WO2015079509A1 - Lithium ion-conductive oxide and electrical storage device - Google Patents

Lithium ion-conductive oxide and electrical storage device Download PDF

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WO2015079509A1
WO2015079509A1 PCT/JP2013/081832 JP2013081832W WO2015079509A1 WO 2015079509 A1 WO2015079509 A1 WO 2015079509A1 JP 2013081832 W JP2013081832 W JP 2013081832W WO 2015079509 A1 WO2015079509 A1 WO 2015079509A1
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lithium ion
conductive oxide
lithium
ion conductive
oxygen
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PCT/JP2013/081832
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French (fr)
Japanese (ja)
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孝博 山木
純 川治
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株式会社日立製作所
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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
    • C01G25/00—Compounds of zirconium
    • C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
    • 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
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the present invention relates to lithium ion conductive oxides and storage devices.
  • a lithium ion secondary battery is an electricity storage device having two electrode layers containing an active material capable of absorbing and desorbing lithium ions, and an electrolyte for conducting lithium ions interposed therebetween.
  • Lithium ion secondary batteries are characterized by high volumetric energy density and weight energy density as compared with other secondary batteries. Therefore, it is widely used as a power source for portable devices such as mobile phones and notebook computers. Furthermore, application to industrial applications such as power supplies for mobile units such as hybrid vehicles and electric vehicles and power supplies for power generation systems such as solar power generation and wind power generation is also in progress.
  • lithium ion secondary batteries currently put to practical use use an electrolyte solution using a flammable organic solvent as an electrolyte. Therefore, there is a risk of liquid leakage or ignition. Therefore, a highly safe lithium ion secondary battery with less risk is desired.
  • the ceramic electrolyte material is, for example, a sulfide-based material containing a lithium-sulfur bond. It is characterized in that the atomic radius of sulfur is large and the polarizability is high, so that it is excellent in lithium conductivity and easily deformed by an external pressure, so that the contact between the electrolyte and the electrode is excellent.
  • sulfides are unstable in the atmosphere, and there are problems in production and use, such as generation of hydrogen sulfide by absorption of water.
  • the ceramic electrolyte material is an oxide material which is stable in the atmosphere and is excellent in heat resistance.
  • a phosphate-based material containing a lithium-oxygen-phosphorus bond there is a phosphate-based material containing a lithium-oxygen-phosphorus bond.
  • NASICON-type glass ceramics Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 ; LAGP and Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 are known.
  • these phosphoric acid materials have problems in reduction resistance, and can not be used on the negative electrode side which is a reduction environment.
  • lithium ion conductive oxides having lithium, lanthanum and zirconium as main constituent elements have been reported.
  • This material is excellent in reduction resistance, is stable even in contact with lithium, and can be used at a site where it is in contact with a negative electrode. That is, since they are excellent in chemical stability, they are suitable as solid electrolytes for all solid lithium secondary batteries excellent in high temperature durability. However, its lithium ion conductivity was not always sufficient.
  • Patent Document 1 the oxide mainly containing lithium, lanthanum and zirconium takes Li 7 La 3 Zr 2 O 12 as a basic chemical composition, and has a so-called garnet type structure of cubic crystal as its crystal structure. By taking it, it is stated that it exhibits excellent lithium ion conductivity.
  • Patent Document 2 and Patent Document 3 disclose various element substitution bodies to Li, La and Zr sites in order to improve the ion conductivity of this Li 7 La 3 Zr 2 O 12 .
  • An object of the present invention is to provide a lithium ion conductive oxide excellent in lithium ion conductivity.
  • a lithium ion conductive oxide excellent in lithium ion conductivity can be provided. Problems, configurations, and effects other than those described above will be apparent from the description of the embodiments below.
  • Li 7 La 3 Zr 2 O 12 which is a cubic Li—La—Zr—O-based solid electrolyte material, is composed of lithium ions and a polyanion skeleton through which lithium ions can pass.
  • the polyanion skeleton is a partial structure consisting of La-oxygen bond and Zr-oxygen bond other than Li.
  • a dodecahedral structure in which eight atoms of oxygen are coordinated around La, and six oxygen atoms around Zr Consists of an ordered octahedral structure. Lithium ions conduct by passing through the voids formed by this polyanion skeleton.
  • the fact that the ratio of lithium ions is too small as the chemical composition means that the number of lithium ions responsible for lithium conductivity decreases, and the conductivity decreases.
  • the ratio of lithium ions is too high, the above-mentioned voids may be filled with lithium ions, and the migration destination of lithium ions may decrease, whereby the conductivity may be lowered.
  • the lithium ion conductive oxide in one embodiment of the present invention contains lithium, lanthanum, zirconium, oxygen as a chemical composition.
  • lithium, lanthanum, zirconium and oxygen are main constituent elements as chemical compositions, and halogen is added.
  • the added halogen is preferably replaced with oxygen which constitutes the crystal structure of the lithium ion conductive oxide.
  • the garnet-type lithium-lanthanum-zirconium oxide is not particularly limited as long as it is a compound having lithium, lanthanum, zirconium and oxygen as main constituent elements and having a garnet-type crystal structure.
  • garnet-type Li 7 La 3 Zr 2 O 12 is preferable.
  • part of divalent oxygen is replaced by monovalent halogen, and the ratio of lithium decreases to maintain charge neutrality. That is, it is presumed that the lithium ion can easily pass by increasing the space in which the lithium ion can move, and the function of enhancing the conductivity can be obtained.
  • the shape of the lithium ion conductive oxide of the present invention is distorted by replacement of oxygen and halogen having different ion radius and electronegativity in the aforementioned polyanion skeleton. It is presumed that this distortion increases the size of the air gap, facilitates the passage of lithium ions, and has the effect of enhancing the conductivity.
  • Fluorine is particularly desirable as the halogen to be added. Although its effect is not clear, it is presumed that the polyanion skeleton has an effect of making the strain gap larger because fluorine is more electronegative than oxygen. In addition, since the ion radius is close to that of oxygen as compared with other halogens, there is a feature that it is difficult to form different phases even if the substitution amount is increased.
  • the composition ratio of the halogen to be added is preferably 0.5% or more and 10% or less of the ratio of oxygen atoms in the basic composition of the lithium ion conductive oxide, particularly 2% or more and 10% or less, and further 2% or more and 7% The following are more preferable. If it is less than 0.5%, the effect of the addition may not be sufficiently obtained, and if it exceeds 10%, there is a possibility of the formation of impurities or different phases.
  • the lithium ion conductive oxide in one embodiment of the present invention has high ion conductivity because the crystal structure is mainly cubic, in particular cubic as a whole. This is because the passage of lithium ions becomes continuous because the voids formed by the polyanion skeleton are continuously formed. Depending on the composition and production conditions, for example, tetragonal crystals other than cubic crystals may occur, but it is desirable to keep cubic crystals.
  • the lattice constant a of cubic crystals in the lithium ion conductive oxide is preferably 1.310 nm to 1.285 nm.
  • the lithium ion conductive oxide in one Embodiment of this invention can substitute the cation suitably by elements other than the main structure element.
  • the site of lithium can be replaced by Al or Ga.
  • La or Zr can be replaced with another transition metal element such as Nb, Ta, Ti, or Va, or a point light metal element such as Si or Ge.
  • the present invention controls its anion, and the effect of substitution of such a cationic element does not disturb the intention of the present invention.
  • the chemical composition and crystal structure of the solid electrolyte in the battery it can be known by disassembling the battery in an inert atmosphere, taking out the solid electrolyte, performing appropriate pretreatment and performing instrumental analysis.
  • the crystal structure can be known by structural analysis by X-ray diffraction or electron beam diffraction.
  • the chemical composition can be known by inductively coupled plasma spectroscopy (ICP), photoelectron spectroscopy (XPS) analysis, X-ray fluorescence (XRF) analysis or the like.
  • the manufacturing method of lithium ion conductive oxide in one embodiment of this invention, It can prepare by the method similar to the synthesis method of a general inorganic compound. That is, it can be prepared by weighing a plurality of compounds serving as raw materials so as to obtain a desired chemical composition, mixing uniformly, and firing. Furthermore, the shaped product (pellet) of the lithium ion conductive oxide of the present invention can be obtained by shaping and heat-treating the obtained fired product.
  • the suitable oxide of Li, La, and Zr, a hydroxide, carbonate, a sulfate, nitrate, and various organic acid salts can be used.
  • each halide can be used depending on the type of halogen to be added.
  • a compound containing two or more cations as a raw material. For example, it is possible to obtain a complex compound raw material by neutralization precipitation from a solution in which an organic acid salt or alkoxide of Li, La or Zr is dissolved, or by solvent drying.
  • the steps of mixing / pulverizing, molding, firing, and heat treatment of the raw materials may be repeated as necessary.
  • mixing and pulverizing conditions, heat treatment and calcination conditions and the like can be appropriately selected.
  • raw materials may be appropriately added when the mixing steps are repeated, and the target composition ratio may be obtained in the final firing step.
  • baking or heat treatment be included in the preparation process. Specifically, baking or heat treatment at 1000 ° C. or more and 1200 ° C. or less is desirable.
  • the raw material composition should have an excess of the volatile component with respect to the desired composition, and the pellet may be covered with the powder of the same component, in some cases, with the excessive volatile component added.
  • means such as using a baking vessel with a lid are effective.
  • a plurality of transition metal oxides may be heat-treated at high temperature to prepare a composite oxide, and then heat-treated at a lower temperature with volatile lithium or halide.
  • the method of mixing the raw materials is not particularly limited, and a planetary ball mill, a jet mill, an attritor, etc. can be used, and dry or wet mixing can be used.
  • a solvent used for wet mixing lower alcohols such as ethanol can be used.
  • the means for molding is not particularly limited, and a crushed sample may be added to a mold to use uniaxial pressing, hot pressing, cold isostatic pressing (CIP), hot isostatic pressing (HIP) or the like.
  • CIP cold isostatic pressing
  • HIP hot isostatic pressing
  • Other manufacturing methods are also possible, for example, sputtering film formation.
  • the lithium ion conductive oxide in one embodiment of the present invention can be applied to a storage device that utilizes lithium ion conduction.
  • FIG. 1 is a schematic cross-sectional view showing an example of the all-solid-state lithium battery which is one of the electricity storage devices according to an embodiment of the present invention.
  • the all solid lithium battery 100 includes a positive electrode layer 13, an electrolyte layer 12, a negative electrode layer 11, a battery case 14 also serving as a negative electrode terminal, a packing 15, a lid 16 also serving as a positive electrode terminal, and the like.
  • FIG. 2 is a schematic cross-sectional view of a laminated structure including the positive electrode layer 13, the electrolyte layer 12, and the negative electrode layer 11.
  • the positive electrode layer 13 comprises a positive electrode active material 25 capable of absorbing and desorbing lithium ions, a solid electrolyte 23 capable of conducting lithium ions, a current collector (not shown) such as aluminum, and optionally a carbon material etc. Have the agent 24.
  • the negative electrode layer 11 includes a negative electrode active material 21 capable of absorbing and desorbing lithium ions, a solid electrolyte 23 capable of conducting lithium ions, a current collector (not shown) such as copper and nickel, and optionally a carbon material And a negative electrode conductive agent 22.
  • the electrolyte layer 12 has a solid electrolyte 23.
  • the lithium ion conductive oxide of the present invention is contained as a solid electrolyte 23 in at least one of the positive electrode layer 13, the negative electrode layer 11, and the electrolyte layer 12 in the all solid lithium battery which is one of the electricity storage devices of the present invention.
  • the material of the battery case 14 and the lid 16 may be aluminum, stainless steel, nickel plated steel, or the like. Also, an exterior such as an aluminum laminate sheet lined with an insulating resin can be used.
  • the packing 15 is configured to maintain an inert atmosphere in the all solid lithium battery 100.
  • a fluorine resin such as tetrafluoroethylene can be used.
  • the laminated structure which consists of the negative electrode layer 11, the electrolyte layer 12, and the positive electrode layer 13 as shown in FIG.
  • a preparation method of the laminated structure which consists of the negative electrode layer 11, the electrolyte layer 12, and the positive electrode layer 13 as shown in FIG.
  • there is a method in which the negative electrode layer 11, the electrolyte layer 12, the positive electrode layer 13, or the positive electrode layer 13, the electrolyte layer 12, and the negative electrode layer 11 are sequentially stacked on the current collector.
  • a green sheet method can also be used.
  • the positive electrode active material 25 used in the all solid lithium secondary battery of the present embodiment is not particularly limited, and any known positive electrode active material capable of inserting and extracting lithium ions can be used.
  • a layered oxide that can be represented by the general formula LiMO 2 (where M is at least one transition metal).
  • M includes Ni, Co, Mn, Fe, Ti, Zr, Al, Mg, Cr, V and the like.
  • a spinel type oxide represented by a general formula LiMn 2-X M X O 4 (M is Co, Ni, Cu, etc.)
  • a layered solid solution oxide in which LiMO 2 and Li 2 MO 3 are solid-solved
  • a polyanion compound of the general formula LixMyAz (A is at least one of PO 4 , SiO 4 and BO 3 ) represented by olivine oxide (LiMPO 4 ) can be used.
  • LiMPO 4 olivine oxide
  • one obtained by adhering or coating a carbonaceous substance may be used.
  • the negative electrode active material 21 is not particularly limited, and any known negative electrode active material capable of inserting and extracting lithium ions can be used.
  • various carbon materials typified by graphite, metal lithium, alloy materials such as TiSn alloy and TiSi alloy, nitrides such as LiCoN, and oxides such as Li 4 Ti 5 O 12 and LiTiO 4 can be used.
  • the negative electrode conductive agent 22 and the positive electrode conductive agent 24 are not particularly limited as long as they are chemically stable in the electrode and have high electron conductivity.
  • Various carbon materials such as carbon black and carbon fibers, and metal powders such as gold, silver, copper, nickel, aluminum and titanium can also be used.
  • the above electrical storage device There is no limitation in particular in the form of the above electrical storage device.
  • a strip type positive electrode layer 13, an electrolyte layer 12, and a wound type obtained by winding a negative electrode layer 11 in a cylindrical or elliptical shape a stacked type in which a positive electrode layer 13, an electrolyte layer 12 and a negative electrode layer 11 are stacked.
  • a plurality of stacks may be stacked in series and may be of a tandem type housed in one outer package.
  • These storage devices have shapes such as a button type, a cylinder type, a square type, and a laminate type.
  • the application of the storage device of the present embodiment is not particularly limited.
  • power supplies such as electric vehicles and hybrid type electric vehicles, industrial equipment such as elevators having a system for recovering at least a part of kinetic energy, power supplies for various business use and household storage systems, and It can be used as various large power sources such as power sources for natural energy power generation systems such as solar light and wind power.
  • power supplies for various business use and household storage systems can be used as various large power sources such as power sources for natural energy power generation systems such as solar light and wind power.
  • it can also be used as various small-sized power supplies such as various types of portable devices, information devices, household electric devices, and electric tools.
  • the lithium ion conductive oxide (Li 6.2 La 3 Zr 2 O 11.2 F 0.8 ) in this example was prepared as follows.
  • Li (OH) ⁇ H 2 O, La (OH) 3 , ZrO 2 and LiF were used as raw materials. These raw materials were weighed based on a predetermined composition ratio. Here, Li (OH) ⁇ H 2 O was weighed in excess of 10%, and LiF was weighed in excess of 20%. These were dry mixed in a planetary crusher.
  • the lithium ion conductive oxide (Li 6.6 La 3 Zr 2 O 11.6 F 0.4 ) in this example was prepared as follows.
  • Example 2 In the same manner as in Example 1, weighing was performed based on a predetermined composition ratio. Here, Li (OH) ⁇ H 2 O was weighed in excess of 10%, and LiF was weighed in excess of 25%. Thereafter, the pellet was prepared in the same manner as in Example 1 to obtain a pellet of this example.
  • the lithium ion conductive oxide (Li 7 La 3 Zr 2 O 12 ) in this comparative example was prepared as follows.
  • Example 2 It was weighed based on the predetermined composition ratio as in Example 1 except for LiF. Here, Li (OH) ⁇ H 2 O was weighed at a 10% excess. Thereafter, the pellet was prepared in the same manner as in Example 1 to obtain a pellet of this comparative example.
  • the lithium ion conductive oxide (Li 6.5 La 3 Zr 2 O 11.5 Cl 0.5 ) in this example was prepared as follows.
  • Li (OH) ⁇ H 2 O, La (OH) 3 , ZrO 2 and LiCl were used as raw materials.
  • La (OH) 3 and ZrO 2 with a molar ratio of 1: 1 were dry-mixed by a planetary crusher, placed in an alumina crucible with a lid, sintered in an air atmosphere at 1400 ° C. for 24 hours by an electric furnace, and the same again Dry mixing and firing to obtain a composite oxide powder of La and Zr.
  • Li (OH) .H 2 O, La (OH) 3 and LiCl were weighed based on a predetermined composition ratio. Here, an excess of 10% of Li (OH) .H 2 O and an excess of 20% of LiCl were weighed. These were dry mixed in a planetary crusher.
  • the lithium ion conductive oxide (Li 6.7 La 3 Zr 2 O 11.7 Br 0.3 ) in this example was prepared as follows.
  • the lithium ion conductive oxide (Li 6.7 La 3 Zr 2 O 11.7 I 0.3 ) in this example was prepared as follows.
  • the lithium ion conductive oxide (Li 7 La 3 Zr 2 O 12 ) in this comparative example was prepared as follows.
  • Example 3 The same raw material as Example 3 except for LiCl was weighed based on a predetermined composition ratio. Here, Li (OH) ⁇ H 2 O was weighed at a 10% excess. Thereafter, the pellet was prepared in the same manner as in Example 3 to obtain a pellet of this comparative example.
  • the ion conductivity was evaluated using an alternating current impedance method.
  • a gold thin film with a thickness of about 200 nm was formed on both sides of the produced pellet by sputtering to form an electrode.
  • Current and voltage lines were attached from a gold electrode in an argon atmosphere glove box, and AC impedance measurement was performed at 25 ° C. The resistance value was determined from the radius of the obtained arc, and the conductivity was calculated using the electrode area and the sample thickness. In each sample, it was confirmed that the direct current resistance was very high, and the electron conductivity in the sample was sufficiently lower than the ion conductivity.
  • Table 1 shows the compositions of the lithium ion conductive oxides of Examples and Comparative Examples, and the evaluation of the ionic conductivity of the prepared pellets.
  • the ion conductivity of the lithium ion conductive oxide in Example 1, Example 2, Example 3, Example 4, Example 5, Example 5, Comparative Example 1 and Comparative Example 2 was 0.39 mS / cm, 0. 0, respectively. It was 32 mS / cm, 0.26 mS / cm, 0.24 mS / cm, 0.23 mS / cm, 0.23 mS / cm, and 0.17 mS / cm.
  • the ion conductivity of the lithium ion conductive oxides of Example 1 and Example 2 of Table 1 is higher than that of Comparative Example 1, and there is an effect of being excellent in lithium ion conductivity. Furthermore, the ion conductivity of the lithium ion conductive oxides of Example 3, Example 4 and Example 5 in Table 1 is higher than that of Comparative Example 2, and there is an effect of being excellent in lithium ion conductivity.
  • an all solid lithium battery of the present invention using the lithium ion conductive oxide of Example 1 as a solid electrolyte and an all solid lithium battery using the lithium ion conductive oxide of Comparative Example 1 were prepared.
  • the positive electrode layer 13 was formed as follows. A solid electrolyte powder having an average particle size of 0.8 ⁇ m, ketjen black as a conductive agent, and lithium borate (Li 3 BO 3 ) as a sintering aid are added to LiCoO 2 powder having an average particle size of 12 ⁇ m. After mixing in a mortar at a weight ratio of 60: 25: 10: 5, in particular, an ethyl cellulose solution was added and mixed to prepare a positive electrode paste. The solid electrolyte powder used in the heat treatment of Example 1 and Comparative Example 1 was a powder which was heat-treated without being pelletized.
  • pellets of 0.8 mm thickness prepared in Example 1 and Comparative Example 1 were used as the electrolyte layer 12.
  • the positive electrode paste was applied to one surface of the pellet, and heat treatment was performed at 400 ° C. for 30 minutes and at 700 ° C. for 2 hours to bake the positive electrode layer 13.
  • the thickness of the positive electrode layer 13 was about 20 ⁇ m.
  • a gold thin film having a thickness of about 200 nm was formed on the positive electrode layer 13 side by sputtering to form a current collection layer.
  • Li foil was stuck on the electrolyte layer side in the argon atmosphere glove box. Current and voltage lines were attached from the gold electrode and the Li foil respectively.
  • Table 1 shows the evaluation results of the type and discharge capacity of the solid electrolyte of the all solid lithium battery prepared.
  • the battery using the lithium ion conductive oxide of Example 1 had a higher discharge capacity than the battery using the lithium ion conductive oxide of Comparative Example 1.
  • Negative electrode layer 12 Electrolyte layer 13: Positive electrode layer 14: Battery case 15: Packing 16: Lid 21: Negative electrode active material 22: Negative electrode conductive agent 23: Solid electrolyte 24: Positive electrode conductive agent 25: Positive electrode active material

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Abstract

The purpose of the present invention is to provide a lithium ion-conductive oxide having excellent lithium ion conductivity. A lithium ion-conductive oxide having a chemical composition containing lithium, lanthanum, zirconium and oxygen, wherein a halogen is added to the lithium ion-conductive oxide, the basic chemical composition of the lithium ion-conductive oxide is represented by the formula Li7-δLa3Zr2O12-δXδ (wherein X = at least one element selected from F, Cl, Br and I; and 0 < δ < 1), and the content of the halogen is 0.5 to 10% inclusive relative to the content of oxygen in the lithium ion-conductive oxide.

Description

リチウムイオン伝導性酸化物および蓄電デバイスLithium ion conductive oxide and storage device
　本発明は、リチウムイオン伝導性酸化物および蓄電デバイスに関する。 The present invention relates to lithium ion conductive oxides and storage devices.
　リチウムイオン二次電池は、リチウムイオンを吸蔵・放出することのできる活物質を含んだ２つの電極層と、その間にあるリチウムイオンを伝導する電解質とを有する蓄電デバイスである。リチウムイオン二次電池は他の二次電池と比較して、体積エネルギー密度および重量エネルギー密度が高い特徴がある。そのため、携帯電話やノートパソコンなどのポータブル機器用電源として広く用いられている。さらに、ハイブリッド自動車および電気自動車などの移動体用電源や、太陽光発電や風力発電などの発電システム用の電力貯蔵用電源、など産業用途への適用も進められている。 A lithium ion secondary battery is an electricity storage device having two electrode layers containing an active material capable of absorbing and desorbing lithium ions, and an electrolyte for conducting lithium ions interposed therebetween. Lithium ion secondary batteries are characterized by high volumetric energy density and weight energy density as compared with other secondary batteries. Therefore, it is widely used as a power source for portable devices such as mobile phones and notebook computers. Furthermore, application to industrial applications such as power supplies for mobile units such as hybrid vehicles and electric vehicles and power supplies for power generation systems such as solar power generation and wind power generation is also in progress.
　現在実用化されているリチウムイオン二次電池の多くが、電解質に可燃性の有機系溶媒を用いた電解液を使用している。そのため、液漏れや発火などの危険性がある。従って、これらの危険性の少ない高安全なリチウムイオン二次電池が望まれている。 Many of the lithium ion secondary batteries currently put to practical use use an electrolyte solution using a flammable organic solvent as an electrolyte. Therefore, there is a risk of liquid leakage or ignition. Therefore, a highly safe lithium ion secondary battery with less risk is desired.
　この課題の解決のため、電解質にリチウムイオン伝導性を有する固体電解質を用いたリチウムイオン二次電池の開発が進められている。特に固体電解質としてリチウムイオンを伝導する構造を有するセラミクス材料を用いた全固体リチウム二次電池は、高温での耐久性にも優れたものとして注目されている。 In order to solve this problem, development of a lithium ion secondary battery using a solid electrolyte having lithium ion conductivity as an electrolyte is in progress. In particular, an all solid lithium secondary battery using a ceramic material having a structure that conducts lithium ions as a solid electrolyte is attracting attention as one excellent in durability at high temperatures.
　このセラミクス電解質材料には、例えばリチウム－硫黄結合を含んだ硫化物系材料がある。その特徴は硫黄の原子半径が大きくかつ分極率が高いことから、リチウム伝導性に優れ、かつ外部圧力によって変形しやすいことから、電解質と電極との接触性が優れる特徴がある。しかし硫化物は大気中で不安定であり、水分吸収により硫化水素を発生させるなどの、製造上、使用上の課題がある。 The ceramic electrolyte material is, for example, a sulfide-based material containing a lithium-sulfur bond. It is characterized in that the atomic radius of sulfur is large and the polarizability is high, so that it is excellent in lithium conductivity and easily deformed by an external pressure, so that the contact between the electrolyte and the electrode is excellent. However, sulfides are unstable in the atmosphere, and there are problems in production and use, such as generation of hydrogen sulfide by absorption of water.
　セラミクス電解質材料としては他に、大気中でも安定であり、耐熱性に優れる酸化物系材料がある。例えば、リチウム－酸素－リン結合を含んだリン酸系材料がある。ＮＡＳＩＣＯＮ型のガラスセラミックスＬｉ1.5Ａｌ0.5Ｇｅ1.5（ＰＯ4）3；ＬＡＧＰやＬｉ1.3Ａｌ0.3Ｔｉ1.7（ＰＯ4）3が知られている。しかしこれらのリン酸系材料は耐還元性に課題があり、還元環境である負極側で使用することができない。 Another example of the ceramic electrolyte material is an oxide material which is stable in the atmosphere and is excellent in heat resistance. For example, there is a phosphate-based material containing a lithium-oxygen-phosphorus bond. NASICON-type glass ceramics Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 ; LAGP and Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 are known. However, these phosphoric acid materials have problems in reduction resistance, and can not be used on the negative electrode side which is a reduction environment.
　最近、リチウム、ランタン、ジルコニウムを主構成元素とするリチウムイオン伝導性酸化物が報告されている。本材料は耐還元性に優れており、リチウムと接触させても安定であり負極と接触する部位でも使用できる。すなわち化学的安定性に優れていることから、高温耐久性に優れた全固体リチウム二次電池用の固体電解質として適している。しかしそのリチウムイオン伝導性は必ずしも十分ではなかった。 Recently, lithium ion conductive oxides having lithium, lanthanum and zirconium as main constituent elements have been reported. This material is excellent in reduction resistance, is stable even in contact with lithium, and can be used at a site where it is in contact with a negative electrode. That is, since they are excellent in chemical stability, they are suitable as solid electrolytes for all solid lithium secondary batteries excellent in high temperature durability. However, its lithium ion conductivity was not always sufficient.
　特許文献１には、このリチウム、ランタン、ジルコニウムを主構成元素とする酸化物は、基本化学組成としてＬｉ7Ｌａ3Ｚｒ2Ｏ12をとり、その結晶構造として立方晶の、通称ガーネット型構造をとることで、優れたリチウムイオン伝導性を発現することが述べられている。特許文献２および特許文献３には、このＬｉ7Ｌａ3Ｚｒ2Ｏ12をイオン伝導性を向上するべくＬｉ、Ｌａ、Ｚｒサイトへの各種元素置換体が開示されている。 In Patent Document 1, the oxide mainly containing lithium, lanthanum and zirconium takes Li 7 La 3 Zr 2 O 12 as a basic chemical composition, and has a so-called garnet type structure of cubic crystal as its crystal structure. By taking it, it is stated that it exhibits excellent lithium ion conductivity. Patent Document 2 and Patent Document 3 disclose various element substitution bodies to Li, La and Zr sites in order to improve the ion conductivity of this Li 7 La 3 Zr 2 O 12 .
特開２０１１－１９５３７３号公報JP, 2011-195373, A 特開２００９－２３６２３号公報JP, 2009-23623, A 特開２０１０－２７２３４４号公報JP, 2010-272344, A
　上述の特許文献において、立方晶のＬｉ7Ｌａ3Ｚｒ2Ｏ12のカチオン元素を置換することによる性能向上が図られてきたが、そのイオン伝導度は、必ずしも十分ではなかった。本発明の目的は、リチウムイオン伝導性に優れたリチウムイオン伝導性酸化物を提供することにある。 In the above-mentioned patent documents, although the performance improvement was attempted by substituting the cation element of cubic Li 7 La 3 Zr 2 O 12 , the ion conductivity was not necessarily sufficient. An object of the present invention is to provide a lithium ion conductive oxide excellent in lithium ion conductivity.
　上記課題を解決するための本発明の特徴は、例えば以下の通りである。 The features of the present invention for solving the above problems are, for example, as follows.
　化学組成としてリチウム、ランタン、ジルコニウム、酸素を含むリチウムイオン伝導性酸化物であって、リチウムイオン伝導性酸化物にハロゲンが添加されているリチウムイオン伝導性酸化物。 A lithium ion conductive oxide containing lithium, lanthanum, zirconium and oxygen as a chemical composition, wherein a halogen is added to the lithium ion conductive oxide.
　本発明により、リチウムイオン伝導性に優れたリチウムイオン伝導性酸化物を提供できる。上記した以外の課題、構成および効果は以下の実施形態の説明により明らかにされる。 According to the present invention, a lithium ion conductive oxide excellent in lithium ion conductivity can be provided. Problems, configurations, and effects other than those described above will be apparent from the description of the embodiments below.
本発明の一実施形態における蓄電デバイスの一つである全固体リチウム電池の一例を示す断面模式図である。It is a cross-sectional schematic diagram which shows an example of the all-solid-state lithium battery which is one of the electrical storage devices in one Embodiment of this invention. 負極層、電解質層、正極層からなる積層構造の模式図である。It is a schematic diagram of the laminated structure which consists of a negative electrode layer, an electrolyte layer, and a positive electrode layer.
　以下、図面等を用いて、本発明の実施形態について説明する。以下の説明は本発明の内容の具体例を示すものであり、本発明がこれらの説明に限定されるものではなく、本明細書に開示される技術的思想の範囲内において当業者による様々な変更および修正が可能である。また、本発明を説明するための全図において、同一の機能を有するものは、同一の符号を付け、その繰り返しの説明は省略する場合がある。 Hereinafter, embodiments of the present invention will be described using the drawings and the like. The following description shows specific examples of the content of the present invention, and the present invention is not limited to these descriptions, and various modifications by those skilled in the art can be made within the scope of the technical idea disclosed herein. Changes and modifications are possible. Moreover, in all the drawings for explaining the present invention, what has the same function may attach the same numerals, and may omit explanation of the repetition.
　立方晶のＬｉ－Ｌａ－Ｚｒ－Ｏ系固体電解質材料であるＬｉ7Ｌａ3Ｚｒ2Ｏ12は、リチウムイオンと、リチウムイオンが通過できるポリアニオン骨格からなる。ポリアニオン骨格とは、Ｌｉ以外のＬａ－酸素結合およびＺｒ－酸素結合からなる部分構造で、理想的にはＬａ周囲に酸素が８原子配位する十二面体構造と、Ｚｒ周囲に酸素６原子が配意する八面体構造からなる。リチウムイオンはこのポリアニオン骨格で構成される空隙を通過することで伝導する。 Li 7 La 3 Zr 2 O 12, which is a cubic Li—La—Zr—O-based solid electrolyte material, is composed of lithium ions and a polyanion skeleton through which lithium ions can pass. The polyanion skeleton is a partial structure consisting of La-oxygen bond and Zr-oxygen bond other than Li. Ideally, a dodecahedral structure in which eight atoms of oxygen are coordinated around La, and six oxygen atoms around Zr Consists of an ordered octahedral structure. Lithium ions conduct by passing through the voids formed by this polyanion skeleton.
　ここで、その化学組成としてリチウムイオンの比率が小さすぎることは、リチウム伝導性を担うリチウムイオンの数が少なくなることで、その伝導性は低下する。一方で、リチウムイオンの比率が高すぎると上記の空隙がリチウムイオンで埋まり、リチウムイオンの移動先が減少することで伝導性が低下する可能性がある。 Here, the fact that the ratio of lithium ions is too small as the chemical composition means that the number of lithium ions responsible for lithium conductivity decreases, and the conductivity decreases. On the other hand, if the ratio of lithium ions is too high, the above-mentioned voids may be filled with lithium ions, and the migration destination of lithium ions may decrease, whereby the conductivity may be lowered.
　本発明の一実施形態におけるリチウムイオン伝導性酸化物は、化学組成としてリチウム、ランタン、ジルコニウム、酸素を含む。特に、化学組成としてリチウム、ランタン、ジルコニウム、酸素を主構成元素とし、ハロゲンが添加されている。添加されているハロゲンは、リチウムイオン伝導性酸化物の結晶構造を構成する酸素と置換されていることが好ましい。 The lithium ion conductive oxide in one embodiment of the present invention contains lithium, lanthanum, zirconium, oxygen as a chemical composition. In particular, lithium, lanthanum, zirconium and oxygen are main constituent elements as chemical compositions, and halogen is added. The added halogen is preferably replaced with oxygen which constitutes the crystal structure of the lithium ion conductive oxide.
　ガーネット型リチウムランタンジルコニウム酸化物は、リチウム、ランタン、ジルコニウム、酸素を主要構成元素として含有し、ガーネット型の結晶構造を有した化合物であれば特に制限されない。例えば、ガーネット型Ｌｉ7Ｌａ3Ｚｒ2Ｏ12が好ましい。一部の酸素がハロゲンと置換されているリチウムイオン伝導性酸化物の基本組成は、Ｌｉ7+x―δＬａ3+xＺｒ2-xＯ12―δＸδ（Ｘ＝Ｆ、Ｃｌ、Ｂｒ、Ｉの１種以上、ｘ≠０、－３＜ｘ＜２、０＜δ＜１）、特に、Ｌｉ7―δＬａ3Ｚｒ2Ｏ12―δＸδ（Ｘ＝Ｆ、Ｃｌ、Ｂｒ、Ｉの１種以上、０＜δ＜１）と記載される。その基本組成で分かるように、２価の酸素の一部が１価のハロゲンで置き換わり、電荷中性を保つためリチウムの比率が低下する。すなわちリチウムイオンが移動できる空隙を増やすことで、リチウムイオンが通過しやすくなり、伝導性を高める作用があると推定される。 The garnet-type lithium-lanthanum-zirconium oxide is not particularly limited as long as it is a compound having lithium, lanthanum, zirconium and oxygen as main constituent elements and having a garnet-type crystal structure. For example, garnet-type Li 7 La 3 Zr 2 O 12 is preferable. The basic composition of the lithium ion conductive oxide in which a part of the oxygen is replaced with halogen is Li 7 + x − δ La 3 + x Zr 2-x O 12 − δ x δ (X = F, Cl, Br And one or more kinds of I, x ≠ 0, -3 <x <2, 0 <δ <1), in particular, Li 7-δ La 3 Zr 2 O 12-δ X δ (X = F, Cl, Br, It is described that one or more kinds of I, 0 <δ <1). As can be seen from the basic composition, part of divalent oxygen is replaced by monovalent halogen, and the ratio of lithium decreases to maintain charge neutrality. That is, it is presumed that the lithium ion can easily pass by increasing the space in which the lithium ion can move, and the function of enhancing the conductivity can be obtained.
　さらに、本発明のリチウムイオン伝導性酸化物は、前述のポリアニオン骨格において、酸素とイオン半径と電気陰性度の異なるハロゲンが置き換わることで、形状に歪みが生ずると考えられる。この歪みにより空隙の大きさが増大し、リチウムイオンが通過しやすくなり、伝導性を高める作用があると推定される。 Furthermore, it is considered that the shape of the lithium ion conductive oxide of the present invention is distorted by replacement of oxygen and halogen having different ion radius and electronegativity in the aforementioned polyanion skeleton. It is presumed that this distortion increases the size of the air gap, facilitates the passage of lithium ions, and has the effect of enhancing the conductivity.
　添加されるハロゲンとしては特にフッ素が望ましい。その作用は明らかではないが、フッ素は酸素より電気陰性度が強いことから、ポリアニオン骨格がより歪み空隙がより大きくなる作用があると推定される。また他のハロゲンと比較し、酸素とイオン半径が近いことから、置換量を多くしても異相ができにくい特徴がある。 Fluorine is particularly desirable as the halogen to be added. Although its effect is not clear, it is presumed that the polyanion skeleton has an effect of making the strain gap larger because fluorine is more electronegative than oxygen. In addition, since the ion radius is close to that of oxygen as compared with other halogens, there is a feature that it is difficult to form different phases even if the substitution amount is increased.
　添加されるハロゲンの組成比は、リチウムイオン伝導性酸化物の基本組成における酸素原子の比率の０．５％以上１０％以下が好ましく、特に２％以上１０％以下、更には２％以上７％以下がより好ましい。０．５％より少ないと添加の効果が十分に得られない恐れがあり、１０％を超えると不純物や異相の生成の恐れが生ずるためである。 The composition ratio of the halogen to be added is preferably 0.5% or more and 10% or less of the ratio of oxygen atoms in the basic composition of the lithium ion conductive oxide, particularly 2% or more and 10% or less, and further 2% or more and 7% The following are more preferable. If it is less than 0.5%, the effect of the addition may not be sufficiently obtained, and if it exceeds 10%, there is a possibility of the formation of impurities or different phases.
　本発明の一実施形態におけるリチウムイオン伝導性酸化物は、結晶構造として主として立方晶、特に全体として立方晶であることで高いイオン伝導度が得られる。これは、ポリアニオン骨格による空隙が連続的に構成されることで、リチウムイオンの通過経路が連続的になるためである。組成や製造条件により立方晶以外の例えば正方晶が生ずる場合もあるが、立方晶を保つことが望ましい。リチウムイオン伝導性酸化物における立方晶の格子定数ａは１．３１０ｎｍ～１．２８５ｎｍであることが望ましい。 The lithium ion conductive oxide in one embodiment of the present invention has high ion conductivity because the crystal structure is mainly cubic, in particular cubic as a whole. This is because the passage of lithium ions becomes continuous because the voids formed by the polyanion skeleton are continuously formed. Depending on the composition and production conditions, for example, tetragonal crystals other than cubic crystals may occur, but it is desirable to keep cubic crystals. The lattice constant a of cubic crystals in the lithium ion conductive oxide is preferably 1.310 nm to 1.285 nm.
　また、本発明の一実施形態におけるリチウムイオン伝導性酸化物は、そのカチオンを主構成元素以外の元素で適宜置換することができる。例えばリチウムのサイトをＡｌやＧａに置換することができる。さらに例えば、ＬａもしくはＺｒを他のＮｂ，Ｔａ，Ｔｉ，Ｖａなどの遷移金属元素や、Ｓｉ，Ｇｅなどの点軽金属元素で置換することもできる。本発明はそのアニオンを制御するもので、このようなカチオン元素の置換による効果は、本発明の意図を妨げるものではない。 Moreover, the lithium ion conductive oxide in one Embodiment of this invention can substitute the cation suitably by elements other than the main structure element. For example, the site of lithium can be replaced by Al or Ga. Furthermore, for example, La or Zr can be replaced with another transition metal element such as Nb, Ta, Ti, or Va, or a point light metal element such as Si or Ge. The present invention controls its anion, and the effect of substitution of such a cationic element does not disturb the intention of the present invention.
　電池内の固体電解質の化学組成や結晶構造を知るには、電池を不活性雰囲気内で解体して固体電解質を取り出し、適切な前処理を施し機器分析を行うことで知ることができる。結晶構造については、Ｘ線回折や電子線回折による構造解析により知ることができる。化学組成については誘導結合プラズマ分光法（ＩＣＰ）、光電子分光（ＸＰＳ）分析、蛍光Ｘ線（ＸＲＦ）分析などで知ることができる。 In order to know the chemical composition and crystal structure of the solid electrolyte in the battery, it can be known by disassembling the battery in an inert atmosphere, taking out the solid electrolyte, performing appropriate pretreatment and performing instrumental analysis. The crystal structure can be known by structural analysis by X-ray diffraction or electron beam diffraction. The chemical composition can be known by inductively coupled plasma spectroscopy (ICP), photoelectron spectroscopy (XPS) analysis, X-ray fluorescence (XRF) analysis or the like.
　本発明の一実施形態におけるリチウムイオン伝導性酸化物の製法に特に限定はないが、一般的な無機化合物の合成方法と同様の方法で調製できる。すなわち、原料となる複数の化合物を所望の化学組成となるよう秤量し、均質に混合し焼成することで調製できる。さらに、得られた焼成物を成形、さらに熱処理することで本発明のリチウムイオン伝導性酸化物の成形体（ペレット）を得ることができる。 Although there is no limitation in particular in the manufacturing method of lithium ion conductive oxide in one embodiment of this invention, It can prepare by the method similar to the synthesis method of a general inorganic compound. That is, it can be prepared by weighing a plurality of compounds serving as raw materials so as to obtain a desired chemical composition, mixing uniformly, and firing. Furthermore, the shaped product (pellet) of the lithium ion conductive oxide of the present invention can be obtained by shaping and heat-treating the obtained fired product.
　原料となる化合物としては、Ｌｉ、Ｌａ、Ｚｒの好適な酸化物、水酸化物、炭酸塩、硫酸塩、硝酸塩、各種の有機酸塩を用いることができる。さらに添加するハロゲンの種類によって、各々のハロゲン化物を用いることができる。また、２つ以上のカチオンを含む化合物を原料として用いることも可能である。例えば、Ｌｉ、Ｌａ、Ｚｒの有機酸塩あるいはアルコキシドを溶解した溶液からの中和沈殿、溶媒乾燥による複合化合物原料を得ることができる。 As a compound used as a raw material, the suitable oxide of Li, La, and Zr, a hydroxide, carbonate, a sulfate, nitrate, and various organic acid salts can be used. Further, each halide can be used depending on the type of halogen to be added. It is also possible to use a compound containing two or more cations as a raw material. For example, it is possible to obtain a complex compound raw material by neutralization precipitation from a solution in which an organic acid salt or alkoxide of Li, La or Zr is dissolved, or by solvent drying.
　原料の混合・粉砕、成形、焼成、熱処理の工程は、必要に応じて繰り返す工程としてもよい。その際は、混合・粉砕条件、熱処理・焼成条件などは適宜に選択できる。また、混合、焼成工程を繰り返す製造工程とする場合は、混合工程を繰り返す際に原料を適宜追加し、最終の焼成工程において目的とする組成比になるようにしてもよい。 The steps of mixing / pulverizing, molding, firing, and heat treatment of the raw materials may be repeated as necessary. In that case, mixing and pulverizing conditions, heat treatment and calcination conditions and the like can be appropriately selected. In the case of repeating the mixing and firing steps, raw materials may be appropriately added when the mixing steps are repeated, and the target composition ratio may be obtained in the final firing step.
　結晶構造として主として立方晶であるリチウムイオン伝導性酸化物を得るため、あるいは緻密なペレットを得るためには、調製過程に高温の焼成もしくは熱処理が含まれることが望ましい。具体的には、１０００℃以上１２００℃以下の焼成もしくは熱処理が望ましい。 In order to obtain a lithium ion conductive oxide which is mainly cubic as a crystal structure, or to obtain a dense pellet, it is desirable that high temperature baking or heat treatment be included in the preparation process. Specifically, baking or heat treatment at 1000 ° C. or more and 1200 ° C. or less is desirable.
　一方で、リチウムやハロゲンは揮発しやすい成分であり、このため高温の焼成もしくは熱処理ではこれらの成分が揮発する恐れがある。そこで所望の化学組成とするには、所望の組成に対し、揮発成分を過剰にした原料組成とすること、ペレットの周囲に同成分の、場合によっては揮発成分を過剰に加えた粉体で覆うこと、さらには、ふた付きの焼成容器とする、などの手段が有効である。 On the other hand, lithium and halogen are easily volatile components, and there is a possibility that these components may be volatile in high temperature baking or heat treatment. Therefore, in order to obtain the desired chemical composition, the raw material composition should have an excess of the volatile component with respect to the desired composition, and the pellet may be covered with the powder of the same component, in some cases, with the excessive volatile component added. Furthermore, means such as using a baking vessel with a lid are effective.
　また、予め複数の遷移金属の酸化物を高温で熱処理して複合酸化物を調製し、その後、揮発しやすいリチウムやハロゲン化物とより低温で熱処理することもできる。 Alternatively, a plurality of transition metal oxides may be heat-treated at high temperature to prepare a composite oxide, and then heat-treated at a lower temperature with volatile lithium or halide.
　原料の混合方法は特に限定されず、遊星ボールミル、ジェットミル、アトライターなどを用いることができ、また乾式、湿式混合を用いることができる。湿式混合に用いる溶媒としては、エタノールなどの低級アルコールを用いることができる。 The method of mixing the raw materials is not particularly limited, and a planetary ball mill, a jet mill, an attritor, etc. can be used, and dry or wet mixing can be used. As a solvent used for wet mixing, lower alcohols such as ethanol can be used.
　成形の手段に特に限定はなく、金型に粉砕試料を加え、一軸加圧や、ホットプレス、冷間当方成形（ＣＩＰ）、熱間等方成型（ＨＩＰ）などを用いることができる。これ以外の製法も可能であり、例えばスパッタリング製膜も可能である。 The means for molding is not particularly limited, and a crushed sample may be added to a mold to use uniaxial pressing, hot pressing, cold isostatic pressing (CIP), hot isostatic pressing (HIP) or the like. Other manufacturing methods are also possible, for example, sputtering film formation.
　本発明の一実施形態におけるリチウムイオン伝導性酸化物は、リチウムイオンの伝導を利用する蓄電デバイスに適用が可能である。 The lithium ion conductive oxide in one embodiment of the present invention can be applied to a storage device that utilizes lithium ion conduction.
　例えば、蓄電デバイスとして全固体リチウム電池にリチウムイオン伝導性酸化物を適用できる。図１にその構成の一例を示す。図１は、本発明の一実施形態における蓄電デバイスの一つである全固体リチウム電池の一例を示す断面模式図である。全固体リチウム電池１００は、正極層１３、電解質層１２、負極層１１、負極端子を兼ねる電池ケース１４、パッキン１５、正極端子を兼ねる蓋１６、などから構成される。 For example, lithium ion conductive oxide can be applied to an all solid lithium battery as a storage device. An example of the configuration is shown in FIG. FIG. 1 is a schematic cross-sectional view showing an example of the all-solid-state lithium battery which is one of the electricity storage devices according to an embodiment of the present invention. The all solid lithium battery 100 includes a positive electrode layer 13, an electrolyte layer 12, a negative electrode layer 11, a battery case 14 also serving as a negative electrode terminal, a packing 15, a lid 16 also serving as a positive electrode terminal, and the like.
　図２に、正極層１３、電解質層１２、負極層１１からなる積層構造の断面図模式図を示す。正極層１３はリチウムイオンを吸蔵・放出可能な正極活物２５と、リチウムイオンを伝導可能な固体電解質２３と、アルミニウムなどの集電体（図示なし）と、必要により炭素材料などからなる正極導電剤２４を有する。同様に負極層１１はリチウムイオンを吸蔵・放出可能な負極活物質２１と、リチウムイオンを伝導可能な固体電解質２３と、銅やニッケルなどの集電体（図示なし）と、必要により炭素材料などからなる負極導電剤２２を有する。電解質層１２は固体電解質２３を有する。本発明の蓄電デバイスの一つである全固体リチウム電池は、正極層１３、負極層１１、電解質層１２の少なくともひとつに、本発明のリチウムイオン伝導性酸化物が固体電解質２３として含まれる。 FIG. 2 is a schematic cross-sectional view of a laminated structure including the positive electrode layer 13, the electrolyte layer 12, and the negative electrode layer 11. The positive electrode layer 13 comprises a positive electrode active material 25 capable of absorbing and desorbing lithium ions, a solid electrolyte 23 capable of conducting lithium ions, a current collector (not shown) such as aluminum, and optionally a carbon material etc. Have the agent 24. Similarly, the negative electrode layer 11 includes a negative electrode active material 21 capable of absorbing and desorbing lithium ions, a solid electrolyte 23 capable of conducting lithium ions, a current collector (not shown) such as copper and nickel, and optionally a carbon material And a negative electrode conductive agent 22. The electrolyte layer 12 has a solid electrolyte 23. The lithium ion conductive oxide of the present invention is contained as a solid electrolyte 23 in at least one of the positive electrode layer 13, the negative electrode layer 11, and the electrolyte layer 12 in the all solid lithium battery which is one of the electricity storage devices of the present invention.
　電池ケース１４および蓋１６の材質は、アルミニウム、ステンレス鋼、ニッケルメッキ鋼製などを用いることができる。また絶縁性樹脂を内張りしたアルミラミネートシートのような外装を用いることができる。パッキン１５は、全固体リチウム電池１００内の不活性雰囲気を保つために構成されている。パッキン１５の材質として、四フッ化エチレンなどのフッ素樹脂などを用いることができる。 The material of the battery case 14 and the lid 16 may be aluminum, stainless steel, nickel plated steel, or the like. Also, an exterior such as an aluminum laminate sheet lined with an insulating resin can be used. The packing 15 is configured to maintain an inert atmosphere in the all solid lithium battery 100. As a material of the packing 15, a fluorine resin such as tetrafluoroethylene can be used.
　図２に示したような、負極層１１、電解質層１２、正極層１３からなる積層構造の作製法としては、特に限定されない。例えば、電解質層１２の両面に負極層１１と正極層１３を付与し、そのあとに集電体を積層する方法がある。また、集電体に、負極層１１、電解質層１２、正極層１３あるいは正極層１３、電解質層１２、負極層１１の順に積層する方法がある。 It does not specifically limit as a preparation method of the laminated structure which consists of the negative electrode layer 11, the electrolyte layer 12, and the positive electrode layer 13 as shown in FIG. For example, there is a method of applying the negative electrode layer 11 and the positive electrode layer 13 to both surfaces of the electrolyte layer 12 and then laminating a current collector. In addition, there is a method in which the negative electrode layer 11, the electrolyte layer 12, the positive electrode layer 13, or the positive electrode layer 13, the electrolyte layer 12, and the negative electrode layer 11 are sequentially stacked on the current collector.
　電解質層１２、正極層１３、負極層１１の作製法として、グリーンシート法を用いることもできる。これは、活物質、導電剤、固体電解質などの粉体とエチルセルロースに代表されるバインダ樹脂を混合したペーストを平滑基材の上に塗布し、乾燥後、基材からはがしたシートを熱処理し、バインダ樹脂の除去と粉体の焼結を実施するものである。図２の積層体を得るのに、各々のグリーンシートを積層し、一括で熱処理することで各層が焼結した積層体を得ることもできる。 As a method of manufacturing the electrolyte layer 12, the positive electrode layer 13, and the negative electrode layer 11, a green sheet method can also be used. This applies a paste obtained by mixing a powder such as an active material, a conductive agent, a solid electrolyte, and a binder resin typified by ethyl cellulose on a smooth substrate, and after drying, heat-treats the sheet peeled off from the substrate. , Removal of the binder resin and sintering of the powder. In order to obtain the laminate of FIG. 2, it is also possible to obtain a laminate in which the respective layers are sintered by laminating the respective green sheets and performing heat treatment at one time.
　本実施形態の全固体リチウム二次電池に用いる正極活物質２５は特に限定されず、リチウムイオンを吸蔵・放出可能である既知の正極活物質を使用することができる。たとえば一般式ＬｉＭＯ2（Ｍは少なくとも１種の遷移金属）で表せる層状型酸化物がある。ここで、ＭはＮｉ、Ｃｏ、Ｍｎ、Ｆｅ、Ｔｉ、Ｚｒ、Ａｌ、Ｍｇ、Ｃｒ、Ｖなどが挙げられる。その他にも、一般式ＬｉＭｎ2-XＭXＯ4（ＭはＣｏ、Ｎｉ、Ｃｕなど）で表記されるスピネル型酸化物、ＬｉＭＯ2とＬｉ2ＭＯ3とが固溶した層状固溶体酸化物、オリビン酸化物（ＬｉＭＰＯ4）に代表される一般式ＬｉｘＭｙＡｚ（Ａは、ＰＯ4、ＳｉＯ4、ＢＯ3の少なくとも１種）のポリアニオン化合物、などを用いることができる。上記の化合物粒子の表面に導電性を付与するため炭素質の物質を付着、あるいは被覆したものを用いてもよい。 The positive electrode active material 25 used in the all solid lithium secondary battery of the present embodiment is not particularly limited, and any known positive electrode active material capable of inserting and extracting lithium ions can be used. For example, there is a layered oxide that can be represented by the general formula LiMO 2 (where M is at least one transition metal). Here, M includes Ni, Co, Mn, Fe, Ti, Zr, Al, Mg, Cr, V and the like. Besides, a spinel type oxide represented by a general formula LiMn 2-X M X O 4 (M is Co, Ni, Cu, etc.), a layered solid solution oxide in which LiMO 2 and Li 2 MO 3 are solid-solved, A polyanion compound of the general formula LixMyAz (A is at least one of PO 4 , SiO 4 and BO 3 ) represented by olivine oxide (LiMPO 4 ) can be used. In order to impart conductivity to the surface of the above-mentioned compound particle, one obtained by adhering or coating a carbonaceous substance may be used.
　負極活物質２１に特に限定はなく、リチウムイオンを吸蔵・放出可能である既知の負極活物質を使用することができる。たとえば、黒鉛に代表される各種の炭素材料、金属リチウム、ＴｉＳｎ合金、ＴｉＳｉ合金などの合金材料、ＬｉＣｏＮなどの窒化物、Ｌｉ4Ｔｉ5Ｏ12、ＬｉＴｉＯ4などの酸化物を用いることができる。 The negative electrode active material 21 is not particularly limited, and any known negative electrode active material capable of inserting and extracting lithium ions can be used. For example, various carbon materials typified by graphite, metal lithium, alloy materials such as TiSn alloy and TiSi alloy, nitrides such as LiCoN, and oxides such as Li 4 Ti 5 O 12 and LiTiO 4 can be used.
　負極導電剤２２および正極導電剤２４も電極内で化学的に安定であり、かつ電子伝導性の高いものであれば特には限定されない。カーボンブラックや炭素繊維などの各種炭素材料や、金、銀、銅、ニッケル、アルミニウム、チタン等の金属粉も使用可能である。 The negative electrode conductive agent 22 and the positive electrode conductive agent 24 are not particularly limited as long as they are chemically stable in the electrode and have high electron conductivity. Various carbon materials such as carbon black and carbon fibers, and metal powders such as gold, silver, copper, nickel, aluminum and titanium can also be used.
　以上の蓄電デバイスの形態に特に限定はない。帯状の正極層１３、電解質層１２、負極層１１を円筒形あるいは楕円形に捲回した捲回型、正極層１３、電解質層１２、負極層１１を積層体した積層型、などがある。特に全固体電池においては、複数の積層体を直列に積層し一つの外装に収めるタンデム型とすることもできる。これらの蓄電デバイスにはボタン型、円筒型、角型、ラミネート型などの形状を有する。 There is no limitation in particular in the form of the above electrical storage device. There are a strip type positive electrode layer 13, an electrolyte layer 12, and a wound type obtained by winding a negative electrode layer 11 in a cylindrical or elliptical shape, a stacked type in which a positive electrode layer 13, an electrolyte layer 12 and a negative electrode layer 11 are stacked. In particular, in the case of an all-solid-state battery, a plurality of stacks may be stacked in series and may be of a tandem type housed in one outer package. These storage devices have shapes such as a button type, a cylinder type, a square type, and a laminate type.
　本実施形態の蓄電デバイスの用途は特に限定されない。例えば、電気自動車やハイブリッド型電気自動車などの動力用電源や、運動エネルギーの少なくとも一部を回収するシステムを有するエレベータなどの産業用機器、各種業務用や家庭用の蓄電システム用の電源、さらには太陽光や風力などの自然エネルギー発電システム用電源など、各種大型電源として用いることができる。また、各種携帯型機器や情報機器、家庭用電気機器、電動工具などの各種小型電源としても用いることができる。 The application of the storage device of the present embodiment is not particularly limited. For example, power supplies such as electric vehicles and hybrid type electric vehicles, industrial equipment such as elevators having a system for recovering at least a part of kinetic energy, power supplies for various business use and household storage systems, and It can be used as various large power sources such as power sources for natural energy power generation systems such as solar light and wind power. In addition, it can also be used as various small-sized power supplies such as various types of portable devices, information devices, household electric devices, and electric tools.
　以下、本実施形態のリチウムイオン伝導性酸化物およびそれを部材として用いた蓄電デバイスの詳細な実施例を示し、具体的に説明する。但し、本発明は以下に述べる実施例に限定されるものではない。 Hereinafter, detailed examples of the lithium ion conductive oxide of the present embodiment and an electricity storage device using the same as a member will be shown and specifically described. However, the present invention is not limited to the examples described below.
　本実施例におけるリチウムイオン伝導性酸化物（Ｌｉ6.2Ｌａ3Ｚｒ2Ｏ11.2Ｆ0.8）を次のとおり調製した。 The lithium ion conductive oxide (Li 6.2 La 3 Zr 2 O 11.2 F 0.8 ) in this example was prepared as follows.
　原料として、Ｌｉ（ＯＨ）・Ｈ2Ｏ、Ｌａ（ＯＨ）3、ＺｒＯ2、ＬｉＦを用いた。これらの原料を所定の組成比を基に秤量した。ここで、Ｌｉ（ＯＨ）・Ｈ2Ｏは１０％の過剰量、ＬｉＦは２０％の過剰量を秤量した。これらを、遊星型粉砕機で乾式混合した。 As raw materials, Li (OH) · H 2 O, La (OH) 3 , ZrO 2 and LiF were used. These raw materials were weighed based on a predetermined composition ratio. Here, Li (OH) · H 2 O was weighed in excess of 10%, and LiF was weighed in excess of 20%. These were dry mixed in a planetary crusher.
　その後、蓋付のアルミナるつぼに入れ、９００℃１２時間空気雰囲気で焼成した。この焼成物を再び遊星型粉砕機で粉砕した。粉砕後の焼成粉末１ｇを超鋼ダイスに入れ、一軸プレスにより直径１０ｍｍのペレットとした。酸化マグネシウム製の緻密質るつぼにペレットを投入し、るつぼの残容積を焼成物粉末で満たしてふたをし、アルゴン雰囲気で１２００℃で２４時間熱処理し、本実施例のペレットを得た。 Then, it was put in a covered alumina crucible and fired in an air atmosphere at 900 ° C. for 12 hours. The fired product was crushed again by a planetary crusher. 1 g of the fired powder after grinding was placed in a super steel die and made into pellets of 10 mm in diameter by uniaxial pressing. The pellet was charged into a dense crucible made of magnesium oxide, the remaining volume of the crucible was filled with the powder of the sintered product, the lid was covered, and heat treatment was performed at 1200 ° C. for 24 hours in an argon atmosphere to obtain the pellet of this example.
　得られたペレットをＸ線回折で測定した結果、立方晶であることが確認された。 As a result of measuring the obtained pellet by X-ray diffraction, it was confirmed to be cubic.
　本実施例におけるリチウムイオン伝導性酸化物（Ｌｉ6.6Ｌａ3Ｚｒ2Ｏ11.6Ｆ0.4）を次のとおり調製した。 The lithium ion conductive oxide (Li 6.6 La 3 Zr 2 O 11.6 F 0.4 ) in this example was prepared as follows.
　実施例１と同様に所定の組成比を基に秤量した。ここでＬｉ（ＯＨ）・Ｈ2Ｏは１０％の過剰量、ＬｉＦは２５％の過剰量を秤量した。以後、実施例１と同様に調製し、本実施例のペレットを得た。 In the same manner as in Example 1, weighing was performed based on a predetermined composition ratio. Here, Li (OH) · H 2 O was weighed in excess of 10%, and LiF was weighed in excess of 25%. Thereafter, the pellet was prepared in the same manner as in Example 1 to obtain a pellet of this example.
　得られたペレットをＸ線回折で測定した結果、立方晶であることが確認された。 As a result of measuring the obtained pellet by X-ray diffraction, it was confirmed to be cubic.
比較例１Comparative Example 1
　本比較例におけるリチウムイオン伝導性酸化物（Ｌｉ7Ｌａ3Ｚｒ2Ｏ12）を次のとおり調製した。 The lithium ion conductive oxide (Li 7 La 3 Zr 2 O 12 ) in this comparative example was prepared as follows.
　ＬｉＦを除き実施例１と同様に所定の組成比を基に秤量した。ここでＬｉ（ＯＨ）・Ｈ2Ｏは１０％の過剰量を秤量した。以後、実施例１と同様に調製し、本比較例のペレットを得た。 It was weighed based on the predetermined composition ratio as in Example 1 except for LiF. Here, Li (OH) · H 2 O was weighed at a 10% excess. Thereafter, the pellet was prepared in the same manner as in Example 1 to obtain a pellet of this comparative example.
　得られたペレットをＸ線回折で測定した結果、立方晶であることが確認された。 As a result of measuring the obtained pellet by X-ray diffraction, it was confirmed to be cubic.
　本実施例におけるリチウムイオン伝導性酸化物（Ｌｉ6.5Ｌａ3Ｚｒ2Ｏ11.5Ｃｌ0.5）を次のとおり調製した。 The lithium ion conductive oxide (Li 6.5 La 3 Zr 2 O 11.5 Cl 0.5 ) in this example was prepared as follows.
　原料として、Ｌｉ（ＯＨ）・Ｈ2Ｏ、Ｌａ（ＯＨ）3、ＺｒＯ2、ＬｉＣｌを用いた。まずモル比１：１のＬａ（ＯＨ）3とＺｒＯ2、とを遊星型粉砕機で乾式混合後、蓋付のアルミナるつぼに入れ、電気炉により１４００℃２４時間空気雰囲気で焼成し、再度同様の乾式混合と焼成を行い、ＬａとＺｒの複合酸化物粉末を得た。この複合酸化物粉末に加え、Ｌｉ（ＯＨ）・Ｈ2Ｏ、Ｌａ（ＯＨ）3、ＬｉＣｌを所定の組成比を基に秤量した。ここで、Ｌｉ（ＯＨ）・Ｈ2Ｏは１０％の過剰量、ＬｉＣｌは２０％の過剰量を秤量した。これらを、遊星型粉砕機で乾式混合した。 As raw materials, Li (OH) · H 2 O, La (OH) 3 , ZrO 2 and LiCl were used. First, La (OH) 3 and ZrO 2 with a molar ratio of 1: 1 were dry-mixed by a planetary crusher, placed in an alumina crucible with a lid, sintered in an air atmosphere at 1400 ° C. for 24 hours by an electric furnace, and the same again Dry mixing and firing to obtain a composite oxide powder of La and Zr. In addition to this composite oxide powder, Li (OH) .H 2 O, La (OH) 3 and LiCl were weighed based on a predetermined composition ratio. Here, an excess of 10% of Li (OH) .H 2 O and an excess of 20% of LiCl were weighed. These were dry mixed in a planetary crusher.
　その後、蓋付のアルミナるつぼに入れ、原料のハロゲン化リチウムの分解とハロゲンの揮発を考慮して、電気炉により６５０℃１２時間空気雰囲気で焼成した。この焼成物を再び遊星型粉砕機で粉砕した。粉砕後の焼成粉末１ｇを超鋼ダイスに入れ、一軸プレスにより直径１０ｍｍのペレットとした。酸化マグネシウム製の緻密質るつぼにペレットを投入し、るつぼの残容積を焼成物粉末で満たしてふたをし、アルゴン雰囲気で１２００℃で２４時間熱処理し、本実施例のペレットを得た。 Then, it was placed in a covered alumina crucible and fired in an electric furnace at 650 ° C. for 12 hours in an air atmosphere in consideration of decomposition of raw material lithium halide and volatilization of halogen. The fired product was crushed again by a planetary crusher. 1 g of the fired powder after grinding was placed in a super steel die and made into pellets of 10 mm in diameter by uniaxial pressing. The pellet was charged into a dense crucible made of magnesium oxide, the remaining volume of the crucible was filled with the powder of the sintered product, the lid was covered, and heat treatment was performed at 1200 ° C. for 24 hours in an argon atmosphere to obtain the pellet of this example.
　得られたペレットをＸ線回折で測定した結果、立方晶であることが確認された。 As a result of measuring the obtained pellet by X-ray diffraction, it was confirmed to be cubic.
　本実施例におけるリチウムイオン伝導性酸化物（Ｌｉ6.7Ｌａ3Ｚｒ2Ｏ11.7Ｂｒ0.3）を次のとおり調製した。 The lithium ion conductive oxide (Li 6.7 La 3 Zr 2 O 11.7 Br 0.3 ) in this example was prepared as follows.
　ＬｉＣｌに代わりＬｉＢｒを用いた以外は実施例３と同様に調製した。ＬｉＢｒの過剰量は３０％とした。 It was prepared in the same manner as in Example 3 except that LiBr was used instead of LiCl. The excess amount of LiBr was 30%.
　得られたペレットをＸ線回折で測定した結果、立方晶であることが確認された。 As a result of measuring the obtained pellet by X-ray diffraction, it was confirmed to be cubic.
　本実施例におけるリチウムイオン伝導性酸化物（Ｌｉ6.7Ｌａ3Ｚｒ2Ｏ11.7Ｉ0.3）を次のとおり調製した。 The lithium ion conductive oxide (Li 6.7 La 3 Zr 2 O 11.7 I 0.3 ) in this example was prepared as follows.
　ＬｉＢｒに代わりＬｉＩを用いた以外は実施例４と同様に調製した。ＬｉＩの過剰量は３０％とした。 It was prepared in the same manner as in Example 4 except that LiI was used instead of LiBr. The excess amount of LiI was 30%.
　得られたペレットをＸ線回折で測定した結果、立方晶であることが確認された。 As a result of measuring the obtained pellet by X-ray diffraction, it was confirmed to be cubic.
比較例２Comparative example 2
　本比較例におけるリチウムイオン伝導性酸化物（Ｌｉ7Ｌａ3Ｚｒ2Ｏ12）を次のとおり調製した。 The lithium ion conductive oxide (Li 7 La 3 Zr 2 O 12 ) in this comparative example was prepared as follows.
　ＬｉＣｌを除く実施例３と同じ原料を所定の組成比を基に秤量した。ここでＬｉ（ＯＨ）・Ｈ2Ｏは１０％の過剰量を秤量した。以後、実施例３と同様に調製し、本比較例のペレットを得た。 The same raw material as Example 3 except for LiCl was weighed based on a predetermined composition ratio. Here, Li (OH) · H 2 O was weighed at a 10% excess. Thereafter, the pellet was prepared in the same manner as in Example 3 to obtain a pellet of this comparative example.
　得られたペレットをＸ線回折で測定した結果、立方晶であることが確認された。 As a result of measuring the obtained pellet by X-ray diffraction, it was confirmed to be cubic.
　＜イオン伝導度評価＞
　イオン伝導度は、交流インピーダンス法を用いて評価した。作製したペレットの両面に厚さ約２００ｎｍの金薄膜をスパッタ法で製膜し電極とした。アルゴン雰囲気のグローブボックス内で金電極から電流、電圧線を取り付け、交流インピーダンス測定を２５℃で実施した。得られた円弧の半径から抵抗値を求め、電極面積、試料厚みを用いて伝導度を算出した。尚、いずれの試料においても、直流抵抗は非常に高く、試料内の電子伝導度はイオン伝導度に比べて十分に低いことを確認した。 <Evaluation of ion conductivity>
The ion conductivity was evaluated using an alternating current impedance method. A gold thin film with a thickness of about 200 nm was formed on both sides of the produced pellet by sputtering to form an electrode. Current and voltage lines were attached from a gold electrode in an argon atmosphere glove box, and AC impedance measurement was performed at 25 ° C. The resistance value was determined from the radius of the obtained arc, and the conductivity was calculated using the electrode area and the sample thickness. In each sample, it was confirmed that the direct current resistance was very high, and the electron conductivity in the sample was sufficiently lower than the ion conductivity.
　表１に各実施例及び比較例のリチウムイオン伝導性酸化物の組成と、調整したペレットのイオン伝導度評価を示す。実施例１、実施例２、実施例３、実施例４、実施例５、比較例１、比較例２におけるリチウムイオン伝導性酸化物のイオン伝導度は、それぞれ、０．３９ｍＳ／ｃｍ、０．３２ｍＳ／ｃｍ、０．２６ｍＳ／ｃｍ、０．２４ｍＳ／ｃｍ、０．２３ｍＳ／ｃｍ、０．２３ｍＳ／ｃｍ、０．１７ｍＳ／ｃｍであった。 Table 1 shows the compositions of the lithium ion conductive oxides of Examples and Comparative Examples, and the evaluation of the ionic conductivity of the prepared pellets. The ion conductivity of the lithium ion conductive oxide in Example 1, Example 2, Example 3, Example 4, Example 5, Example 5, Comparative Example 1 and Comparative Example 2 was 0.39 mS / cm, 0. 0, respectively. It was 32 mS / cm, 0.26 mS / cm, 0.24 mS / cm, 0.23 mS / cm, 0.23 mS / cm, and 0.17 mS / cm.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１の実施例１と実施例２のリチウムイオン伝導性酸化物のイオン伝導度は比較例１と比べ高く、リチウムイオン伝導性に優れる効果があった。さらに、表１の実施例３、実施例４および実施例５のリチウムイオン伝導性酸化物のイオン伝導度は比較例２と比べ高く、リチウムイオン伝導性に優れる効果があった。 The ion conductivity of the lithium ion conductive oxides of Example 1 and Example 2 of Table 1 is higher than that of Comparative Example 1, and there is an effect of being excellent in lithium ion conductivity. Furthermore, the ion conductivity of the lithium ion conductive oxides of Example 3, Example 4 and Example 5 in Table 1 is higher than that of Comparative Example 2, and there is an effect of being excellent in lithium ion conductivity.
　＜蓄電デバイスの作成＞
　蓄電デバイスとして、固体電解質として実施例１のリチウムイオン伝導性酸化物を用いた本発明の全固体リチウム電池と、比較例１のリチウムイオン伝導性酸化物を用いた全固体リチウム電池を作成した。 <Creating storage device>
As an electricity storage device, an all solid lithium battery of the present invention using the lithium ion conductive oxide of Example 1 as a solid electrolyte and an all solid lithium battery using the lithium ion conductive oxide of Comparative Example 1 were prepared.
　正極層１３を以下のように作成した。平均粒径が１２μｍのＬｉＣｏＯ2粉末に対し、平均粒径が０．８μｍの固体電解質粉末、導電剤としてのケッチェンブラック、焼結助材としてのホウ酸リチウム（Ｌｉ3ＢＯ3）をそれぞれの重量比で６０：２５：１０：５で乳鉢にとりわけ、混合したのち、エチルセルロース溶液を加え混合し正極ペーストを作製した。固体電解質粉末は、実施例１および比較例１の熱処理において、ペレット化せずに熱処理した粉末を用いた。 The positive electrode layer 13 was formed as follows. A solid electrolyte powder having an average particle size of 0.8 μm, ketjen black as a conductive agent, and lithium borate (Li 3 BO 3 ) as a sintering aid are added to LiCoO 2 powder having an average particle size of 12 μm. After mixing in a mortar at a weight ratio of 60: 25: 10: 5, in particular, an ethyl cellulose solution was added and mixed to prepare a positive electrode paste. The solid electrolyte powder used in the heat treatment of Example 1 and Comparative Example 1 was a powder which was heat-treated without being pelletized.
　次いで、電解質層１２として実施例１および比較例１で調製した０．８ｍｍ厚のペレットを用いた。ペレットの片面に正極ペーストを塗布し、４００℃で３０分、７００℃で２時間熱処理し、正極層１３を焼き付けた。正極層１３の厚みは約２０μｍであった。その後、正極層１３側に厚さ約２００ｎｍの金薄膜をスパッタ法で製膜し集電層とした。 Next, pellets of 0.8 mm thickness prepared in Example 1 and Comparative Example 1 were used as the electrolyte layer 12. The positive electrode paste was applied to one surface of the pellet, and heat treatment was performed at 400 ° C. for 30 minutes and at 700 ° C. for 2 hours to bake the positive electrode layer 13. The thickness of the positive electrode layer 13 was about 20 μm. Thereafter, a gold thin film having a thickness of about 200 nm was formed on the positive electrode layer 13 side by sputtering to form a current collection layer.
　アルゴン雰囲気のグローブボックス内で電解質層側にＬｉ箔を貼りつけた。金電極、Ｌｉ箔各々から電流、電圧線を取り付けた。 Li foil was stuck on the electrolyte layer side in the argon atmosphere glove box. Current and voltage lines were attached from the gold electrode and the Li foil respectively.
　＜全固体リチウム電池の評価＞
　作製した全固体リチウム電池の充放電試験を行った。電流は０．０２ＣＡ相当とし、充電は４．３Ｖの定電流充電、放電は３．０Ｖの定電流放電とした。放電時の放電容量を評価した。実施例１、比較例１における全固体リチウム電池の放電容量は、それぞれ、１０５ｍＡｈ／ｇ、８７ｍＡｈ／ｇであった。 <Evaluation of all solid lithium battery>
The charge and discharge test of the produced all solid lithium battery was done. The current was set to be equivalent to 0.02 CA, the charge was constant current charge of 4.3 V, and the discharge was constant current discharge of 3.0 V. The discharge capacity at the time of discharge was evaluated. The discharge capacities of all the solid lithium batteries in Example 1 and Comparative Example 1 were 105 mAh / g and 87 mAh / g, respectively.
　表１に作成した全固体リチウム電池の固体電解質の種類と放電容量の評価結果を示す。実施例１のリチウムイオン伝導性酸化物を用いた電池は比較例１のそれを用いた電池に比べ放電容量が高い効果が得られた。 Table 1 shows the evaluation results of the type and discharge capacity of the solid electrolyte of the all solid lithium battery prepared. The battery using the lithium ion conductive oxide of Example 1 had a higher discharge capacity than the battery using the lithium ion conductive oxide of Comparative Example 1.
１１：負極層
１２：電解質層
１３：正極層
１４：電池ケース
１５：パッキン
１６：蓋
２１：負極活物質
２２：負極導電剤
２３：固体電解質
２４：正極導電剤
２５：正極活物質 11: Negative electrode layer 12: Electrolyte layer 13: Positive electrode layer 14: Battery case 15: Packing 16: Lid 21: Negative electrode active material 22: Negative electrode conductive agent 23: Solid electrolyte 24: Positive electrode conductive agent 25: Positive electrode active material

Claims (7)

  1. 　化学組成としてリチウム、ランタン、ジルコニウム、酸素を含むリチウムイオン伝導性酸化物であって、
    　前記リチウムイオン伝導性酸化物にハロゲンが添加されているリチウムイオン伝導性酸化物。     A lithium ion conductive oxide containing lithium, lanthanum, zirconium, oxygen as a chemical composition,
    Lithium ion conductive oxide in which halogen is added to the lithium ion conductive oxide.
  2. 　請求項１において、
    　前記酸素の一部が前記ハロゲンで置換されているリチウムイオン伝導性酸化物。     In claim 1,
    The lithium ion conductive oxide in which a part of the oxygen is substituted by the halogen.
  3. 　請求項１乃至２のいずれかにおいて、
    　前記リチウムイオン伝導性酸化物の基本組成はＬｉ7-δＬａ3Ｚｒ2Ｏ12-δＸδ（Ｘ＝Ｆ、Ｃｌ、Ｂｒ、Ｉの１種以上、０＜δ＜１）であるリチウムイオン伝導性酸化物。     In any one of claims 1 to 2,
    The basic composition of the lithium ion conductive oxide is a lithium ion having a composition of Li 7-δ La 3 Zr 2 O 12-δ X δ (where X is at least one of F, Cl, Br and I, 0 <δ <1). Conductive oxide.
  4. 　請求項１乃至３のいずれかにおいて、
    　前記ハロゲンがフッ素であるリチウムイオン伝導性酸化物。     In any one of claims 1 to 3,
    Lithium ion conductive oxide in which the halogen is fluorine.
  5. 　請求項１乃至４のいずれかにおいて、
    　前記ハロゲンの組成比は、前記リチウムイオン伝導性酸化物における前記酸素の比率の０．５％以上１０％以下であるリチウムイオン伝導性酸化物。     In any one of claims 1 to 4,
    The lithium ion conductive oxide, wherein the composition ratio of the halogen is 0.5% or more and 10% or less of the ratio of the oxygen in the lithium ion conductive oxide.
  6. 　請求項１乃至４のいずれかにおいて、
    　前記リチウムイオン伝導性酸化物の結晶構造は立方晶であるリチウムイオン伝導性酸化物。     In any one of claims 1 to 4,
    The crystal structure of the lithium ion conductive oxide is cubic crystal.
  7. 　請求項１乃至５のいずれかのリチウムイオン伝導性酸化物を用いた蓄電デバイス。 An electricity storage device using the lithium ion conductive oxide according to any one of claims 1 to 5.
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