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WO2018131337A1 - Batterie tout solide et son procédé de fabrication - Google Patents

Batterie tout solide et son procédé de fabrication Download PDF

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Publication number
WO2018131337A1
WO2018131337A1 PCT/JP2017/043739 JP2017043739W WO2018131337A1 WO 2018131337 A1 WO2018131337 A1 WO 2018131337A1 JP 2017043739 W JP2017043739 W JP 2017043739W WO 2018131337 A1 WO2018131337 A1 WO 2018131337A1
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Prior art keywords
solid electrolyte
solid
negative electrode
layer
positive electrode
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PCT/JP2017/043739
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English (en)
Japanese (ja)
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渉平 鈴木
誠之 廣岡
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株式会社日立製作所
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Publication of WO2018131337A1 publication Critical patent/WO2018131337A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an all-solid-state battery and a manufacturing method thereof.
  • An all-solid lithium secondary battery using a non-flammable or flame-retardant solid electrolyte can have high heat resistance. Further, since there is no leakage of the electrolyte and the electrolyte does not volatilize, the safety of the battery can be improved. Therefore, the module cost can be reduced and the energy density can be increased.
  • an oxide solid electrolyte or a hydride-based solid electrolyte can be used as the solid electrolyte. Since the oxide solid electrolyte is electrochemically stable at the positive electrode potential and chemically stable in the air, a safe and highly heat-resistant battery can be produced. Further, the hydride-based solid electrolyte is excellent in reduction resistance, and can generally be used without forming a high resistance layer with a highly reducing material used for the negative electrode of a lithium ion secondary battery.
  • Patent Document 1 discloses an all-solid battery to which an oxide solid electrolyte and a hydride-based solid electrolyte are applied.
  • a crystalline solid electrolyte such as Li 3 BO 3 or LiVO 3 is used as the oxide solid electrolyte.
  • an object of the present invention is to provide a low-resistance all-solid battery.
  • an all solid state battery includes a positive electrode layer including a positive electrode active material and a first solid electrolyte, a negative electrode layer including a negative electrode active material and lithium hydride, a positive electrode layer, and a negative electrode.
  • FIG. 1 is a schematic cross-sectional view showing an all solid state battery according to an embodiment of the present invention. Schematic sectional view of a positive electrode layer, a solid electrolyte layer, and a negative electrode layer in one embodiment of the present invention Schematic sectional view of a positive electrode layer, a solid electrolyte layer, and a negative electrode layer in one embodiment of the present invention
  • FIG. 1 is a schematic cross-sectional view showing an all solid state battery according to an embodiment of the present invention.
  • An all-solid lithium ion secondary battery will be described as an all-solid battery.
  • the all solid lithium ion secondary battery 100 includes a negative electrode layer 40, a positive electrode layer 60, a solid electrolyte layer 50 disposed between the negative electrode layer 40 and the positive electrode layer 60, a negative electrode current collector 10, and a positive electrode current collector. 20 and a battery case 30 for storing them.
  • the negative electrode current collector 10 is electrically connected to the negative electrode layer 40.
  • the negative electrode current collector 10 for example, a copper foil having a thickness of 10 to 100 ⁇ m, a copper perforated foil having a thickness of 10 to 100 ⁇ m and a pore diameter of 0.1 to 10 mm, an expanded metal, and a foam metal plate are used. In addition to copper, those formed of stainless steel, titanium, nickel or the like are also applicable.
  • any current collector can be used without being limited by the material, shape, manufacturing method and the like.
  • the positive electrode current collector 20 is electrically connected to the positive electrode layer 60.
  • an aluminum foil having a thickness of 10 to 100 ⁇ m, an aluminum perforated foil having a thickness of 10 to 100 ⁇ m and a pore diameter of 0.1 to 10 mm, an expanded metal, a foam metal plate, or the like is used.
  • aluminum those formed of stainless steel, titanium or the like are also applicable.
  • any current collector can be used without being limited by the material, shape, manufacturing method and the like.
  • Battery case 30 accommodates negative electrode current collector 10, positive electrode current collector 20, negative electrode layer 40, solid electrolyte layer 50, and positive electrode layer 60.
  • the shape of the battery case 30 is selected according to the shape of the electrode group composed of the positive electrode layer 60, the solid electrolyte layer 50, and the negative electrode layer 40, such as a cylindrical shape, a flat oval shape, a flat oval shape, and a square shape. Also good.
  • the material of the battery case 30 may be any material that is corrosion resistant to the nonaqueous electrolyte. Examples of the battery case material include aluminum, stainless steel, and nickel-plated steel.
  • FIG. 2 is a schematic cross-sectional view of a positive electrode layer, a solid electrolyte layer, and a negative electrode layer in one embodiment of the present invention.
  • the solid electrolyte layer 50 is sandwiched between the negative electrode layer 40 and the positive electrode layer 60.
  • the negative electrode layer 40 includes at least a negative electrode active material 41 and a lithium hydride 42.
  • the lithium hydride 42 is dispersed between the particles of the negative electrode active material. When the lithium hydride 42 enters between the particles of the negative electrode active material, the conductivity of lithium ions is increased.
  • the negative electrode layer 40 may contain a conductive additive or a binder 43. By including a conductive additive, the electron conductivity in the negative electrode can be improved. Moreover, the mechanical strength of an electrode can be improved by including a binder.
  • the positive electrode layer 60 includes at least a positive electrode active material 61 and a first solid electrolyte 62.
  • the first solid electrolyte is dispersed between the positive electrode active material particles. When the first solid electrolyte is dispersed and filled so as to fill the gaps between the particles of the positive electrode active material, an electrode with low resistance can be obtained.
  • the positive electrode layer 60 may contain a conductive additive or a binder 63.
  • the solid electrolyte layer 50 includes at least a second solid electrolyte 51.
  • a crystalline oxide electrolyte 52 may be included.
  • the first solid electrolyte 62 and the second solid electrolyte 51 are made of an oxide represented by the general formula Li x A y O z (A is at least one of S, B, C, P, Al, and Ti). Contains glass.
  • This solid electrolyte material has a lower Young's modulus than other oxide-based solid electrolytes. Therefore, the interface between the electrode layer and the solid electrolyte layer can be densely formed. As a result, the interface resistance between the electrode layer and the solid electrolyte layer can be reduced. Moreover, a battery can be produced only by pressing without firing at a high temperature.
  • FIG. 3 is a schematic cross-sectional view of a positive electrode layer, a solid electrolyte layer, and a negative electrode layer in another embodiment.
  • the configuration of the negative electrode layer 40 is different from the schematic cross-sectional view of FIG.
  • the negative electrode layer 40 is composed of a layer containing a negative electrode active material and a layer containing a lithium hydride 42. That is, the negative electrode active material and the lithium hydride are laminated in layers to form the negative electrode layer 40.
  • the layer containing lithium hydride is formed on the solid electrolyte layer side.
  • the interface resistance between the negative electrode layer and the solid electrolyte layer can be reduced.
  • the thickness of the lithium hydride layer is preferably 10 ⁇ m or less.
  • the configuration shown in FIG. 3 is suitable when metallic lithium or metallic indium is used as the negative electrode active material.
  • the positive electrode layer 60 includes a positive electrode active material 61 and a first solid electrolyte 62. In addition to the positive electrode active material and the first solid electrolyte, a conductive additive and a positive electrode binder may be included.
  • the positive electrode active material 61 may contain one or more of the above materials. In the positive electrode active material 61, lithium ions are desorbed in the charging process, and lithium ions desorbed from the negative electrode active material in the negative electrode layer 40 are inserted in the discharging process.
  • the particle diameter of the positive electrode active material 61 is normally defined so as to be equal to or less than the thickness of the positive electrode layer 60. If the positive electrode active material 61 powder has coarse particles having a size equal to or greater than the thickness of the mixture layer, the coarse particles are removed in advance by sieving or airflow classification to produce particles having a thickness of the mixture layer or less. Is preferred.
  • a glass containing an oxide represented by a general formula Li x A y O z (A is at least one of S, B, C, P, Al, and Ti) can be used.
  • the glass described above has high lithium ion conductivity, exhibits good oxidation resistance with respect to the potential of the positive electrode active material 61, and can enter the gaps between the positive electrode active materials 61.
  • the glass may be partially crystallized.
  • the Young's modulus of the first solid electrolyte is preferably lower than 100 GPa, more preferably lower than 70 GPa.
  • a material having a Young's modulus lower than 100 GPa is easily deformed by pressure and can easily enter the voids of the positive electrode active material.
  • the first solid electrolyte is preferably a glass containing at least two of Li 3 BO 3 , Li 2 CO 3 and Li 2 SO 4 .
  • Li 3 BO 3 —Li 2 SO 4 —Li 2 CO 3 glass or Li 3 BO 3 —Li 2 CO 3 glass can be used.
  • P 2 O 5 , B 2 O 3 , SiO 2 , Al 2 O 3 and the like can be further added to these glasses.
  • oxides such as Li 3 PO 4 and Li 4 SiO 4 and lithium halides such as LiI, LiCl, and LiF may be added.
  • the Li concentration of the first solid electrolyte is preferably not less than the Li concentration of the positive electrode active material. By setting the Li concentration of the first solid electrolyte to be equal to or higher than the Li concentration of the positive electrode active material, it is possible to suppress the generation of the high resistance material due to the side reaction.
  • the glass containing an oxide represented by the general formula Li x A y O z can form a dense positive electrode layer by applying pressure.
  • the glass material is fluidized by heating at a glass transition temperature Tg1 or higher. Therefore, it becomes easy to fill the space between the active materials with the first solid electrolyte by using the glass material.
  • the glass transition temperature Tg1 of the first solid electrolyte is preferably equal to or lower than the glass transition temperature Tg2 of the second solid electrolyte described later.
  • the glass transition temperature T g1 of the first solid electrolyte than the second solid electrolyte glass transition temperature T g2 of it can be hot pressed at a temperature below T g1 or T g2.
  • T g1 or more and less than T g2 By hot pressing at a temperature of T g1 or more and less than T g2, the shape change of the solid electrolyte layer can be suppressed and a dense positive electrode layer can be obtained.
  • glass transition temperature Tg1 is less than melting
  • the difference of the sulfur component contained in the glass containing the oxide represented by this is demonstrated.
  • the sulfur component in the sulfide solid electrolyte is S 2 ⁇ , which may react with moisture in the air to produce H 2 S having the same sulfur component.
  • the sulfur component contained in Li 2 SO 4 is S 6+ and is stable against moisture and does not generate H 2 S.
  • the positive electrode layer may contain another solid electrolyte in addition to the first solid electrolyte.
  • oxonitride glass such as Li—P—O—N or Li—B—O—N can be mixed in the positive electrode layer.
  • the positive electrode active material 61 is generally oxide-based and has high electric resistance
  • a conductive auxiliary agent for supplementing electric conductivity may be used.
  • the positive electrode layer 60 includes a positive electrode conductive agent or a positive electrode binder
  • examples of the positive electrode conductive agent include acetylene black, carbon black, and carbon materials such as graphite or amorphous carbon.
  • oxide particles exhibiting electronic conductivity such as indium-tin-oxide (ITO) and antimony-tin-oxide (ATO) can be used.
  • the positive electrode binder 63 having a binding ability can be mixed with the powder to bond the powders to each other and to be bonded to the positive electrode current collector 20 at the same time.
  • the positive electrode binder 63 include styrene-butadiene rubber, carboxymethyl cellulose, polyvinylidene fluoride (PVdF), and a mixture thereof.
  • the content of the first solid electrolyte and the positive electrode active material is preferably specified between 10:90 and 70:30 by weight.
  • the higher the active material ratio the higher the energy density of the battery, which is preferable.
  • the weight ratio of the first solid electrolyte and the positive electrode active material is more preferably between 20:80 and 60:40.
  • the negative electrode layer 40 includes a negative electrode active material 41 and a lithium hydride 42.
  • Examples of the negative electrode active material 41 include carbon materials capable of reversibly inserting and desorbing lithium ions, silicon-based materials such as Si and SiO, lithium titanate with or without a substitution element, lithium vanadium composite oxide, An alloy of lithium and metal, or lithium metal can be used.
  • Examples of the alloy of lithium and metal include an alloy of lithium and tin, aluminum, antimony, or the like.
  • the carbon material is made of natural graphite, a composite carbonaceous material in which a film is formed on natural graphite by a dry CVD method or a wet spray method, a resin material such as epoxy or phenol, or a pitch-based material obtained from petroleum or coal. And artificial graphite and non-graphitizable carbon material produced by firing.
  • the negative electrode active material 41 may contain one or more of the above materials. In the negative electrode active material 41, an insertion / extraction reaction or a conversion reaction of lithium ions proceeds in a charge / discharge process.
  • the particle size is usually specified so as to be equal to or less than the thickness of the negative electrode layer 40.
  • the coarse particles are removed in advance by sieving classification or wind classification to produce particles having a thickness equal to or smaller than the thickness of the negative electrode layer 40. It is preferable.
  • the particle size of the negative electrode active material 41 is 0.1 ⁇ m to 10 ⁇ m. The smaller the active material particle size, the shorter the Li diffusion distance in the active material, so that the battery resistance is lowered. However, agglomeration is likely to occur, so that the active material utilization rate is lowered.
  • an electrolyte material that is durable with respect to the negative electrode potential and that can enter the voids formed between the negative electrode active materials 41 can be used.
  • a compound represented by a composition formula Li (MH n ) and a solid solution of this compound and any of LiI, LiB, LiCl, and LiBH 4 can be used.
  • (MH n ) is a complex ion
  • M is a non-metallic element such as B or N or a metallic element such as Al or Ni.
  • Examples of (MH n ) include (NH 2 ) ⁇ , (BH 4 ) ⁇ and (AlH 4 ) ⁇ .
  • Li 2 B 12 H 12 or Li 2 B 10 H 10 can be used as the lithium hydride.
  • an alkali metal element or an alkaline earth metal element may be included.
  • acetylene black, carbon black, and carbon materials such as graphite or amorphous carbon can be used.
  • the negative electrode binder styrene-butadiene rubber, carboxymethyl cellulose, polyvinylidene fluoride (PVDF), a mixture thereof, or the like can be used.
  • the ratio of the negative electrode active material and the lithium hydride is preferably defined between 10:90 and 70:30 by weight.
  • the higher the active material ratio the higher the energy density of the battery, which is preferable.
  • the weight ratio of Li hydride to the negative electrode active material is more preferably between 20:80 and 60:40.
  • the proportion of the negative electrode active material in the negative electrode layer 40 is a value close to 100 by weight.
  • the solid electrolyte layer 50 includes at least a second solid electrolyte.
  • the second solid electrolyte is a glass containing an oxide represented by a general formula Li x A y O z (A is at least one of S, B, C, P, Al, and Ti).
  • This glass material has high lithium ion conductivity.
  • the Young's modulus is low, the interface between the electrode layer and the solid electrolyte can be formed densely, being easily deformed by pressure.
  • the Young's modulus of the second solid electrolyte is preferably lower than 100 GPa, more preferably lower than 70 GPa.
  • the second solid electrolyte is preferably a glass containing at least two of Li 3 BO 3 , Li 2 CO 3 and Li 2 SO 4 .
  • Li 3 BO 3 —Li 2 SO 4 —Li 2 CO 3 glass or Li 3 BO 3 —Li 2 CO 3 glass can be used.
  • P 2 O 5 , B 2 O 3 , SiO 2 , Al 2 O 3 and the like can be further added to these glass solid electrolyte materials.
  • oxides such as Li 3 PO 4 and Li 4 SiO 4 and lithium halides such as LiI, LiCl, and LiF may be added.
  • the Li concentration of the second solid electrolyte is preferably equal to or higher than the Li concentration of the first solid electrolyte. This is to prevent Li from diffusing from the first solid electrolyte to the second solid electrolyte and reducing the Li concentration of the first solid electrolyte.
  • the glass containing an oxide represented by the general formula Li x A y O z can form a dense electrolyte layer by applying pressure.
  • the thickness of the electrolyte layer is preferably in the range of 1 to 100 ⁇ m.
  • a short circuit can be suppressed by setting the thickness of the electrolyte layer to 1 ⁇ m or more.
  • the increase in battery resistance can be suppressed by setting the thickness of the electrolyte layer to 100 ⁇ m or less.
  • the solid electrolyte layer 50 may include other solid electrolytes in addition to the second solid electrolyte.
  • the solid electrolyte layer can be mixed with oxonitride glass such as Li—P—O—N or Li—B—O—N.
  • the solid electrolyte layer 50 may include a crystalline oxide electrolyte 52.
  • the crystalline oxide electrolyte 52 include Li 1 + x Ti 2-x Al x P 3 O 12 (hereinafter referred to as LATP) and Li 1 + y Ge 2-y Al y P 3 O 12 (hereinafter referred to as LAGP).
  • LATP Li 1 + x Ti 2-x Al x P 3 O 12
  • LAGP Li 1 + y Ge 2-y Al y P 3 O 12
  • garnet-type solid electrolytes such as NASICON type electrolytes and Li 7 La 3 Zr 2 O 12 (hereinafter referred to as LLZ). Since these solid electrolytes have high room temperature conductivity of about 1 ⁇ 10 ⁇ 3 S ⁇ cm ⁇ 1 , electrolyte resistance can be reduced.
  • the all solid state battery according to an embodiment can be manufactured, for example, by the following method.
  • a method for producing an all-solid-state battery comprising: a positive electrode mixture including a positive electrode active material and a first solid electrolyte; a second solid electrolyte; and a lithium hydride.
  • a fixed electrolyte and a positive electrode mixture are laminated in this order, and a pressurizing step of pressing at a temperature below the glass transition point of the second solid electrolyte and below the melting point of the lithium hydride 42, and lithium in the laminate obtained by the pressurizing step
  • a negative electrode bonding step of bonding a negative electrode active material layer to the hydride side
  • the shape change of the solid electrolyte layer can be suppressed by pressurizing at a temperature lower than the glass transition point of the second solid electrolyte. Moreover, it is preferable that the temperature in a pressurization process shall be less than melting
  • the pressure in the pressurizing step is preferably 300 MPa to 1000 MPa.
  • the atmosphere in the pressurizing step needs to contain no moisture, and is more preferably an inert atmosphere.
  • An all solid state battery may be produced by pressurizing at a temperature below the glass transition point of Li and a melting point of Li hydride.
  • the solid electrolyte material was prepared as follows.
  • Li 3 BO 3 —Li 2 CO 3 —Li 2 SO 4 glass Li 2 SO 4 .H 2 O was heated at 300 ° C. for 2 hours under Ar flow (0.3 L / min) to obtain dehydrated Li 2 SO 4 .
  • Li 3 BO 3 and Li 2 CO 3 were vacuum-dried overnight at 120 ° C.
  • Li 3 BO 3 , Li 2 SO 4 and Li 2 CO 3 were each collected at a molar ratio of 2: 3: 2, and mixed for 15 minutes on a mortar.
  • the resulting mixture was placed in a pot and sealed. This pot was placed in a planetary ball mill (FRITSCH P-7) and milled for 20 hours. In this way, Li 3 BO 3 —Li 2 CO 3 —Li 2 SO 4 glass was prepared.
  • the glass transition temperature of the prepared glass was determined by differential scanning calorimetry, and the temperature was about 200 ° C.
  • Li 3 BO 3 —Li 2 SO 4 glass Li 2 SO 4 and Li 3 BO 3 were dehydrated in the same manner as Li 3 BO 3 —Li 2 CO 3 —Li 2 SO 4 glass. Li 3 BO 3 and Li 2 SO 4 were each collected at a molar ratio of 9: 1 and mixed on a mortar for 15 minutes. The resulting mixture was placed in a pot and sealed. This pot was placed in a planetary ball mill (FRITSCH P-7) and milled for 20 hours. In this way, Li 3 BO 3 —Li 2 SO 4 glass was prepared. The glass transition temperature of the prepared glass was about 280 ° C.
  • LiCoO 2 (hereinafter referred to as LCO) coated with LiNbO 3 was used.
  • the thickness of the LiNbO 3 coating layer was about 6 nm.
  • LiNbO 3 coating was carried out using a tumbling fluidized coating apparatus (Paurec, MP-01).
  • a battery was fabricated in the Ar-substituted glove box as follows.
  • a hydride electrolyte, a second solid electrolyte, and a positive electrode mixture powder were sequentially deposited in a 10 mm diameter die and pressed at 25 ° C. and 700 MPa.
  • LiBH 4 manufactured by Aldrich was used as the hydride electrolyte
  • Li 3 BO 3 —Li 2 SO 4 glass was used as the second solid electrolyte.
  • metallic lithium was superimposed on the hydride electrolyte side of the obtained pellets, placed in a bipolar cell, and the battery was fabricated by crimping the four corners of the cell.
  • the produced battery was changed to 80 ° C., and the battery resistance was evaluated using an impedance analyzer (1252A, manufactured by Solartron). The battery resistance was measured and found to be 120 ⁇ ⁇ cm 2 .
  • a battery was produced in the same manner as in Example 1 except that the press temperature at the time of battery production was 200 ° C.
  • the battery resistance of the produced battery was 50 ⁇ ⁇ cm 2 .
  • a battery was fabricated in the same manner as in Example 1, except that the second solid electrolyte was Li 3 BO 3 —Li 2 CO 3 —Li 2 SO 4 glass.
  • the battery resistance of the produced battery was 120 ⁇ ⁇ cm 2 .
  • a battery was fabricated in the same manner as in Example 1 except that the first solid electrolyte used for the positive electrode mixture powder was Li 3 BO 3 —Li 2 SO 4 glass.
  • the battery resistance of the produced battery was 200 ⁇ ⁇ cm 2 .
  • Example 1 A battery was fabricated in the same manner as in Example 1 except that the hydride electrolyte was not applied.
  • the battery resistance of the produced battery was 4 ⁇ 10 5 ⁇ ⁇ cm 2 .
  • the first solid electrolyte used for the second solid electrolyte and the positive electrode mixture powder is a crystalline solid electrolyte Li 3 BO 3 —Li 2 CO 3.
  • lithium A battery was produced in the same manner as in Example 1 except that the hydride was bonded to the press.
  • the battery resistance of the produced battery was 1 ⁇ 10 5 ⁇ ⁇ cm 2 .
  • Example 3 A battery was fabricated in the same manner as in Example 1, except that the first solid electrolyte used for the positive electrode mixture powder was Li 3 BO 3 —Li 2 SO 4 glass and the press temperature was 280 ° C. The battery resistance of the produced battery was 2 ⁇ 10 4 ⁇ ⁇ cm 2 .
  • Li 3 BO 3 —Li 2 SO 4 glass was used for the first solid electrolyte
  • Li 3 BO 3 —Li 2 CO 3 —Li 2 SO 4 glass was used for the second solid electrolyte
  • the press temperature was 200 ° C.
  • a battery was fabricated in the same manner as Example 1 except for the above. The produced battery was short-circuited and the resistance could not be measured.
  • the positive electrode layer and the solid electrolyte layer are represented by the general formula Li x A y O z (A is at least one of S, B, C, P, Al, and Ti) as a solid electrolyte. It has been found that the battery resistance can be significantly reduced by using the oxide to be added and adding lithium hydride to the negative electrode layer. It was found that by configuring the battery with soft electrolytes, the interface resistance between the electrode layer and the solid electrolyte layer can be reduced, and a battery with low resistance can be provided.
  • Comparative Example 1 in which the negative electrode layer did not contain lithium hydride was a solid battery having a very high battery resistance of 4 ⁇ 10 5 ⁇ cm 2 . This is presumably because the interface resistance between the negative electrode layer and the solid electrolyte layer is high.
  • Comparative Example 2 in which a crystalline oxide solid electrolyte was used for the positive electrode layer and the solid electrolyte layer, good contact at the interface between the positive electrode layer and the solid electrolyte layer was not obtained by pressing, so that 1 ⁇ 10 5 ⁇ cm 2 is considered.
  • Examples 1 to 4 were pressurized at a temperature lower than the glass transition point of the second solid electrolyte.
  • the press temperature is lower than the glass transition point of the second solid electrolyte, the shape change of the solid electrolyte layer can be suppressed, and a short circuit can be prevented.
  • Example 2 was pressurized at a temperature below the glass transition point of the second solid electrolyte and above the glass transition point of the first solid electrolyte. Therefore, it is possible to cause the first solid electrolyte to undergo a glass transition while suppressing a change in the shape of the solid electrolyte layer. As a result, a dense positive electrode layer could be formed.

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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Conductive Materials (AREA)

Abstract

La présente invention vise à fournir une batterie tout solide ayant une faible résistance de batterie. À cette fin, la présente batterie tout solide est caractérisée en ce qu'elle possède : une couche d'électrode positive contenant un matériau actif d'électrode positive et un premier électrolyte solide ; une couche d'électrode négative contenant une matière active d'électrode négative et un hydrure de lithium ; et une couche d'électrolyte solide disposée entre la couche d'électrode positive et la couche d'électrode négative et contenant un deuxième électrolyte solide, le premier électrolyte solide et le second électrolyte solide étant un verre contenant un oxyde représenté par la formule générale LixAyOz (A est au moins un élément parmi S, B, C, P, Al, et Ti).
PCT/JP2017/043739 2017-01-13 2017-12-06 Batterie tout solide et son procédé de fabrication WO2018131337A1 (fr)

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JP2017003777A JP2020064701A (ja) 2017-01-13 2017-01-13 全固体電池、およびその製造方法
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109687016A (zh) * 2018-12-24 2019-04-26 郑州新世纪材料基因组工程研究院有限公司 一种锂离子固体电解质及其制备方法
CN111969252A (zh) * 2020-08-31 2020-11-20 蜂巢能源科技有限公司 固态电池及其制备方法
CN115377348A (zh) * 2022-09-30 2022-11-22 苏州清陶新能源科技有限公司 正极材料层、正极和锂离子电池
WO2024202357A1 (fr) * 2023-03-30 2024-10-03 株式会社村田製作所 Batterie à semi-conducteurs
WO2024202358A1 (fr) * 2023-03-30 2024-10-03 株式会社村田製作所 Batterie à électrolyte solide

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* Cited by examiner, † Cited by third party
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JP7634256B2 (ja) * 2021-01-08 2025-02-21 国立研究開発法人産業技術総合研究所 酸化物固体電解質、電極合材、および全固体リチウムイオン電池

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JP2009206090A (ja) * 2008-01-31 2009-09-10 Ohara Inc リチウムイオン二次電池の製造方法
WO2015151144A1 (fr) * 2014-03-31 2015-10-08 株式会社日立製作所 Batterie rechargeable au lithium tout solide
JP2016201310A (ja) * 2015-04-13 2016-12-01 株式会社日立製作所 全固体リチウム二次電池
WO2017002234A1 (fr) * 2015-07-01 2017-01-05 株式会社日立製作所 Dispositif de recherche de ressources souterraines et système de recherche de ressources souterraines
JP2017004910A (ja) * 2015-06-16 2017-01-05 株式会社日立製作所 リチウムイオン二次電池

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Publication number Priority date Publication date Assignee Title
JP2009206090A (ja) * 2008-01-31 2009-09-10 Ohara Inc リチウムイオン二次電池の製造方法
WO2015151144A1 (fr) * 2014-03-31 2015-10-08 株式会社日立製作所 Batterie rechargeable au lithium tout solide
JP2016201310A (ja) * 2015-04-13 2016-12-01 株式会社日立製作所 全固体リチウム二次電池
JP2017004910A (ja) * 2015-06-16 2017-01-05 株式会社日立製作所 リチウムイオン二次電池
WO2017002234A1 (fr) * 2015-07-01 2017-01-05 株式会社日立製作所 Dispositif de recherche de ressources souterraines et système de recherche de ressources souterraines

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109687016A (zh) * 2018-12-24 2019-04-26 郑州新世纪材料基因组工程研究院有限公司 一种锂离子固体电解质及其制备方法
CN111969252A (zh) * 2020-08-31 2020-11-20 蜂巢能源科技有限公司 固态电池及其制备方法
CN115377348A (zh) * 2022-09-30 2022-11-22 苏州清陶新能源科技有限公司 正极材料层、正极和锂离子电池
WO2024202357A1 (fr) * 2023-03-30 2024-10-03 株式会社村田製作所 Batterie à semi-conducteurs
WO2024202358A1 (fr) * 2023-03-30 2024-10-03 株式会社村田製作所 Batterie à électrolyte solide

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