WO2015079509A1 - Oxyde conducteur d'ion lithium et dispositif de stockage électrique - Google Patents

Oxyde conducteur d'ion lithium et dispositif de stockage électrique 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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English (en)
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

La présente invention concerne un oxyde conducteur d'ion lithium ayant une excellente conductivité d'ion lithium. L'invention concerne un oxyde conducteur d'ion lithium ayant une composition chimique contenant du lithium, du lanthane, du zirconium et de l'oxygène, un halogène étant ajouté à l'oxyde conducteur d'ion lithium, la composition chimique de base de l'oxyde conducteur d'ion lithium étant représentée par la formule Li7-δLa3Zr2O12-δXδ (dans laquelle X = au moins un élément choisi parmi F, Cl, Br et I ; et 0 < δ < 1), et la teneur de l'halogène étant de 0,5 à 10 % inclus par rapport à la teneur d'oxygène dans l'oxyde conducteur d'ion lithium.
PCT/JP2013/081832 2013-11-27 2013-11-27 Oxyde conducteur d'ion lithium et dispositif de stockage électrique WO2015079509A1 (fr)

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CN105070944A (zh) * 2015-07-30 2015-11-18 中国科学院西安光学精密机械研究所 一种f-和y3+离子协同掺杂的nasicon型锂离子固体电解质及其制备方法
JP2020087770A (ja) * 2018-11-28 2020-06-04 セイコーエプソン株式会社 固体電解質、固体電解質の製造方法、二次電池、電子機器
JP2020098674A (ja) * 2018-12-17 2020-06-25 セイコーエプソン株式会社 電解質、電池、電子機器、電解質および電池の製造方法
JPWO2020137043A1 (ja) * 2018-12-28 2021-11-11 パナソニックＩｐマネジメント株式会社 リチウムイオン伝導性固体電解質材料、およびこれを用いた電池
WO2021250985A1 (fr) * 2020-06-08 2021-12-16 パナソニックＩｐマネジメント株式会社 Matériau d'électrolyte solide, et batterie dans laquelle celui-ci est utilisé
WO2021256036A1 (fr) * 2020-06-15 2021-12-23 株式会社カネカ Oxyde de type grenat conducteur d'ions lithium
CN113892206A (zh) * 2019-07-04 2022-01-04 松下知识产权经营株式会社 电池
CN114303267A (zh) * 2019-08-30 2022-04-08 昭和电工株式会社 锂离子传导性氧化物
JP7171826B1 (ja) 2021-06-02 2022-11-15 住友化学株式会社 リチウム含有酸化物及び固体電解質の製造方法
US11735765B2 (en) 2021-01-08 2023-08-22 Samsung Electronics Co., Ltd. Solid ion conductor, solid electrolyte including the solid ion conductor, electrochemical device including the solid electrolyte, and method of preparing the solid ion conductor
US11961962B2 (en) 2020-07-02 2024-04-16 Samsung Electronics Co., Ltd. Solid ion conductor compound, solid electrolyte including the same, electrochemical cell including the same, and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006260887A (ja) * 2005-03-16 2006-09-28 Japan Science & Technology Agency 多孔質固体電極及びそれを用いた全固体リチウム二次電池
JP2012018792A (ja) * 2010-07-07 2012-01-26 National Univ Corp Shizuoka Univ 固体電解質材料およびリチウム電池
WO2013128759A1 (fr) * 2012-03-02 2013-09-06 日本碍子株式会社 Matière céramique électrolyte solide et son procédé de fabrication
JP2013182836A (ja) * 2012-03-02 2013-09-12 Honda Motor Co Ltd リチウムイオン伝導性電解質及びそれを用いるリチウムイオン二次電池
WO2013136446A1 (fr) * 2012-03-13 2013-09-19 株式会社 東芝 Oxyde conducteur d'ions lithium, batterie rechargeable à électrolyte solide, et bloc d'éléments de batterie
JP2013256435A (ja) * 2012-05-14 2013-12-26 Toyota Central R&D Labs Inc ガーネット型リチウムイオン伝導性酸化物の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006260887A (ja) * 2005-03-16 2006-09-28 Japan Science & Technology Agency 多孔質固体電極及びそれを用いた全固体リチウム二次電池
JP2012018792A (ja) * 2010-07-07 2012-01-26 National Univ Corp Shizuoka Univ 固体電解質材料およびリチウム電池
WO2013128759A1 (fr) * 2012-03-02 2013-09-06 日本碍子株式会社 Matière céramique électrolyte solide et son procédé de fabrication
JP2013182836A (ja) * 2012-03-02 2013-09-12 Honda Motor Co Ltd リチウムイオン伝導性電解質及びそれを用いるリチウムイオン二次電池
WO2013136446A1 (fr) * 2012-03-13 2013-09-19 株式会社 東芝 Oxyde conducteur d'ions lithium, batterie rechargeable à électrolyte solide, et bloc d'éléments de batterie
JP2013256435A (ja) * 2012-05-14 2013-12-26 Toyota Central R&D Labs Inc ガーネット型リチウムイオン伝導性酸化物の製造方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
GREGORY T.HITZ ET AL.: "Highly Li-Stuffed Garnet-Type Li7+xLa3Zr2-xYxO12", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 160, no. 8, 28 May 2013 (2013-05-28), pages A1248 - A1255 *
HENRIK BUSCHMANN ET AL.: "Lithium metal electrode kinetics and ionic conductivity of the solid lithium ion conductors ''Li7La3Zr2O12'' and Li7-xLa3Zr2-xTaxO12 with garnet-type structure", JOURNAL OF POWER SOURCES, vol. 206, 2012, pages 236 - 244 *
SHINGO OHTA ET AL.: "High lithium ionic conductivity in the garnet-type oxide Li7-xLa3(Zr2-x,Nbx)O12(X=0-2)", JOURNAL OF POWER SOURCES, vol. 196, 2011, pages 3342 - 3345 *

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105070944A (zh) * 2015-07-30 2015-11-18 中国科学院西安光学精密机械研究所 一种f-和y3+离子协同掺杂的nasicon型锂离子固体电解质及其制备方法
JP2020087770A (ja) * 2018-11-28 2020-06-04 セイコーエプソン株式会社 固体電解質、固体電解質の製造方法、二次電池、電子機器
JP7155944B2 (ja) 2018-11-28 2022-10-19 セイコーエプソン株式会社 固体電解質、固体電解質の製造方法、二次電池、電子機器
JP2020098674A (ja) * 2018-12-17 2020-06-25 セイコーエプソン株式会社 電解質、電池、電子機器、電解質および電池の製造方法
EP3905270A4 (fr) * 2018-12-28 2022-02-23 Panasonic Intellectual Property Management Co., Ltd. Matériau d'électrolyte solide conducteur des ions lithium et accumulateur l'utilisant
JPWO2020137043A1 (ja) * 2018-12-28 2021-11-11 パナソニックＩｐマネジメント株式会社 リチウムイオン伝導性固体電解質材料、およびこれを用いた電池
JP7417951B2 (ja) 2018-12-28 2024-01-19 パナソニックＩｐマネジメント株式会社 リチウムイオン伝導性固体電解質材料、およびこれを用いた電池
CN113892206A (zh) * 2019-07-04 2022-01-04 松下知识产权经营株式会社 电池
EP3996179A4 (fr) * 2019-07-04 2022-08-03 Panasonic Intellectual Property Management Co., Ltd. Batterie
US12113166B2 (en) 2019-07-04 2024-10-08 Panasonic Intellectual Property Management Co., Ltd. Battery
JP7535703B2 (ja) 2019-07-04 2024-08-19 パナソニックＩｐマネジメント株式会社 電池
CN114303267A (zh) * 2019-08-30 2022-04-08 昭和电工株式会社 锂离子传导性氧化物
CN114303267B (zh) * 2019-08-30 2024-04-02 株式会社力森诺科 锂离子传导性氧化物
WO2021250985A1 (fr) * 2020-06-08 2021-12-16 パナソニックＩｐマネジメント株式会社 Matériau d'électrolyte solide, et batterie dans laquelle celui-ci est utilisé
WO2021256036A1 (fr) * 2020-06-15 2021-12-23 株式会社カネカ Oxyde de type grenat conducteur d'ions lithium
CN115667180A (zh) * 2020-06-15 2023-01-31 株式会社钟化 锂离子传导性石榴石型氧化物
US11961962B2 (en) 2020-07-02 2024-04-16 Samsung Electronics Co., Ltd. Solid ion conductor compound, solid electrolyte including the same, electrochemical cell including the same, and preparation method thereof
US11735765B2 (en) 2021-01-08 2023-08-22 Samsung Electronics Co., Ltd. Solid ion conductor, solid electrolyte including the solid ion conductor, electrochemical device including the solid electrolyte, and method of preparing the solid ion conductor
JP2022185465A (ja) * 2021-06-02 2022-12-14 住友化学株式会社 リチウム含有酸化物及び固体電解質の製造方法
WO2022255413A1 (fr) 2021-06-02 2022-12-08 住友化学株式会社 Oxyde contenant du lithium et procédé de préparation d'électrolyte solide
JP7171826B1 (ja) 2021-06-02 2022-11-15 住友化学株式会社 リチウム含有酸化物及び固体電解質の製造方法

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