WO2021251409A1 - 固体電解質材料、固体電解質、固体電解質の製造方法および全固体電池 - Google Patents

固体電解質材料、固体電解質、固体電解質の製造方法および全固体電池 Download PDF

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WO2021251409A1
WO2021251409A1 PCT/JP2021/021835 JP2021021835W WO2021251409A1 WO 2021251409 A1 WO2021251409 A1 WO 2021251409A1 JP 2021021835 W JP2021021835 W JP 2021021835W WO 2021251409 A1 WO2021251409 A1 WO 2021251409A1
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solid electrolyte
group
compound
lithium
solid
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French (fr)
Japanese (ja)
Inventor
良輔 清
建燦 李
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Resonac Holdings Corp
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Showa Denko KK
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Priority to CN202180041262.0A priority Critical patent/CN115699216B/zh
Priority to JP2021549097A priority patent/JPWO2021251409A1/ja
Priority to US18/009,216 priority patent/US20230216085A1/en
Priority to EP21822996.1A priority patent/EP4167321A4/en
Priority to KR1020227044461A priority patent/KR20230013091A/ko
Publication of WO2021251409A1 publication Critical patent/WO2021251409A1/ja
Priority to JP2022028445A priority patent/JP2022063360A/ja
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    • H—ELECTRICITY
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    • 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
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
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    • 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
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    • C01—INORGANIC CHEMISTRY
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    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/10—Compounds containing boron and oxygen
    • C01B35/12—Borates
    • C01B35/121—Borates of alkali metal
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    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
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    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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    • 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
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
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    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • One embodiment of the present invention relates to a solid electrolyte material, a solid electrolyte, a method for producing a solid electrolyte, or an all-solid-state battery.
  • an inorganic solid electrolyte As the solid electrolyte, an inorganic solid electrolyte has attracted attention, and as the inorganic solid electrolyte, mainly oxide-based and sulfide-based solid electrolytes are known.
  • oxide-based and sulfide-based solid electrolytes are known.
  • a sulfide-based solid electrolyte When a sulfide-based solid electrolyte is used, there are advantages such as being able to manufacture a battery by cold pressing, but it is unstable with respect to humidity and harmful hydrogen sulfide gas may be generated, so it is safe. Development of oxide-based solid electrolytes is underway in terms of properties and the like.
  • Non-Patent Document 1 states that LiTa 2 PO 8 , which has a monoclinic crystal structure, has high lithium ion conductivity (total conductivity (25 ° C.): 2.5 ⁇ . It is described that 10 -4 S ⁇ cm -1) is shown.
  • Oxide-based solid electrolytes have extremely high grain boundary resistance, and in order to obtain ionic conductivity that can be used in all-solid-state batteries, not only the solid electrolyte powder is pressure-molded, but also a high-density sintered body is used. There is a need. Then, in order to obtain such a high-density sintered body, it was necessary to fire it at a high temperature of, for example, about 1100 ° C. Further, when manufacturing an all-solid-state battery using an oxide-based solid electrolyte, it is necessary to sintered the battery together with a positive electrode material, a negative electrode material, and the like in order to obtain high ionic conductivity.
  • One embodiment of the present invention provides a solid electrolyte material capable of obtaining a sintered body having sufficient ionic conductivity even when fired at a low temperature (eg, 900 ° C. or lower).
  • the configuration example of the present invention is as follows.
  • a solid electrolyte which is a sintered body of the solid electrolyte material according to any one of [1] to [7].
  • a positive electrode having a positive electrode active material and a positive electrode Negative electrode with negative electrode active material and negative electrode A solid electrolyte layer between the positive electrode and the negative electrode, Including The solid electrolyte layer comprises the solid electrolyte according to [8] or [9]. All-solid-state battery.
  • the positive electrode active material is LiM3PO 4 [M3 is one or more elements selected from the group consisting of Mn, Co, Ni, Fe, Al, Ti and V, or two elements V and O. ], LiM5VO 4 [M5 is one or more elements selected from the group consisting of Fe, Mn, Co, Ni, Al and Ti. ], Li 2 M6P 2 O 7 [M6 is one or more elements selected from the group consisting of Fe, Mn, Co, Ni, Al, Ti and V, or two elements of V and O.
  • M7 is Ti, Ge, Al, Ga and Zr. It is one or more elements selected from the group consisting of. ], Li 1 + x8 Al x8 M8 2-x8 (PO 4 ) 3 [0 ⁇ x8 ⁇ 0.8, M8 is one or more elements selected from the group consisting of Ti and Ge.
  • the negative electrode active material is LiM3PO 4 [M3 is one or more elements selected from the group consisting of Mn, Co, Ni, Fe, Al, Ti and V, or two elements V and O. ], LiM5VO 4 [M5 is one or more elements selected from the group consisting of Fe, Mn, Co, Ni, Al and Ti. ], Li 2 M6P 2 O 7 [M6 is one or more elements selected from the group consisting of Fe, Mn, Co, Ni, Al, Ti and V, or two elements of V and O.
  • M7 is Ti, Ge, Al, Ga and Zr. It is one or more elements selected from the group consisting of. ], Li 1 + x8 Al x8 M8 2-x8 (PO 4 ) 3 [0 ⁇ x8 ⁇ 0.8, M8 is one or more elements selected from the group consisting of Ti and Ge.
  • M9 is, Mg, Al, be one or more elements selected from the group consisting of Ga and Zn
  • M10 is one or more elements selected from the group consisting of Zn, Al, Ga, Si, Ge, P and Ti
  • a9 are M9.
  • Is the average valence of, and b9 is the average valence of M10.
  • a sintered body having sufficient ionic conductivity, particularly sufficient lithium ion conductivity can be obtained even when fired at a low temperature (eg, 900 ° C. or lower). Therefore, by using the solid electrolyte material according to the embodiment of the present invention, it is excellent in economic efficiency, and a solid having sufficient ionic conductivity while suppressing decomposition and alteration of other materials such as positive electrode and negative electrode materials. An all-solid-state battery containing an electrolyte can be easily produced.
  • the solid electrolyte material according to the embodiment of the present invention contains lithium, tantalum, boron, phosphorus and oxygen as constituent elements, and has the highest peak intensity among the peaks of 11 B-NMR.
  • the peak position of the peak with a large value is in the range of -15.0 to -5.0 ppm.
  • the peak position of the peak having the highest peak intensity is preferable from the viewpoint that the firing temperature for obtaining a sintered body having sufficient ionic conductivity can be further lowered. It is in the range of -13.0 to -7.0 ppm.
  • the 11 B-NMR spectrum can be obtained by the method described in the following Examples.
  • the material is preferably amorphous.
  • the fact that the material is amorphous means that no peak is observed (a broad peak is observed) in an X-ray diffraction (XRD) diagram, that is, it is observed in the range of 20 ° ⁇ 2 ⁇ ⁇ 40 °. It can be judged from the fact that the half width of the diffraction peak having the maximum intensity is larger than 0.15 °. In other words, when the half width of the diffraction peak is 0.15 ° or less, it is judged to be a crystal. Since the present material is amorphous, the solid electrolyte obtained from the present material, particularly the solid electrolyte (sintered body) obtained by firing the present material, tends to exhibit higher ionic conductivity.
  • the shape, size, and the like of the present material are not particularly limited, but are preferably in the form of particles (powder), and the average particle size (D50) of the present material is preferably 0.1 to 10 ⁇ m, more preferably 0. It is 1 to 5 ⁇ m.
  • the average particle size of the present material is within the above range, the solid electrolyte obtained from the present material, particularly the solid electrolyte (sintered body) obtained by firing the present material, tends to exhibit higher ionic conductivity. It is in.
  • the elements constituting this material are not particularly limited as long as they include lithium, tantalum, boron, phosphorus and oxygen, and are a group consisting of Bi, Nb, Zr, Ga, Sn, Hf, W, Mo, Si, Al and Ge. It may contain one or more elements selected from the above.
  • the content of the lithium element in this material is preferably 5.0 to 20.0 atomic%, more preferably 9.0, from the viewpoint that a solid electrolyte having higher lithium ion conductivity can be easily obtained. It is ⁇ 15.0 atomic%.
  • each element in this material for example, a standard powder sample containing Mn, Co, and Ni in a ratio of 1: 1: 1 as a lithium-containing transition metal oxide such as LiCoO 2 is used.
  • Auger electron spectroscopy (AES) can be measured by the absolute intensity quantification method.
  • AES Auger electron spectroscopy
  • it can be obtained by a conventionally known quantitative analysis.
  • an acid can be added to a sample for thermal decomposition, the thermal decomposition product is defined, and the content of each element in the present material can be determined using a high frequency inductively coupled plasma (ICP) emission spectrometer.
  • ICP inductively coupled plasma
  • the content of the tantalum element in this material is preferably 10.6 to 16.6 atomic%, more preferably 11.0, from the viewpoint that a solid electrolyte having higher lithium ion conductivity can be easily obtained. It is ⁇ 16.0 atomic%.
  • the content of the elemental boron in the present material is preferably 0.1 to 5.0 atomic%, more preferably, from the viewpoint that the firing temperature for obtaining a sintered body having sufficient ionic conductivity can be further lowered. Is 0.5 to 3.0 atomic%.
  • the content of the phosphorus element in this material is preferably 5.3 to 8.8 atomic%, more preferably 5.8, from the viewpoint that a solid electrolyte having higher lithium ion conductivity can be easily obtained. ⁇ 8.3 atomic%.
  • the present material contains one or more elements selected from the group consisting of Bi, Nb, Zr, Ga, Sn, Hf, W, Mo, Si, Al and Ge, each of the metal elements in the present material.
  • the content is preferably 0.1 to 5.0 atomic%, more preferably 0.1 to 3.0, from the viewpoint that a solid electrolyte having higher ionic conductivity tends to be easily obtained. Atomic%.
  • This material contains, for example, lithium, tantalum, boron, phosphorus and oxygen as constituent elements in a method (I) including a crushing step of crushing a material to be crushed containing lithium, tantalum, boron, phosphorus and oxygen as constituent elements. It is preferably produced as the component (Z).
  • the crushing step it is preferable to crush and mix the obtained material so that it becomes amorphous by a mechanochemical reaction and / or the average particle size of the material is within the above range.
  • Examples of the crushing step include a method of crushing using a roll rolling mill, a ball mill, a small diameter ball mill (bead mill), a medium stirring mill, an air flow crusher, a mortar, an automatic kneading mortar, a tank mortar, a jet mill, and the like. Be done.
  • a method of pulverizing and mixing using a ball mill or a bead mill is preferable from the viewpoint that a solid electrolyte having higher ionic conductivity can be easily obtained when a solid electrolyte is obtained from this material, and the diameter is large.
  • a method of pulverizing and mixing with a ball mill using 0.1 to 10 mm balls is more preferable.
  • the time of the crushing step is preferably 0.5 to 48 from the viewpoint that the material becomes amorphous by the mechanochemical reaction and the present material having an average particle size (D50) in the above range can be easily obtained.
  • the time more preferably 2 to 48 hours.
  • the mixture may be mixed while being pulverized while being heated, but it is usually carried out at room temperature. Further, the pulverization step may be performed in the atmosphere, but it is preferably performed in an atmosphere of nitrogen gas and / or argon gas in which the oxygen gas content is adjusted in the range of 0 to 20% by volume.
  • the raw material used for the material to be crushed is preferably an inorganic compound from the viewpoint of ease of handling.
  • the raw material may be produced and obtained by a conventionally known method, or a commercially available product may be used.
  • Examples of the material to be pulverized include a method (i) using a compound containing a lithium atom, a compound containing a tantalum atom, a compound containing a boron atom, and a compound containing a phosphorus atom. Further, in the method (i), Bi, Nb, Zr, Ga, Sn, Hf, W, Mo, Si can be lowered in order to obtain a sintered body having sufficient ionic conductivity.
  • Examples of the compound containing a lithium atom include lithium carbonate (Li 2 CO 3 ), lithium oxide (Li 2 O), lithium hydroxide (LiOH), lithium acetate (LiCH 3 COO) and hydrates thereof. .. Among these, lithium carbonate, lithium hydroxide, and lithium acetate are preferable because they are easily decomposed and reacted.
  • the compound containing a lithium atom one kind may be used, or two or more kinds may be used.
  • Examples of the compound containing a tantalum atom include tantalum pentoxide (Ta 2 O 5 ) and tantalum nitrate (Ta (NO 3 ) 5 ). Among these, tantalum pentoxide is preferable from the viewpoint of cost. As the compound containing a tantalum atom, one kind may be used, or two or more kinds may be used.
  • Examples of the compound containing a boron atom include LiBO 2 , LiB 3 O 5 , Li 2 B 4 O 7 , Li 3 B 11 O 18 , Li 3 BO 3 , Li 3 B 7 O 12 , and Li 4 B 2 O 5.
  • Li 6 B 4 O 9 Li 3-x5 B 1-x5 C x5 O 3 (0 ⁇ x5 ⁇ 1), Li 4-x6 B 2-x6 C x6 O 5 (0 ⁇ x6 ⁇ 2), Li 2.4
  • Examples thereof include Al 0.2 BO 3 , Li 2.7 Al 0.1 BO 3 , B 2 O 3 , and H 3 BO 3.
  • the compound containing a boron atom one kind may be used, or two or more kinds may be used.
  • a phosphate As the compound containing a phosphorus atom, a phosphate is preferable, and as the phosphate, diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ) and dihydrogen phosphate 1 are easy to decompose and react. Ammonium (NH 4 H 2 PO 4 ) can be mentioned. As the compound containing a phosphorus atom, one kind may be used, or two or more kinds may be used.
  • This material is selected from the group consisting of Bi, Nb, Zr, Ga, Sn, Hf, W and Mo as a method including a crushing step of crushing a material to be crushed containing lithium, tantalum, boron, phosphorus and oxygen as constituent elements.
  • the pulverization target material is a compound containing a lithium atom.
  • a method (i') using a compound containing a tantalum atom, a compound containing a boron atom, a compound containing a phosphorus atom, a compound containing the element M1 and / or a compound containing the element M2 can be mentioned.
  • the compound containing the element M1 is not particularly limited, but an inorganic compound is preferable from the viewpoint of ease of handling, and examples thereof include oxides and nitrates of M1. Among these, oxides are preferable from the viewpoint of cost.
  • the compound containing M1 one kind may be used, or two or more kinds may be used.
  • examples of the compound containing a niobium atom include Nb 2 O 5 , LiNbO 3 , LiNb 3 O 8 , and NbPO 5 .
  • the compound containing a niobium atom one kind may be used, or two or more kinds may be used.
  • examples of the compound containing a bismuth atom include LiBiO 2 , Li 3 BiO 3 , Li 4 Bi 2 O 5 , Li 2.4 Al 0.2 BiO 3 , and Bi 2 O 3 .
  • the compound containing a bismuth atom one kind may be used, or two or more kinds may be used.
  • examples of the oxide include gallium oxide (Ga 2 O 3 ) and tin oxide (SnO 2), respectively.
  • examples of the oxide include zirconium oxide (ZrO 2 ), hafnium oxide (HfO 2 ), tungsten oxide (WO 3 ), molybdenum oxide (MoO 3 ) and the like, respectively. Will be.
  • Tungous acid (H 2 WO 4 ) and molybdenum acid (H 2 MoO 4 ) can also be used.
  • the compound containing the element M2 is not particularly limited, but an inorganic compound is preferable from the viewpoint of ease of handling, and examples thereof include an oxide of M2.
  • an inorganic compound is preferable from the viewpoint of ease of handling, and examples thereof include an oxide of M2.
  • the compound containing the element M2 one kind may be used, or two or more kinds may be used.
  • the compounds containing a silicon atom include, for example, SiO 2 , Li 2 SiO 3 , Li 2 Si 2 O 5 , Li 2 Si 3 O 7 , Li 4 SiO 4 , Li 6 Si 2 O 7 , Li 8 SiO 6 .
  • the compound containing a silicon atom one kind may be used, or two or more kinds may be used.
  • examples of the oxide include germanium oxide (GeO 2 ) and aluminum oxide (Al 2 O 3), respectively.
  • the mixing ratio of the raw materials may be, for example, an amount such that the content of each constituent element in the obtained material is within the above range.
  • the compound containing the lithium atoms may be used in excess of about 10 to 20%.
  • the compound containing a phosphorus atom may be excessively used by about 0.1 to 10%.
  • each raw material may be mixed in advance before the crushing step, but in the crushing step, each raw material is crushed and mixed (crushed and mixed). Is preferable.
  • the compound (a) and the compound (b) may be mixed in advance before the pulverization step, but in the pulverization step, the compound (a) and the compound (b) are mixed. It is preferable to mix while crushing (crushing and mixing).
  • the compound (a) is a compound containing lithium, tantalum, phosphorus and oxygen as constituent elements, preferably an oxide containing these elements, and preferably a lithium ion conductive compound containing these elements. More preferred.
  • the compound (a) used in the method (ii) may be one kind or two or more kinds.
  • the compound (a) is preferably a compound having a monoclinic structure.
  • the fact that compound (a) has a monoclinic structure is determined, for example, by Rietveld analysis of the X-ray diffraction (XRD) figure of compound (a), specifically by the method of the following example. be able to.
  • XRD X-ray diffraction
  • the compound (a) specifically contains lithium, tantalum, phosphorus and oxygen as constituent elements, and is one or more selected from the group consisting of Bi, Nb, Zr, Ga, Sn, Hf, W and Mo.
  • the compound (a1) which may contain the element M1 of the above, lithium, tantalum, phosphorus and oxygen are contained as constituent elements, and further, one or more elements M2 selected from the group consisting of Si, Al and Ge are contained.
  • a good compound (a2) and the like can be mentioned.
  • the compound (a) is preferably a compound containing only lithium, tantalum, phosphorus and oxygen as constituent elements, and LiTa 2 PO 8 is more preferable. ..
  • the compound (a1) is preferably a compound in which LiTa 2 PO 8 or a part of Ta of LiTa 2 PO 8 is substituted with the element M1, and preferably has a monoclinic structure.
  • the compound (a1) is specifically composed of the composition formula Li [ 1+ (5-a) x ] Ta 2-x M1 x PO 8 [M1 is Bi, Nb, Zr, Ga, Sn, Hf, W and It is one or more elements selected from the group consisting of Mo, 0.0 ⁇ x ⁇ 1.0, and a is the average valence of M1. ] Is preferable.
  • Bi, Nb, W, and Mo are more preferable, and Bi, Nb, and W are further preferable for M1 from the viewpoint of increasing the lithium ion conductivity at the crystal grain boundaries.
  • Bi and Nb are preferable, and Bi and Nb are particularly preferable.
  • the x is preferably 0.95 or less, more preferably 0.90 or less, still more preferably 0.85 or less, still more preferably 0.80 or less, and particularly preferably 0.75 or less.
  • x is in the above range, the lithium ion conductivity at the grain boundaries tends to be high in the solid electrolyte obtained by using the compound (a).
  • the amount of Li varies according to the average valence of M1 so that the charge neutrality of the compound (a) described above can be obtained.
  • the average valence represented by a can be obtained as follows.
  • the compound (a2) is preferably a compound in which LiTa 2 PO 8 or a part of P of LiTa 2 PO 8 is substituted with the element M2, and preferably has a monoclinic structure.
  • the compound (a2) is specifically composed of the composition formula Li [1 + (5-b) y ] Ta 2 P 1-y M2 y O 8 [M2 is selected from the group consisting of Si, Al and Ge1. It is an element of species or more, 0.0 ⁇ y ⁇ 0.7, and b is the average valence of M2. ] Is preferable.
  • Si and Al are more preferable, and Si is further preferable, from the viewpoint of increasing the lithium ion conductivity at the crystal grain boundaries.
  • the y is preferably 0.65 or less, more preferably 0.60 or less, still more preferably 0.55 or less.
  • the total ion conductivity which is the total of the lithium ion conductivity in the crystal grains and at the crystal grain boundaries, tends to be high.
  • the average valence represented by b can be obtained in the same manner as the calculation method of the average valence a described above.
  • the method for producing the compound (a) is not particularly limited, and for example, a conventionally known production method such as a solid phase reaction or a liquid phase reaction can be adopted. Specific examples of the manufacturing method include a method including at least one step of mixing step and firing step.
  • the mixing step in the method for producing the compound (a) includes, for example, a compound containing a lithium atom (eg, oxide, carbon oxide), a compound containing a tantalum atom (eg, an oxide, a glass oxide), which is a raw material.
  • a compound containing a phosphorus atom eg, an ammonium salt
  • a compound containing the element M1 eg, an oxide
  • a compound containing the element M2 eg, an oxide
  • Be done as each of the raw materials, one kind may be used, or two or more kinds may be used.
  • a method of mixing the raw materials for example, a method of mixing using a roll rolling mill, a ball mill, a small diameter ball mill (bead mill), a medium stirring mill, an air flow crusher, a mortar, an automatic kneading mortar, a tank mortar, a jet mill, or the like. Can be mentioned.
  • the mixing ratio of the raw materials may be, for example, a stoichiometric ratio so as to obtain a desired composition of the compound (a).
  • the compound containing the lithium atoms may be used in excess of about 10 to 20%.
  • the compound containing a phosphorus atom may be excessively used by about 0.1 to 10%.
  • the mixing may be carried out in the atmosphere, but is preferably carried out in an atmosphere of nitrogen gas and / or argon gas having an oxygen gas content adjusted in the range of 0 to 20% by volume.
  • the mixture obtained in the mixing step is fired.
  • a crushing step using a ball mill, a mortar or the like may be provided for the purpose of crushing or reducing the particle size of the baked product obtained in the baking step.
  • a reaction intermediate may be present in the first firing. In this case, it is preferable to perform the first firing, perform the pulverization step, and then further perform the firing step.
  • the firing step may be performed in the atmosphere, but it is preferably performed in the atmosphere of nitrogen gas and / or argon gas in which the oxygen gas content is adjusted in the range of 0 to 20% by volume.
  • the firing temperature is preferably 800 to 1200 ° C, more preferably 950 to 1100 ° C, and even more preferably 950 to 1000 ° C, although it depends on the firing time.
  • the calcination temperature is within the above range, lithium atoms are less likely to flow out of the system, and the compound (a) having high ionic conductivity tends to be easily obtained.
  • the firing time (total firing time when the firing step is performed several times) is preferably 1 to 16 hours, more preferably 3 to 12 hours, although it depends on the firing temperature.
  • the firing time is within the above range, lithium atoms are less likely to flow out of the system, and a compound having high ionic conductivity tends to be easily obtained.
  • the calcined product obtained after the calcining process is left in the atmosphere, it may absorb moisture or react with carbon dioxide to deteriorate. Therefore, it is preferable that the calcined product obtained after the calcining step is transferred to a dehumidified inert gas atmosphere and stored when the temperature drops to 200 ° C. or lower after the calcining step.
  • the boron compound (b) is a compound different from the compound (a).
  • the compound (b) used in the method (ii) may be one kind or two or more kinds.
  • the compound (b) is preferably an inorganic compound, more preferably a compound containing lithium or hydrogen as a constituent element, and further preferably a composite oxide containing lithium as a constituent element.
  • the compound (b) may be produced and obtained by a conventionally known method, or a commercially available product may be used.
  • the compound (b) is preferably a crystalline compound.
  • the fact that compound (b) is a crystalline compound can be determined, for example, from the X-ray diffraction (XRD) figure of compound (b).
  • Examples of the compound (b) include LiBO 2 , LiB 3 O 5 , Li 2 B 4 O 7 , Li 3 B 11 O 18 , Li 3 BO 3 , Li 3 B 7 O 12 , Li 4 B 2 O 5 , and so on.
  • Li 6 B 4 O 9 Li 3-x5 B 1-x5 C x5 O 3 (0 ⁇ x5 ⁇ 1), Li 4-x6 B 2-x6 C x6 O 5 (0 ⁇ x6 ⁇ 2), Li 2.4 Al 0.2 BO 3 , Li 2.7 Al 0.1 BO 3 , B 2 O 3 , and H 3 BO 3 .
  • the method for producing the compound (b) is not particularly limited, and for example, a conventionally known production method such as a solid phase reaction or a liquid phase reaction can be adopted. Specific examples of the manufacturing method include a method including a mixing step and a firing step. A commercially available product may be used as the compound (b).
  • the mixing step for example, in the case of producing a composite oxide containing lithium as a constituent element, a compound containing a lithium atom and a compound containing a boron atom, which are raw materials, are mixed. Depending on the type of compound (b), this mixing step may not be performed.
  • the compound containing a lithium atom is not particularly limited, but an inorganic compound is preferable from the viewpoint of ease of handling, and examples of the inorganic compound containing a lithium atom include lithium carbonate (Li 2 CO 3 ) and lithium oxide (Li 2 O). ), Lithium hydroxide (LiOH), lithium acetate (LiCH 3 COO) and hydrates thereof. Among these, lithium carbonate is preferable because it is easily decomposed and reacted. It is also preferable to use lithium hydroxide monohydrate (LiOH ⁇ H 2 O). As the compound containing a lithium atom, one kind may be used, or two or more kinds may be used.
  • the compound containing a boron atom is not particularly limited, but an inorganic compound is preferable from the viewpoint of ease of handling, and examples of the inorganic compound containing a boron atom include boric acid (H 3 BO 3 ) and boron oxide (B 2 O). 3 ) can be mentioned. Among these, boric acid is preferable. As the compound containing a boron atom, one kind may be used, or two or more kinds may be used.
  • a method of mixing the raw materials for example, a method of mixing using a roll rolling mill, a ball mill, a small diameter ball mill (bead mill), a medium stirring mill, an air flow crusher, a mortar, an automatic kneading mortar, a tank mortar, a jet mill, or the like. Can be mentioned.
  • the mixing ratio of the raw materials may be, for example, a stoichiometric ratio so as to obtain a desired composition of the compound (b).
  • the compound containing the lithium atoms may be used in excess of about 10 to 20%.
  • the mixing may be carried out in the atmosphere, but is preferably carried out in an atmosphere of nitrogen gas and / or argon gas having an oxygen gas content adjusted in the range of 0 to 20% by volume.
  • the firing step the mixture obtained in the mixing step is fired.
  • a crushing step using a ball mill, a mortar or the like may be provided for the purpose of crushing or reducing the particle size of the baked product obtained in the baking step.
  • the firing step may be performed in the atmosphere, but it is preferably performed in the atmosphere of nitrogen gas and / or argon gas in which the oxygen gas content is adjusted in the range of 0 to 20% by volume.
  • the firing temperature is preferably 400 to 1000 ° C, more preferably 500 to 900 ° C, although it depends on the firing time. When the firing temperature is within the above range, lithium atoms are less likely to flow out of the system, and the desired compound (b) tends to be easily obtained.
  • the firing time (total firing time when the firing step is performed several times) is preferably 1 to 48 hours, more preferably 3 to 24 hours, although it depends on the firing temperature.
  • the firing time is within the above range, the lithium atom does not easily flow out of the system, and the desired compound (b) tends to be easily obtained.
  • the calcined product obtained after the calcining process is left in the atmosphere, it may absorb moisture or react with carbon dioxide to deteriorate. Therefore, it is preferable that the calcined product obtained after the calcining step is transferred to a dehumidified inert gas atmosphere and stored when the temperature drops to 200 ° C. or lower after the calcining step.
  • the compound (a) and the compound (b) in an amount such that the content of each constituent element in the obtained material is within the above range.
  • the compound (c) is a compound containing lithium, tantalum, boron, phosphorus and oxygen as constituent elements, and is preferably an oxide containing these elements, and is a lithium ion conductive compound containing these elements. Is more preferable.
  • Compound (c) may contain one or more elements selected from the group consisting of Bi, Nb, Zr, Ga, Sn, Hf, W, Mo, Si, Al and Ge.
  • the compound (c) is preferably a compound having a monoclinic structure.
  • the fact that compound (c) has a monoclinic structure is determined, for example, by Rietveld analysis of the X-ray diffraction (XRD) figure of compound (c), specifically by the method of the following example. be able to.
  • XRD X-ray diffraction
  • the method for producing the compound (c) is not particularly limited, and for example, a conventionally known production method such as a solid phase reaction or a liquid phase reaction can be adopted. Specific examples of the manufacturing method include a method including at least one step of mixing step and firing step.
  • Examples of the mixing step in the method for producing the compound (c) include a compound containing a lithium atom (eg, oxide, hydroxide, carbon oxide) and a compound containing a tantalum atom (eg, an oxide, which are raw materials). Examples thereof include a step of mixing a compound containing a glass oxide), a compound containing a boron atom (eg, an oxide), and a compound containing a phosphorus atom (eg, an ammonium salt). As the compound containing a boron atom, the compound (b) may be used. As each of the raw materials, one kind may be used, or two or more kinds may be used.
  • a lithium atom eg, oxide, hydroxide, carbon oxide
  • a tantalum atom eg, an oxide, which are raw materials. Examples thereof include a step of mixing a compound containing a glass oxide), a compound containing a boron atom (eg, an oxide), and a compound containing a
  • the mixing ratio of the raw materials may be, for example, an amount such that the content of each constituent element in the obtained material is within the above range.
  • the compound containing the lithium atoms may be used in excess of about 10 to 20%.
  • the compound containing a phosphorus atom may be excessively used by about 0.1 to 1.0%.
  • Examples of the mixing method of the raw materials and the conditions (temperature, atmosphere, etc.) at the time of mixing include the same methods and conditions as the mixing step at the time of producing the compound (a).
  • the mixture obtained in the mixing step is fired.
  • a crushing step using a ball mill, a dairy pot, or the like may be provided for the purpose of crushing or reducing the particle size of the baked product obtained in the baking step, but the compound (c).
  • the reaction rate of phase formation is high, so that the desired compound (c) can be produced in one firing step, so that the desired compound (c) can be produced in one firing step. It is preferable to produce the compound (c).
  • Examples of the conditions (temperature, time, atmosphere, etc.) in the firing step include the same conditions as in the firing step when producing the compound (a), and the fired product obtained after the firing step is a compound. For the same reason as in the production of (a), it is preferable to transfer and store the compound (a) in a dehumidified inert gas atmosphere as in the case of producing the compound (a).
  • the solid electrolyte according to one embodiment of the present invention (hereinafter, also referred to as “the present electrolyte”) is preferably a sintered body of the present material obtained by using the present material and obtained by firing the present material. ..
  • the total ionic conductivity of the sintered body of this material obtained by firing this material at 850 ° C. or higher and 900 ° C. or lower is preferably 2.00 ⁇ 10 -4 S ⁇ cm -1 or higher, more preferably 4.00. ⁇ 10 -4 S ⁇ cm -1 or more.
  • the total ionic conductivity of the sintered body of this material obtained by firing this material at 750 ° C. or higher and lower than 850 ° C. is preferably 1.00 ⁇ 10 -4 S ⁇ cm -1 or higher, more preferably 2.00. ⁇ 10 -4 S ⁇ cm -1 or more.
  • the total ionic conductivity of the sintered body of this material obtained by firing this material at 650 ° C or higher and lower than 700 ° C is preferably 1.00 ⁇ 10 -5 S ⁇ cm -1 or higher, more preferably 2.00. ⁇ 10 -5 S ⁇ cm -1 or more.
  • the total ionic conductivity can be measured by the method described in the following Examples.
  • the method for producing the present electrolyte preferably includes a step A of calcining the present material, and more preferably a method of molding the present material and then calcining the material to obtain a sintered body.
  • the firing temperature in the step A is preferably 500 to 900 ° C, more preferably 600 to 850 ° C, and even more preferably 650 to 850 ° C. Since this material is used, a sintered body having sufficient ionic conductivity can be obtained even when fired at such a low temperature.
  • the firing time in the step A is preferably 12 to 144 hours, more preferably 48 to 96 hours, although it depends on the firing temperature.
  • the firing time is within the above range, a sintered body having sufficient ionic conductivity can be obtained even when fired at a low temperature.
  • the firing in the step A may be carried out in the atmosphere, but it is preferably carried out in the atmosphere of nitrogen gas and / or argon gas in which the oxygen gas content is adjusted in the range of 0 to 20% by volume. Further, the firing in the step A may be performed in a reducing gas atmosphere such as a nitrogen-hydrogen mixed gas containing a reducing gas such as hydrogen gas. The ratio of the hydrogen gas contained in the nitrogen-hydrogen mixed gas is, for example, 1 to 10% by volume. As the reducing gas, ammonia gas, carbon monoxide gas, or the like may be used in addition to hydrogen gas.
  • the step A it is preferable to fire the molded product obtained by molding the present material from the viewpoint that a solid electrolyte (sintered body) having higher ionic conductivity can be easily obtained, and the present material is press-molded. It is more preferable to bake the molded product.
  • the pressure for press-molding the present material is not particularly limited, but is preferably 50 to 500 MPa, more preferably 100 to 400 MPa.
  • the shape of the molded body obtained by press-molding the present material is not particularly limited, but it is preferably a shape suitable for the use of the sintered body (solid electrolyte) obtained by firing the molded body.
  • components other than the present material may be used.
  • the other component include conventionally known materials used for solid electrolytes of all-solid-state batteries, and examples of the lithium ion conductive compound include lithium ion conductive materials having structures such as NASICON type and LISION type. Be done.
  • the other components one kind may be used, or two or more kinds may be used.
  • the amount of the other component used is preferably 50% by mass or less, more preferably 30% by mass or less, based on 100% by mass of the total with the present material, and it is preferable not to use the other component.
  • the all-solid-state battery (hereinafter, also referred to as “the battery”) according to the embodiment of the present invention is a positive electrode having a positive electrode active material, a negative electrode having a negative electrode active material, and a solid electrolyte between the positive electrode and the negative electrode.
  • the solid electrolyte layer contains the present electrolyte.
  • the present battery may be a primary battery or a secondary battery, but is preferably a secondary battery from the viewpoint of more exerting the effect of the present invention, and is preferably a lithium ion secondary battery. Is more preferable.
  • the structure of the present battery is not particularly limited as long as a solid electrolyte layer is included between the positive electrode, the negative electrode, and the positive electrode and the negative electrode, and may be a so-called thin film type, laminated type, or bulk type.
  • the solid electrolyte layer is not particularly limited as long as it contains the present electrolyte, and may contain conventionally known additives used for the solid electrolyte layer of the all-solid-state battery, if necessary, but it is preferably made of the present electrolyte.
  • the thickness of the solid electrolyte layer may be appropriately selected depending on the structure (thin film type or the like) of the battery to be formed, but is preferably 50 nm to 1000 ⁇ m, more preferably 100 nm to 100 ⁇ m.
  • the positive electrode is not particularly limited as long as it has a positive electrode active material, but a positive electrode having a positive electrode current collector and a positive electrode active material layer is preferable.
  • the positive electrode active material layer is not particularly limited as long as it contains a positive electrode active material, but preferably contains a positive electrode active material and a solid electrolyte, and may further contain additives such as a conductive auxiliary agent and a sintering aid. ..
  • the thickness of the positive electrode active material layer may be appropriately selected depending on the structure (thin film type, etc.) of the battery to be formed, but is preferably 10 to 200 ⁇ m, more preferably 30 to 150 ⁇ m, and further preferably 50 to 100 ⁇ m. ..
  • the positive positive active material examples include LiCo oxide, LiNiCo oxide, LiNiCoMn oxide, LiNiMn oxide, LiMn oxide, LiMn-based spinel, LiMnNi oxide, LiMnAl oxide, LiMnMg oxide, and LiMnCo oxide.
  • LiMnFe oxide, LiMnZn oxide, LiCrNiMn oxide, LiCrMn oxide, lithium titanate, lithium phosphate metal oxide, transition metal oxide, titanium sulfide, graphite, hard carbon, transition metal-containing lithium nitride, silicon oxide Examples thereof include lithium silicate, lithium metal, lithium alloy, Li-containing solid solution, and lithium-storable metal-to-metal compound.
  • LiNiCoMn oxide, LiNiCo oxide, and LiCo oxide are preferable, and LiNiCoMn oxide is more preferable, from the viewpoint of increasing the capacity and the like.
  • the surface of the positive electrode active material may be coated with lithium niobate, lithium phosphate, lithium borate, or the like, which are ionic conductive oxides.
  • the positive electrode active material used for the positive electrode active material layer may be one kind or two or more kinds.
  • Preferable examples of the positive electrode active material are LiM3PO 4 [M3 is one or more elements selected from the group consisting of Mn, Co, Ni, Fe, Al, Ti and V, or two elements V and O. .. ], LiM5VO 4 [M5 is one or more elements selected from the group consisting of Fe, Mn, Co, Ni, Al and Ti. ], Li 2 M6P 2 O 7 [M6 is one or more elements selected from the group consisting of Fe, Mn, Co, Ni, Al, Ti and V, or two elements of V and O.
  • M7 is Ti, Ge, Al, Ga and Zr. It is one or more elements selected from the group consisting of. ], Li 1 + x8 Al x8 M8 2-x8 (PO 4 ) 3 [0 ⁇ x8 ⁇ 0.8, M8 is one or more elements selected from the group consisting of Ti and Ge.
  • LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , Li 2 CoP 2 O 7 , Li 3 V 2 (PO 4 ) 3 , Li 3 Fe 2 ( PO 4 ) 3 , LiNi 0.5 Mn 1.5 O 4 , and Li 4 Ti 5 O 12 are also mentioned.
  • the positive electrode active material is preferably in the form of particles.
  • the 50% diameter in the volume-based particle size distribution is preferably 0.1 to 30 ⁇ m, more preferably 0.3 to 20 ⁇ m, still more preferably 0.4 to 10 ⁇ m, and particularly preferably 0.5 to 3 ⁇ m.
  • the ratio of the length of the major axis to the length of the minor axis (length of the major axis / length of the minor axis), that is, the aspect ratio of the positive electrode active material is preferably less than 3, more preferably less than 2.
  • the positive electrode active material may form secondary particles.
  • the 50% diameter in the number-based particle size distribution of the primary particles is preferably 0.1 to 20 ⁇ m, more preferably 0.3 to 15 ⁇ m, still more preferably 0.4 to 10 ⁇ m, and particularly preferably 0.5 to 2 ⁇ m. Is.
  • the content of the positive electrode active material in the positive electrode active material layer is preferably 20 to 80% by volume, more preferably 30 to 70% by volume.
  • the positive electrode active material functions favorably, and a battery having a high energy density tends to be easily obtained.
  • the solid electrolyte that can be used for the positive electrode active material layer is not particularly limited, and a conventionally known solid electrolyte can be used, but the present electrolyte is used from the viewpoint of further exerting the effect of the present invention. Is preferable.
  • the solid electrolyte used for the positive electrode active material layer may be one kind or two or more kinds.
  • the conductive auxiliary agent include metal materials such as Ag, Au, Pd, Pt, Cu and Sn, and carbon materials such as acetylene black, ketjen black, carbon nanotubes and carbon nanofibers.
  • metal materials such as Ag, Au, Pd, Pt, Cu and Sn
  • carbon materials such as acetylene black, ketjen black, carbon nanotubes and carbon nanofibers.
  • a compound similar to the compound (b) is preferable.
  • the additive used for the positive electrode active material layer may be one kind or two or more kinds, respectively.
  • the positive electrode current collector is not particularly limited as long as the material is one that conducts electrons without causing an electrochemical reaction.
  • the material of the positive electrode current collector include simple substances of metals such as copper, aluminum, and iron, alloys containing these metals, and conductive metal oxides such as antimony-doped tin oxide (ATO) and tin-doped indium oxide (ITO). Can be mentioned.
  • ATO antimony-doped tin oxide
  • ITO tin-doped indium oxide
  • a current collector having a conductive adhesive layer provided on the surface of the conductor can also be used.
  • the conductive adhesive layer include a layer containing a granular conductive material, a fibrous conductive material, and the like.
  • the negative electrode is not particularly limited as long as it has a negative electrode active material, but a negative electrode having a negative electrode current collector and a negative electrode active material layer is preferable.
  • the negative electrode active material layer is not particularly limited as long as it contains the negative electrode active material, but preferably contains the negative electrode active material and the solid electrolyte, and may further contain additives such as a conductive auxiliary agent and a sintering aid. ..
  • the thickness of the negative electrode active material layer may be appropriately selected according to the structure (thin film type, etc.) of the battery to be formed, but is preferably 10 to 200 ⁇ m, more preferably 30 to 150 ⁇ m, and further preferably 50 to 100 ⁇ m. ..
  • Negative electrode active material examples include lithium alloy, metal oxide, graphite, hard carbon, soft carbon, silicon, silicon alloy, silicon oxide SiO n (0 ⁇ n ⁇ 2), and silicon / carbon composite material.
  • Examples thereof include a composite material containing a silicon domain in the pores of porous carbon, lithium titanate, and graphite coated with lithium titanate.
  • a silicon / carbon composite material or a composite material containing a silicon domain in the pores of porous carbon is preferable because it has a high specific capacity and can increase the energy density and the battery capacity.
  • the silicon domain is amorphous, the size of the silicon domain is 10 nm or less, and the pores derived from the porous carbon are present in the vicinity of the silicon domain. It is a composite material to be included.
  • the negative electrode active material are LiM3PO 4 [M3 is one or more elements selected from the group consisting of Mn, Co, Ni, Fe, Al, Ti and V, or two elements V and O. .. ], LiM5VO 4 [M5 is one or more elements selected from the group consisting of Fe, Mn, Co, Ni, Al and Ti. ], Li 2 M6P 2 O 7 [M6 is one or more elements selected from the group consisting of Fe, Mn, Co, Ni, Al, Ti and V, or two elements of V and O.
  • M7 is Ti, Ge, Al, Ga and Zr. It is one or more elements selected from the group consisting of. ], Li 1 + x8 Al x8 M8 2-x8 (PO 4 ) 3 [0 ⁇ x8 ⁇ 0.8, M8 is one or more elements selected from the group consisting of Ti and Ge.
  • M9 is, Mg, Al, be one or more elements selected from the group consisting of Ga and Zn
  • M10 is one or more elements selected from the group consisting of Zn, Al, Ga, Si, Ge, P and Ti
  • a9 are M9.
  • Is the average valence of, and b9 is the average valence of M10.
  • LiNb 2 O 7 Li 4 Ti 5 O 12
  • Li 4 Ti 5 PO 12 Li 4 Ti 5 PO 12
  • TiO 2 LiSi, and graphite.
  • the negative electrode active material is preferably in the form of particles.
  • the 50% diameter in the volume-based particle size distribution, the aspect ratio, and the 50% diameter in the number-based particle size distribution of the primary particles when the negative electrode active material forms the secondary particles are in the same range as the positive electrode active material. It is preferable to have.
  • the content of the negative electrode active material in the negative electrode active material layer is preferably 20 to 80% by volume, more preferably 30 to 70% by volume.
  • the negative electrode active material functions favorably, and a battery having a high energy density tends to be easily obtained.
  • the solid electrolyte that can be used for the negative electrode active material layer is not particularly limited, and a conventionally known solid electrolyte can be used. However, the present electrolyte is used from the viewpoint of further exerting the effect of the present invention. Is preferable.
  • the solid electrolyte used for the negative electrode active material layer may be one kind or two or more kinds.
  • the conductive auxiliary agent include metal materials such as Ag, Au, Pd, Pt, Cu and Sn, and carbon materials such as acetylene black, ketjen black, carbon nanotubes and carbon nanofibers.
  • metal materials such as Ag, Au, Pd, Pt, Cu and Sn
  • carbon materials such as acetylene black, ketjen black, carbon nanotubes and carbon nanofibers.
  • a compound similar to the compound (b) is preferable.
  • the additive used for the negative electrode active material layer may be one kind or two or more kinds, respectively.
  • the negative electrode current collector the same current collector as the positive electrode current collector can be used.
  • the all-solid-state battery can be formed, for example, by a known powder molding method.
  • the positive electrode current collector, the powder for the positive electrode active material layer, the powder for the solid electrolyte layer, the powder for the negative electrode active material layer, and the negative electrode current collector are superposed in this order, and they are simultaneously powder-molded. Formation of each layer of positive electrode active material layer, solid electrolyte layer and negative electrode active material layer, and connection between positive electrode current collector, positive electrode active material layer, solid electrolyte layer, negative electrode active material layer and negative electrode current collector, respectively. Can be done at the same time.
  • the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer may be powder-molded, respectively. However, when an all-solid-state battery is produced using each of the obtained layers, each layer is pressed. It is preferable to bake.
  • the all-solid-state battery can also be manufactured by, for example, the following method.
  • a paste for forming each layer is prepared by appropriately mixing a solvent, a resin, etc. with the material for forming the positive electrode active material layer, the material for forming the solid electrolyte layer, and the material for forming the negative electrode active material layer, and the paste is used as a base. By applying it on a sheet and drying it, a green sheet for a positive electrode active material layer, a green sheet for a solid electrolyte layer, and a green sheet for a negative electrode active material layer are produced.
  • the green sheet for the positive electrode active material layer, the green sheet for the solid electrolyte layer, and the green sheet for the negative electrode active material layer from which the base sheet was peeled off from each green sheet were sequentially laminated, heat-pressed at a predetermined pressure, and then placed in a container.
  • a laminated structure is produced by enclosing and pressurizing with a hot isotropic press, a cold isotropic press, a hydrostatic press, or the like.
  • the laminated structure is degreased at a predetermined temperature and then fired to prepare a laminated sintered body.
  • the firing temperature in this firing process is preferably the same as the firing temperature in the step A.
  • an all-solid-state battery is formed by forming a positive electrode current collector and a negative electrode current collector on both main surfaces of the laminated sintered body by a sputtering method, a vacuum vapor deposition method, application of a metal paste, or dipping. It can also be made.
  • the obtained mixture is placed in an alumina boat, and the temperature is raised to 500 ° C. under the condition of a heating rate of 10 ° C./min in an atmosphere of air (flow rate: 100 mL / min) using a rotary firing furnace (manufactured by Motoyama Co., Ltd.). Then, it was fired at 500 ° C. for 2 hours to obtain a primary fired product.
  • the obtained primary calcined product is crushed and mixed in a Menou mortar for 15 minutes, the obtained mixture is placed in an alumina boat, and an air (flow rate: 100 mL / min) atmosphere is used in a rotary calcining furnace (manufactured by Motoyama Co., Ltd.). Below, the temperature was raised to 630 ° C. under the condition of a temperature rising rate of 10 ° C./min, and firing was performed at 630 ° C. for 24 hours to obtain a secondary fired product (Li 4 B 2 O 5). The obtained secondary calcined product was cooled to room temperature, then taken out from the rotary calcining furnace, transferred to a dehumidified nitrogen gas atmosphere, and stored.
  • Example 1 An appropriate amount of toluene was added to tantalum pentoxide (Ta 2 O 5 ) (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9%) and pulverized for 2 hours using a zirconia ball mill (zirconia ball: diameter 3 mm). ..
  • lithium carbonate Li 2 CO 3
  • the pulverized tantalum pentoxide Ti 2 O 5
  • Li 4 B 2 O obtained in the above-mentioned Synthesis Example 1 5
  • diammonium hydrogen phosphate (NH 4 ) 2 HPO 4 )
  • lithium, tantalum, boron and phosphorus atomic weight ratio Li: Ta: B: P)
  • the amount of diammonium hydrogen phosphate is 1.065 times the phosphorus atomic weight in Table 1.
  • Example 2 An appropriate amount of toluene was added to niobium pentoxide (Nb 2 O 5 ) (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9%) and pulverized for 2 hours using a zirconia ball mill (zirconia ball: diameter 3 mm). ..
  • the ground niobium pentoxide (Nb 2 O 5 ) was further used, and the atomic number ratios of lithium, tantalum, niobium, boron and phosphorus (Li: Ta: Nb: B: P) were shown in Table 1.
  • An amorphous solid electrolyte material was obtained by producing in the same manner as in Example 1 except that each raw material powder was used so as to pass.
  • Example 3 silicon oxide (SiO 2 ) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.9%) was further used, and the atomic number ratio of lithium, tantalum, boron, phosphorus and silicon (Li: Ta:: B: P: Si) was prepared in the same manner as in Example 1 except that each raw material powder was used so as to be as shown in Table 1, to obtain an amorphous solid electrolyte material.
  • SiO 2 silicon oxide
  • boron, phosphorus and silicon Li: Ta:: B: P: Si
  • Lithium carbonate Li 2 CO 3
  • tantalum pentoxide Ta 2 O 5
  • Diammonium hydrogen phosphate (NH 4 ) 2 HPO 4 )
  • lithium, tantalum and phosphorus atomic weight ratios (Li: Ta: P) are as shown in Table 1.
  • lithium carbonate is weighed so that the amount is 1.1 times the lithium atomic weight in Table 1, and further, it is added in the firing step.
  • diammonium hydrogen phosphate was weighed so that the amount of lithium atom in Table 1 was multiplied by 1.065.
  • An appropriate amount of toluene was added to each of the weighed raw material powders, and the mixture was pulverized and mixed for 2 hours using a zirconia ball mill (zirconia balls: diameter 1 mm).
  • the obtained mixture is placed in an alumina boat, and the temperature is raised to 1000 ° C. under the condition of a heating rate of 10 ° C./min in an atmosphere of air (flow rate: 100 mL / min) using a rotary firing furnace (manufactured by Motoyama Co., Ltd.). Then, it was calcined at 1000 ° C. for 4 hours to obtain a primary calcined product.
  • the obtained primary calcined product is crushed and mixed in a Menou mortar for 15 minutes, the obtained mixture is placed in an alumina boat, and an air (flow rate: 100 mL / min) atmosphere is used in a rotary calcining furnace (manufactured by Motoyama Co., Ltd.). Below, the temperature was raised to 1000 ° C. under the condition of a heating rate of 10 ° C./min, and firing was performed at 1000 ° C. for 1 hour to obtain a secondary fired product.
  • lithium carbonate is weighed so as to be 1.1 times the lithium atomic weight in Table 1, and further suppresses the formation of by-products in the firing step.
  • diammonium hydrogen phosphate was weighed so that the amount of lithium atom in Table 1 was multiplied by 1.065.
  • An appropriate amount of toluene was added to each of the weighed raw material powders, and the mixture was pulverized and mixed for 2 hours using a zirconia ball mill (zirconia balls: diameter 1 mm).
  • the obtained mixture is placed in an alumina boat, and the temperature is raised to 1000 ° C. under the condition of a heating rate of 10 ° C./min in an atmosphere of air (flow rate: 100 mL / min) using a rotary firing furnace (manufactured by Motoyama Co., Ltd.). Then, it was calcined at 1000 ° C. for 4 hours to obtain a primary calcined product.
  • the obtained primary calcined product is crushed and mixed in a Menou mortar for 15 minutes, the obtained mixture is placed in an alumina boat, and an air (flow rate: 100 mL / min) atmosphere is used in a rotary calcining furnace (manufactured by Motoyama Co., Ltd.). Below, the temperature was raised to 1000 ° C. under the condition of a heating rate of 10 ° C./min, and firing was performed at 1000 ° C. for 1 hour to obtain a secondary fired product.
  • Table 1 shows the atomic number ratios (Li: Ta: B: P) of lithium, tantalum, boron, and phosphorus of the obtained secondary fired product and the Li 4 B 2 O 5 obtained in the above-mentioned Synthesis Example 1.
  • 11 B-NMR> An 11 B-NMR spectrum of the obtained solid electrolyte material was obtained by using a device in which a 4 mm CP / MAS probe was attached to a nuclear magnetic resonance spectroscope (NMR; AV500NMR manufactured by Bruker). Specifically, the measurement temperature was set to room temperature, and the measurement was performed by a single pulse method under the conditions of a 90 ° pulse of 4 ⁇ s and a magic angle spinning speed of 10 kHz. The measurement range was -305 to 290 ppm. For the chemical shift, boric acid (H 3 BO 3 ) was used as an external standard (0.3 ppm).
  • XRD ⁇ Powder X-ray diffraction
  • the obtained XRD figure can be obtained from the known analysis software RIETAN-FP (creator; Fujio Izumi's homepage "RIETAN-FP / VENUS system distribution file" (http://fujioizumi.verse.jp/download/download.html)).
  • the crystal structure was confirmed by performing a Rietbelt analysis using (available).
  • Example 1 and Comparative Example 2 The XRD figures of the solid electrolyte materials obtained in Example 1 and Comparative Example 2 are shown in FIGS. 2 and 3, respectively.
  • Table 1 the peak cannot be confirmed as in FIG. 2 (it is a broad peak), and the case where it is amorphous is regarded as “amorphous”, and the range of 20 ° ⁇ 2 ⁇ ⁇ 40 ° is defined as shown in FIG.
  • ⁇ Making pellets> By applying a pressure of 40 MPa with a hydraulic press to the obtained solid electrolyte material using a tablet molding machine, a disk-shaped molded body having a diameter of 10 mm and a thickness of 1 mm is formed, and then CIP (cold hydrostatic isotropic pressure pressing) is performed. ), A pellet was prepared by applying a pressure of 300 MPa to the disk-shaped molded body.
  • ⁇ Total conductivity> By forming gold layers on both sides of the obtained sintered body using a sputtering machine, measurement pellets for ionic conductivity evaluation were obtained. The obtained measurement pellets were kept in a constant temperature bath at 25 ° C. for 2 hours before measurement. Next, at 25 ° C., AC impedance measurement was performed in a frequency range of 1 Hz to 10 MHz using an impedance analyzer (manufactured by Solartron Analytical Co., Ltd., model number: 1260 A) under the condition of an amplitude of 25 mV.
  • an impedance analyzer manufactured by Solartron Analytical Co., Ltd., model number: 1260 A
  • the obtained impedance spectrum is fitted in an equivalent circuit using the equivalent circuit analysis software ZView attached to the device to obtain each lithium ion conductivity in the crystal grain and at the grain boundary, and the total conduction is obtained by totaling these. The degree was calculated. The results are shown in Table 1. The total conductivity of the sintered body obtained by firing at 650 ° C. using the solid electrolyte material obtained in Comparative Example 1 was too low to obtain a measured value.
  • the solid electrolyte material in 1 can obtain a sintered body having sufficient total conductivity even when fired at a low temperature of 900 ° C. or lower.

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PCT/JP2021/021835 2020-06-10 2021-06-09 固体電解質材料、固体電解質、固体電解質の製造方法および全固体電池 Ceased WO2021251409A1 (ja)

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