal lattice of other elements (for example, Al and Mg) or other parts (for example, grain boundaries). This does not exclude the possibility of inclusion.
  • the oxide sintered body preferably contains Al as an additive element for the sintering aid.
  • Al is an element effective in obtaining a highly compact sintered pellet capable of handling a ceramic material having an LLZ crystal structure, and also improves lithium ion conductivity.
  • the form of Al is not particularly limited. As long as the LLZ crystal structure can be confirmed, Al may exist in the crystal lattice or may exist in other than the crystal lattice.
  • the presence of Al can be detected by, for example, ICP (high frequency inductively coupled plasma) emission spectroscopic analysis, EPMA (electron beam microanalyzer) or the like, and the content thereof can be determined.
  • the amount of Al added is not particularly limited as long as it is an amount that can improve the density and lithium ion conductivity without impairing the basic characteristics of the LLZ-based solid electrolyte ceramic material, but is finally limited to LLZ-Al
  • the content is preferably 0.01 to 1% by mass, more preferably 0.05% by mass or more, based on the total weight of the ceramic ceramic powder or sintered body pellet.
  • the Al content exceeds 2% by mass, grain growth becomes remarkable and pores remain, resulting in a decrease in density, resulting in a decrease in lithium ion conductivity, preferably 1.2% by mass or less. It is.
  • the oxide sintered body may further contain Mg as an additive element.
  • Mg is an element that improves density and strength, preferably by adding together with Al to suppress or avoid the occurrence of defects such as uneven firing, cracks, vacancies, and abnormal grain growth.
  • the form of Mg is not particularly limited. As long as the LLZ crystal structure can be confirmed, Mg may exist in the crystal lattice or may exist in other than the crystal lattice.
  • the presence of Mg can be detected by, for example, ICP (high frequency inductively coupled plasma) emission spectroscopic analysis, EPMA (electron beam microanalyzer) or the like, and the content thereof can be determined.
  • the amount of Mg added is not particularly limited as long as it is an amount that can improve the density and strength without impairing the basic characteristics of the LLZ-based solid electrolyte ceramic material, but is not limited to the total weight of the oxide sintered body.
  • Mg content as an additive element other than the substitution element greatly exceeds 1% by mass, the lithium ion conductivity tends to decrease, and is preferably 0.50% by mass or less.
  • a more preferable Mg content is 0.05 to 0.30 mass%.
  • this oxide sintered body contains both Al and Mg as additive elements.
  • Al and Mg are added as a sintering aid and / or a particle growth inhibitor.
  • a garnet-type or garnet-like LLZ-based solid electrolyte ceramic material is increased in size for practical use, defects such as uneven firing, cracks, vacancies, abnormal grain growth, etc. occur, resulting in a decrease in denseness and strength.
  • such a problem is solved by the combined addition of Al and Mg.
  • the ceramic material of the present invention is not limited to a laboratory-scale small size, and even if it is a large size suitable for practical use or mass production, defects such as uneven firing, cracks, vacancies, and abnormal grain growth Etc. can be reduced or avoided to achieve high density and high strength.
  • the ceramic material of the present invention preferably has a sintered body size of more than 20 mm ⁇ 20 mm, more preferably more than 25 mm ⁇ 25 mm, and still more preferably more than 50 mm ⁇ 50 mm. .
  • the thickness of the ceramic material of the present invention is preferably 1 mm or less, more preferably 0.5 mm or less, and further preferably 0.2 mm or less, from the viewpoint of reducing internal resistance when the battery is applied.
  • the ceramic material of the present invention preferably has a density of 4.8 g / cm 3 or more, more preferably 5.0 g / cm 3 or more, and still more preferably 5.1 g / cm 3 or more.
  • the density is 5.0 g / cm 3 or more, the handling property is good and good lithium ion conductivity can be obtained, and even when the plate is thinned, the through holes caused by defects such as vacancies can be obtained. Generation can be suppressed, and it is effective for suppressing lithium dendrite short-circuiting.
  • the density of the ceramic material can be calculated, for example, by measuring the weight and volume of the pellet.
  • the ceramic material of the present invention preferably has a 4-point bending strength measured in accordance with JIS R1601 (2008) of 70 MPa or more, more preferably 100 MPa or more.
  • the lithium ion conductivity of the ceramic material of the present invention is preferably 0.70 mS / cm or more, more preferably 0.80 mS / cm or more, more preferably 0.880 mS / cm or more, and still more preferably 0. 890 mS / cm or more.
  • the lithium ion conductivity is preferably measured by, for example, an AC impedance method or a method that can obtain the same accuracy and accuracy.
  • the ceramic material of the present invention is used as a solid electrolyte material for various applications by utilizing its conductivity and denseness.
  • it can be used for a lithium battery such as a lithium secondary battery and various gas sensor materials such as SOx, NOx, carbon dioxide gas and oxygen, but is particularly preferably used as a solid electrolyte of an all-solid lithium secondary battery.
  • the electrolyte solution on the positive electrode side and the negative electrode side can be completely separated by overlaying or replacing the ceramic material according to the present invention on the separator portion of a normal lithium ion secondary battery using the electrolyte solution.
  • batteries that are expected to be applied with the ceramic material targeted by the present invention include all-solid-state batteries and current lithium ions, including lithium-air batteries and lithium-sulfur batteries that are assumed to use lithium metal for the negative electrode.
  • Various types of batteries can be mentioned up to the battery, and these are collectively referred to as a lithium battery in this specification.
  • a lithium battery in this specification As a means for essentially preventing a dendrite short circuit, it is considered effective to use a dense solid electrolyte made of ceramics as a partition between positive and negative electrodes.
  • secondary batteries using lithium metal as the negative electrode have frequently suffered short-circuit accidents between the positive and negative electrodes due to dendrite (resin-like crystal) precipitates.
  • a lithium battery particularly preferably a lithium secondary battery, comprising a positive electrode, a negative electrode, and a solid electrolyte made of a ceramic material provided between the positive electrode and the negative electrode. Is preferably made of lithium metal or a lithium alloy.
  • the solid electrolyte ceramic material according to the present invention as described above can be manufactured by the following procedure.
  • a raw material powder is prepared that includes main constituent elements that are Li, La, and Zr in a mixing ratio capable of giving a garnet-type or garnet-like crystal structure, and a substitution element that contains Bi and optionally Ta or Nb.
  • the raw material powder is fired in one step or in multiple steps, and an oxide sintered body having a garnet-type or garnet-type similar crystal structure composed of the main constituent elements partially substituted with substitution elements is synthesized as a ceramic material.
  • Al and / or Mg is added as an additional element as desired in the step of preparing the raw material powder and / or the synthesis step.
  • these steps will be specifically described.
  • a raw material powder containing Al and / or Mg as an element that is, a pulverized powder of a raw material for firing is prepared.
  • These constituent metal elements may be contained in the firing raw material as a Li component, a La component, a Zr component, a Bi component, a Ta component or Nb component as required, and an Al component and / or Mg component as desired.
  • the ceramic material of the present invention contains O, O may be contained as a constituent element in a compound of these constituent metal elements.
  • These various raw material components can be in any form such as various metal salts such as metal oxides, metal hydroxides, and metal carbonates containing the respective metal elements, and are not particularly limited.
  • Li 2 CO 3 or LiOH is used as the Li component
  • La (OH) 3 or La 2 O 3 is used as the La component
  • ZrO 2 is used as the Zr component
  • Bi 2 O 3 is used as the Bi component.
  • Ta 2 O 5 is used as the Ta component and Nb 2 O 5 as the Nb component.
  • the raw material powder can contain main constituent elements Li, La, Zr and a substitution element to such an extent that an LLZ crystal structure can be obtained by solid phase reaction or the like.
  • Li component, La component, and Zr component + substitution element component ie Bi component and optionally Ta component or Nb component
  • Bi component and optionally Ta component or Nb component are 7: 3: 2 or a composition close to the composition ratio according to the stoichiometric composition of LLZ. Can be used.
  • the Li component includes an amount slightly increased (for example, about 10%) from the molar ratio equivalent amount based on the stoichiometry of Li in LLZ.
  • the La component and the Zr component can be contained in amounts corresponding to the LLZ molar ratio, respectively.
  • blend so that the molar ratio of Li: La: (Zr + Bi + Ta + Nb) may be 7.7: 3: 2.
  • the Bi component, the Ta component, and the Nb component can be in any form such as a metal oxide, a metal hydroxide, and a metal carbonate containing the respective metal components, and are not particularly limited.
  • Bi components include bismuth oxide (Bi 2 O 3 ), bismuth hyponitrite (Bi 5 O (OH) 9 (NO 3 ) 4 ), bismuth carbonate oxide (Bi 2 (CO 3 ) O 2 ), hydroxide Bismuth (Bi (OH) 3 ) etc. are mentioned.
  • the Nb component include niobium alkoxide containing Nb 2 O 5 , NbCl 5 , Nb, propoxyniobium and the like.
  • the Ta component include Ta 2 O 5 , TaCl 5 , Ta, tantalum alkoxide containing tantalum ethoxide, and the like.
  • Al may be added when preparing the raw material powder. That is, the raw material powder can contain Al-containing powder.
  • the Al component can be in any form such as a metal oxide containing Al, a metal hydroxide, a metal nitrate, a metal organic substance, or a simple metal, and is not particularly limited.
  • Al component Al 2 O 3, Al ( NO 3) 3 ⁇ 9H 2 O, Al (OH) 3, Al, aluminum acetylacetonate, aluminum triethoxide, aluminum butoxide, aluminum propoxide, aluminum methoxide
  • Examples include isobutylaluminum, aluminum sulfate, and aluminum iodide.
  • the addition of Al is preferably performed so that the oxide sintered body contains Al in an amount of 0.01 to 1% by mass, and more preferably 0.05 to 1.2% by mass.
  • the molar ratio of Al / La in the oxide sintered body is preferably 0.008 or more and 0.12 or less, more preferably 0.10 or less.
  • Mg may be added when preparing the raw material powder. That is, the raw material powder can contain Mg-containing powder.
  • the Mg component can be in any form such as a metal oxide containing Mg, a metal hydroxide, a metal nitrate, a metal organic substance, or a simple metal, and is not particularly limited. Examples of Mg component, MgO, MgO 2, Mg ( OH) 2, MgCl 2, MgBr 2, MgI 2, MgH 2, MgB 2, Mg 3 N 2, MgCO 3, Mg (NO 3) 2, MgClO 4 Mg (CH 3 COO) 2 , C 14 H 10 MgO 4 , Mg (CH 3 (CH 2 ) 16 COO) 2 and the like.
  • the addition of Mg is preferably performed so that the oxide sintered body contains Mg in an amount of 0.01 to 1% by mass, and more preferably 0.05 to 0.30% by mass.
  • each of the above components can be used without particular limitation as long as it is industrially produced and available, but preferably has a purity of 95% or more, and more preferably has a purity of 98% or more. It is. Moreover, it is preferable that the water
  • a known raw material powder preparation method in ceramic powder synthesis can be appropriately employed.
  • the raw materials for firing can be uniformly mixed by putting them into a reiki machine or an appropriate ball mill.
  • the preparation conditions of such a raw material for firing are appropriately determined according to the subsequent synthesis step. That is, a raw material for firing containing all the raw material components necessary for the ceramic material of the present invention may be prepared at once, or a part of the raw material components (for example, Li component, La component, Zr component, Bi)
  • a raw material for firing containing a component, Ta component, Nb component, Al component, and Mg component is prepared, and the fired powder (temporary) of the raw material for firing is prepared immediately before the synthesis step.
  • the final component for firing may be obtained by adding the remaining components and the remaining amount (for example, the total amount of Al component and / or Mg component or a part thereof) to (baked powder).
  • firing is performed in a firing container made of an Mg-containing material (hereinafter referred to as a firing sheath) filled with raw material powder, and Mg is diffused from this container to add Mg.
  • Mg-containing material is not particularly limited as long as it is a material that contains Mg so that it can diffuse into the sintered body as it is fired, but MgO is preferred.
  • Mg-containing powder when added to the raw material powder, it is not essential to use a fired sheath made of Mg-containing material. In that case, a fired sheath made of other materials such as alumina is used. May be. Further, in the aspect in which Mg is diffused from the fired sheath, addition of the Mg-containing powder to the raw material powder may also be performed. In any case, the addition of Mg as an additional element other than the substitution element is preferably performed so that the oxide sintered body contains Mg in an amount of 0.01 to 1% by mass, and more preferably, 0.1% by mass. 05 to 0.30% by mass.
  • the firing atmosphere in the synthesis step may be an oxidizing atmosphere containing oxygen or an inert atmosphere made of an inert gas such as Ar, and is not particularly limited.
  • an oxidizing atmosphere containing oxygen or an inert atmosphere made of an inert gas such as Ar By synthesizing the ceramic material in an inert gas atmosphere, it becomes easier to obtain a higher density, and it is an element that tends to be lost during synthesis with respect to La (an element that is difficult to lose during synthesis) in the raw material for firing. ) The ratio of the number of moles of Li is easily maintained even in the sintered body.
  • the raw material is preferably a powder containing an O component such as an oxide. Moreover, even when the ceramic material is synthesized in an oxidizing atmosphere, high density and ionic conductivity can be realized.
  • the second baking step in an inert gas atmosphere or an oxidizing atmosphere in the first baking step and the second baking step described later.
  • the inert gas species include one or more selected from helium (He), argon (Ar), and nitrogen (N), preferably Ar.
  • the firing temperature for synthesis is not particularly limited, but is preferably 800 ° C. or higher, and more preferably 850 ° C. or higher and 1250 ° C. or lower.
  • the oxidizing atmosphere include an air atmosphere and an oxygen atmosphere, but an oxygen atmosphere is preferable, and an oxygen atmosphere of about 100% oxygen is more preferable.
  • the synthesis step includes a first firing step of firing the raw material powder described above to obtain a precursor powder, and pulverizing and firing the obtained precursor powder to obtain an oxide sintered body.
  • a second firing step By such a combination of firing steps, an LLZ crystal structure is easily obtained.
  • the above-described addition by diffusion of Mg is performed, it is preferably performed in the second firing step.
  • the firing container (firing sheath) made of the Mg-containing material filled with the precursor powder. And adding Mg by diffusing Mg from this container.
  • the first firing step is a step of obtaining a precursor powder for easily forming an LLZ crystal structure in the second firing step by performing thermal decomposition of at least a Li component, a La component, a Zr component, and a Bi component. .
  • the precursor powder may already have an LLZ crystal structure.
  • the firing temperature is preferably 850 ° C. or higher and 1150 ° C. or lower.
  • the first baking step may include a step of heating at a lower heating temperature and a step of heating at a higher heating temperature within the above temperature range. By providing such a heating step, a more uniform ceramic powder can be obtained, and a high-quality sintered body can be obtained by the second firing step.
  • the first baking step may be performed in an oxidizing atmosphere such as the air, or may be performed in an inert atmosphere, and it is preferable that an atmosphere corresponding to the raw material is appropriately selected. Considering thermal decomposition, an oxidizing atmosphere is preferable. Further, the first baking step is preferably composed of heat treatment of 850 ° C. or higher and 1150 ° C. or lower once to twice, and heat treatment step of 900 ° C. or higher and 1000 ° C. or lower (more preferably about 950 ° C.) twice. More preferably, it is comprised. In this case, it is preferable that the first baking step is performed for 15 hours to 25 hours in total as the total heating time at the maximum temperature set as the heating temperature as a whole.
  • the firing raw material used in the first firing step may not contain an Al component and / or a Mg component.
  • an Al component and / or an Mg component may be added and fired.
  • the addition of the Al component and / or Mg component may be performed by addition of Al-containing powder and / or Mg-containing powder, or may be performed by diffusion of Al and / or Mg from a fired sheath or setter. .
  • the firing raw material used in the first firing step may contain an Al component and / or a Mg component.
  • the precursor powder containing Al and / or Mg can be obtained, it is not necessary to separately add the Al component and / or Mg component to the precursor powder in the subsequent second firing step. That is, since Al and / or Mg are inherent in the precursor powder, the second firing step is performed in the presence of Al and / or Mg.
  • the firing raw material used in the first firing step includes a part of the necessary amount of the Al component and / or Mg component, and the remaining Al component and / or Mg component is added to the precursor powder in the second firing step. You may make it add.
  • the addition of the Al component and / or Mg component may be performed by addition of Al-containing powder and / or Mg-containing powder, or may be performed by diffusion of Al and / or Mg from the fired sheath.
  • the second baking step is preferably a step of heating the precursor powder obtained in the first baking step at a temperature of 950 ° C. or higher and 1250 ° C. or lower.
  • the precursor powder obtained in the first firing step can be fired to finally obtain a ceramic material having an LLZ crystal structure that is a composite oxide.
  • the heating time at the heating temperature in the second firing step is preferably about 18 hours or more and 50 hours or less. When the time is shorter than 18 hours, the formation of the LLZ ceramics is not sufficient. When the time is longer than 50 hours, it becomes easy to react with the setter via the filling powder, and the crystal growth is not able to maintain the strength as a sample. Because. Preferably, it is 30 hours or more.
  • the second baking step may be performed in an inert gas atmosphere or in an oxidizing atmosphere.
  • the second baking step is preferably performed after forming a molded body containing the precursor powder.
  • a precursor powder or a powder obtained by adding an Al component or Mg component to a precursor powder is pressure-molded using a known press technique and can be used as a desired three-dimensional shape (for example, as a solid electrolyte or separator for a secondary battery) It is preferable to carry out after forming a molded body having a suitable shape and size). By using a molded body, a solid phase reaction is promoted, and a sintered body can be easily obtained.
  • the precursor powder compact is fired and sintered in the second firing step, the compact is preferably embedded in the same powder.
  • the loss of Li can be suppressed and the change in the composition before and after the second firing step can be suppressed.
  • the curvature at the time of baking of a sintered compact can be prevented by pressing a molded object with a setter from the upper and lower sides of a filling powder as needed.
  • the precursor powder compact when the temperature is lowered by using LiOH as the Li raw material in the second firing step, the precursor powder compact can be sintered without being embedded in the same powder. This is because the loss of Li is relatively suppressed by lowering the temperature of the second firing step.
  • the first firing step is carried out using the firing raw material containing the Al component and / or the Mg component.
  • the first firing step is performed using a raw material for firing that does not contain an Al component and / or an Mg component, and the obtained precursor powder is made of Al.
  • the form which adds and mixes a component and / or Mg component, and implements a 2nd baking process, and also the form which implements a 2nd baking process using the baking sheath containing Al and / or Mg are mentioned.
  • any of these forms may be used, or these forms may be appropriately combined.
  • the ceramic material of the present invention can be obtained as an oxide sintered body.
  • Example 1 Production and Evaluation of Oxide Sintered Body Using Ar Atmosphere in the Second Firing Process
  • lithium hydroxide Kelo Chemical Co., Ltd.
  • lanthanum hydroxide Shin-Etsu
  • zirconium oxide Tosoh Corporation
  • tantalum oxide tantalum oxide and bismuth oxide
  • These powders were weighed and blended so as to have the composition shown in Table 1, and ⁇ -Al 2 O 3 was added in an amount of 0.025 in terms of the molar ratio of Al to the garnet composition formula. And mixed to obtain a raw material for firing.
  • the composition shown in Table 1 is a preparation composition, and is included in a larger amount than the target composition in consideration of loss of Li during firing. Therefore, although the charged composition is a composition that does not satisfy the charge compensation of the garnet-type crystal structure, it is understood that a composition that satisfies the charge compensation is obtained after firing due to loss of Li and / or oxygen deficiency. It should be noted that elements other than Li have substantially no loss during firing, and are basically retained after firing at the composition ratio shown in Table 1.
  • the firing raw material is put in a magnesia crucible and heated at 600 ° C./hour in the atmosphere, and held at 950 ° C. for samples 1 to 7 and 900 ° C. for sample 8. Firing was performed under the conditions for a total of 20 hours.
  • the powder obtained in the first baking step and cobblestone were mixed and pulverized for 3 hours using a vibration mill to obtain pulverized powder corresponding to samples 1 to 8 in Table 1.
  • the obtained powder was press-molded at about 100 MPa using a mold to obtain a molded body having a desired shape.
  • the obtained molded body was placed on a magnesia setter, put in the magnesia sheath together with the setter, heated at 200 ° C./hour in an Ar atmosphere, 1030 ° C. and 8 for samples 1 to 7 Was held at 1050 ° C.
  • Electrodes were formed on both surfaces of a sample for measuring lithium ion conductivity by Au sputtering, and then introduced into a glove box in an Ar atmosphere and incorporated into a CR2032 coin cell. The coin cell is taken out into the atmosphere, and AC impedance is measured at a frequency of 0.1 Hz to 1 MHz and a voltage of 10 mV using a Solartron electrochemical measurement system (potentiometer / galvano stud, frequency response analyzer), and the lithium ion conductivity is measured. Calculated. As a result, the lithium ion conductivity of each sample was as shown in Table 1. Samples 1-7 according to the present invention showed higher conductivity than comparative sample 8.
  • Example 2 Production and evaluation of oxide sintered body using oxygen atmosphere in second firing step
  • raw material components for preparing raw materials for firing lithium hydroxide (Kanto Chemical Co., Ltd.), lanthanum hydroxide (Shin-Etsu) Chemical Industry Co., Ltd.), zirconium oxide (Tosoh Corporation), tantalum oxide and bismuth oxide were prepared.
  • composition shown in Table 2 These powders are weighed and blended so as to have the composition shown in Table 2, and ⁇ -Al 2 O 3 is added in an amount that makes the molar ratio of Al to the garnet composition formula 0.1 (samples 9 to 11) or An amount (sample 12) of 0.025 in terms of the molar ratio of Al was added and mixed with a lyker machine to obtain a firing raw material.
  • the composition shown in Table 2 is a charged composition, and is included in a larger amount than the target composition in consideration of loss of Li during firing.
  • the charged composition is a composition that does not satisfy the charge compensation of the garnet-type crystal structure, it is understood that a composition that satisfies the charge compensation is obtained after firing due to loss of Li and / or oxygen deficiency. It should be noted that elements other than Li have virtually no loss during firing, and are basically retained after firing at the composition ratio shown in Table 2.
  • the firing raw material is placed in a magnesia crucible and heated at 600 ° C./hour in the air, and the samples 9 to 11 are held at 950 ° C. and the sample 12 is held at 900 ° C. Then, baking was performed for a total of 20 hours.
  • the powder obtained in the first baking step and cobblestone were mixed and pulverized for 3 hours using a vibration mill to obtain pulverized powder corresponding to samples 9 to 12 in Table 2.
  • the obtained powder was press-molded at about 100 MPa using a mold to obtain a molded body having a desired shape.
  • the obtained molded body was placed on a magnesia setter, and the setter was placed in a magnesia sheath and heated at 200 ° C./hour in an oxygen atmosphere of about 100% oxygen.
  • Sample 12 was held at 1050 ° C.

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Abstract

L'invention concerne un matériau céramique consistant en un matériau céramique électrolytique solide présentant une conductivité par ions lithium, ledit matériau céramique comprenant un corps fritté en oxyde, présentant une structure de type grenat ou une structure cristalline de type grenat, comprenant un constituant élémentaire principal Li, La, Zr et O et un élément de substitution comprenant au moins Bi. Suite à cette invention, une conductivité encore plus haute peut être atteinte dans une céramique électrolytique solide de type LLZ grenat ou de type grenat.
PCT/JP2013/073575 2012-09-04 2013-09-02 Matériau céramique électrolytique solide WO2014038521A1 (fr)

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JP2014170734A (ja) * 2012-12-29 2014-09-18 Murata Mfg Co Ltd 固体電解質用材料
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JP2017168395A (ja) * 2016-03-18 2017-09-21 セイコーエプソン株式会社 固体電解質及びリチウムイオン電池
WO2017159606A1 (fr) * 2016-03-18 2017-09-21 セイコーエプソン株式会社 Électrolyte solide et batterie au lithium-ion
WO2018195011A1 (fr) * 2017-04-17 2018-10-25 Corning Incorporated Composite d'électrolyte solide à grenat de lithium, articles en ruban et procédés associés
CN108736063A (zh) * 2018-06-04 2018-11-02 北京化工大学常州先进材料研究院 锡基掺铋石榴石型固体电解质材料的制备方法
WO2022065521A1 (fr) * 2021-03-31 2022-03-31 第一稀元素化学工業株式会社 Matériau de poudre céramique, procédé de production d'un matériau de poudre céramique, corps moulé, corps fritté et batterie

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JP2014170734A (ja) * 2012-12-29 2014-09-18 Murata Mfg Co Ltd 固体電解質用材料
US20160133990A1 (en) * 2014-11-11 2016-05-12 Purdue Research Foundation Solid-state electrolytes and batteries made therefrom, and methods of making solid-state electrolytes
US11201350B2 (en) * 2014-11-11 2021-12-14 Purdue Research Foundation Solid-state electrolytes and batteries made therefrom, and methods of making solid-state electrolytes
US10439250B2 (en) * 2014-11-11 2019-10-08 Purdue Research Foundation Solid-state electrolytes and batteries made therefrom, and methods of making solid-state electrolytes
JP2017168396A (ja) * 2016-03-18 2017-09-21 セイコーエプソン株式会社 固体電解質及びリチウムイオン電池
US10784534B2 (en) 2016-03-18 2020-09-22 Seiko Epson Corporation Solid electrolyte and lithium ion battery
JP2017168395A (ja) * 2016-03-18 2017-09-21 セイコーエプソン株式会社 固体電解質及びリチウムイオン電池
US10947160B2 (en) 2016-03-18 2021-03-16 Seiko Epson Corporation Solid electrolyte and lithium ion battery
WO2017159606A1 (fr) * 2016-03-18 2017-09-21 セイコーエプソン株式会社 Électrolyte solide et batterie au lithium-ion
WO2017159571A1 (fr) * 2016-03-18 2017-09-21 セイコーエプソン株式会社 Électrolyte solide et accumulateur lithium-ion
US10774004B2 (en) 2016-03-18 2020-09-15 Seiko Epson Corporation Solid electrolyte and lithium ion battery
JP2020516579A (ja) * 2017-04-17 2020-06-11 コーニング インコーポレイテッド リチウム−ガーネット固体電解質複合材料、テープ製品、及びそれらの方法
WO2018195011A1 (fr) * 2017-04-17 2018-10-25 Corning Incorporated Composite d'électrolyte solide à grenat de lithium, articles en ruban et procédés associés
US11296355B2 (en) 2017-04-17 2022-04-05 Corning Incorporated Lithium-garnet solid electrolyte composite, tape articles, and methods thereof
JP7137617B2 (ja) 2017-04-17 2022-09-14 コーニング インコーポレイテッド リチウム－ガーネット固体電解質複合材料、テープ製品、及びそれらの方法
US11749836B2 (en) 2017-04-17 2023-09-05 Corning Incorporated Lithium-garnet solid electrolyte composite, tape articles, and methods thereof
CN108736063A (zh) * 2018-06-04 2018-11-02 北京化工大学常州先进材料研究院 锡基掺铋石榴石型固体电解质材料的制备方法
WO2022065521A1 (fr) * 2021-03-31 2022-03-31 第一稀元素化学工業株式会社 Matériau de poudre céramique, procédé de production d'un matériau de poudre céramique, corps moulé, corps fritté et batterie

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