WO2013137224A1 - Cellule entièrement électronique et son procédé de fabrication - Google Patents

Cellule entièrement électronique et son procédé de fabrication Download PDF

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WO2013137224A1
WO2013137224A1 PCT/JP2013/056729 JP2013056729W WO2013137224A1 WO 2013137224 A1 WO2013137224 A1 WO 2013137224A1 JP 2013056729 W JP2013056729 W JP 2013056729W WO 2013137224 A1 WO2013137224 A1 WO 2013137224A1
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solid electrolyte
solid
negative electrode
layer
electrolyte material
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PCT/JP2013/056729
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English (en)
Japanese (ja)
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剛司 林
倍太 尾内
充 吉岡
武郎 石倉
彰佑 伊藤
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株式会社 村田製作所
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Publication of WO2013137224A1 publication Critical patent/WO2013137224A1/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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/002—Inorganic electrolyte
    • 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 battery and a method for manufacturing the same.
  • the battery having the above configuration has a risk of leakage of the electrolyte.
  • the organic solvent etc. which are used for electrolyte solution are combustible substances. For this reason, it is required to further increase the safety of the battery.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2007-5279 proposes an all-solid lithium secondary battery in which all components are made of solid using a nonflammable solid electrolyte.
  • the solid electrolyte layer has a general formula Li 1 + X M III X Ti IV 2-X (PO 4 ) 3 (where M III is Al, Y, Ga, And at least one metal ion selected from the group consisting of In and La, wherein X is 0 ⁇ X ⁇ 0.6), and the negative electrode active material layer is FePO 4 ,
  • An all-solid lithium secondary battery composed of at least one phosphate compound selected from the group consisting of Li 3 Fe 2 (PO) 4 and LiFeP 2 O 7 is disclosed.
  • Patent Document 1 describes that the phosphoric acid compound constituting the solid electrolyte layer may also serve as the negative electrode active material layer.
  • Patent Document 2 International Publication No. 2008/143027 (hereinafter referred to as Patent Document 2) includes a laminate in which a positive electrode layer containing a positive electrode active material and a negative electrode layer containing a negative electrode active material are laminated via an electrolyte layer containing a solid electrolyte.
  • a multilayer all solid-state lithium ion secondary battery comprising a body is disclosed.
  • This lithium ion secondary battery has an intermediate layer made of a material that functions as an active material or an electrolyte at the interface between the positive electrode layer and / or the negative electrode layer and the electrolyte layer.
  • This intermediate layer is a layer formed by a reaction between the positive electrode active material and / or the negative electrode active material and the solid electrolyte.
  • Li 1 + X M III X Ti IV 2-X (PO 4 ) 3 constituting the solid electrolyte layer is derived from a redox reaction of titanium (Ti). It is known to produce a redox current that In addition, there are components that occur irreversibly as a result of the oxidation-reduction reaction.
  • a negative electrode active material and a solid electrolyte are formed at the interface between the negative electrode layer and the electrolyte layer, and function as a negative electrode active material or a solid electrolyte.
  • the electrode potential of the negative electrode active material is determined by the oxidation-reduction potential of a specific metal element contained in the negative electrode active material
  • the intermediate layer formed by the reaction between the negative electrode active material and the solid electrolyte is the negative electrode active material. It is difficult to have reduction resistance at the electrode potential of the substance. For this reason, there exists a problem that the charging / discharging efficiency of a battery falls.
  • an object of the present invention is to provide an all solid state battery capable of suppressing a decrease in charge / discharge efficiency of the battery and a method for manufacturing the same.
  • the all solid state battery according to the present invention includes a negative electrode layer, a solid electrolyte layer laminated on the negative electrode layer, and an intervening layer interposed between the negative electrode layer and the solid electrolyte layer.
  • the solid electrolyte layer includes a first solid electrolyte material
  • the intervening layer includes a second solid electrolyte material that is different from the first solid electrolyte material.
  • the second solid electrolyte material has a wider potential window than the first solid electrolyte material.
  • the potential window of the second solid electrolyte material includes a lithium potential.
  • the ion conductivity of the second solid electrolyte material is 1.0 ⁇ 10 ⁇ 6 S / cm or more.
  • the firing temperature of the second solid electrolyte material is 1000 ° C. or less.
  • the first solid electrolyte material and the second solid electrolyte material include a lithium-containing phosphate compound.
  • the first solid electrolyte material and the second solid electrolyte material contain a lithium-containing phosphate compound having a NASICON structure.
  • the negative electrode layer includes a third solid electrolyte material, and the second solid electrolyte material is the same as the third solid electrolyte material.
  • the first solid electrolyte material in Li x M y (PO 4) 3 ( Formula, x is 1 ⁇ x ⁇ 2, y is a number within a range of 1 ⁇ y ⁇ 2
  • M preferably contains a lithium-containing phosphate compound represented by the formula (1) containing at least one element selected from the group consisting of Ti, Ge, Al and Ga.
  • the second solid electrolyte material is Li x M1 y M2 z M3 w (PO 4 ) 3 (wherein x is 0.5 ⁇ x ⁇ 4 and y is 0 ⁇ y ⁇ 1).
  • Z is a numerical value in the range of 0 ⁇ z ⁇ 2
  • w is in the range of 0 ⁇ w ⁇ 2
  • M1 includes one or more elements selected from the group consisting of Mg, Ca, Ba and Sr
  • M2 is And one or more elements selected from the group consisting of Al, Cr, In, Sc and Y
  • M3 includes one or more elements selected from the group consisting of Zr, Hf, Nb and Ta). It is preferable to contain a lithium-containing phosphate compound.
  • the negative electrode layer includes a negative electrode active material, and the negative electrode active material includes a compound or an alloy.
  • the negative electrode active material contains a compound
  • the negative electrode active material is one or more selected from the group consisting of TiO 2 , Cr 2 O 3 , Fe 2 O 3 , Fe 3 O 4 , MoO 2, and Nb 2 O 5 . It is preferable that an oxide is included.
  • the negative electrode active material preferably contains silicon or tin.
  • the negative electrode active material preferably contains one or more selected from the group consisting of silicon, silicon oxide, silicon-containing alloy, silicon-containing compound, tin, tin oxide, tin-containing alloy and tin-containing compound. .
  • the manufacturing method of the all-solid battery according to the present invention includes the following steps and features.
  • the second solid electrolyte material has a wider potential window than the first solid electrolyte material.
  • the unfired negative electrode layer, the unfired solid electrolyte layer, and the unfired intervening layer only have to be in the form of a green sheet or a printed layer.
  • the intervening layer interposed between the negative electrode layer and the solid electrolyte layer includes the second solid electrolyte material having a wider potential window than the first solid electrolyte material included in the solid electrolyte layer. It is difficult to reduce at the electrode potential of the negative electrode active material, and functions as a reduction-resistant layer that electrically separates the negative electrode layer and the solid electrolyte layer. Thereby, the fall of the charging / discharging efficiency of a battery can be suppressed.
  • the all-solid battery stack 10 of the present invention includes a positive electrode layer 11, a solid electrolyte layer 13, an intervening layer 14, and a negative electrode layer 12 that are sequentially stacked.
  • the intervening layer 14 is interposed between the negative electrode layer 12 and the solid electrolyte layer 13.
  • the all-solid-state battery laminate 10 is formed of, for example, a rectangular parallelepiped shape and a laminate composed of a plurality of flat layers having a rectangular plane, or a laminate composed of a plurality of disk-shaped layers formed in a cylindrical shape. It is formed.
  • Each of the positive electrode layer 11 and the negative electrode layer 12 includes a solid electrolyte and an electrode active material
  • the solid electrolyte layer 13 includes a solid electrolyte.
  • the solid electrolyte layer 13 includes a first solid electrolyte material as a solid electrolyte, and the intervening layer 14 includes a second solid electrolyte material having a wider potential window than the first solid electrolyte material as a solid electrolyte.
  • Each of the positive electrode layer 11 and the negative electrode layer 12 may contain carbon, a metal, an oxide, etc. as an electronic conductive material.
  • the potential window of the second solid electrolyte material included in the intervening layer 14 is larger than the potential window of the first solid electrolyte material included in the solid electrolyte layer 13.
  • reductive decomposition of the first solid electrolyte material can be suppressed, and a decrease in charge / discharge efficiency can be suppressed. That is, even if the negative electrode layer 12 is configured using a negative electrode active material having a charge / discharge potential equal to or lower than the decomposition voltage of the first solid electrolyte material, reductive decomposition of the first solid electrolyte material can be suppressed, A decrease in discharge efficiency can be suppressed.
  • the potential window of the second solid electrolyte material contains a potential of lithium.
  • the ion conductivity of the second solid electrolyte material is preferably 1.0 ⁇ 10 ⁇ 6 S / cm or more.
  • the firing temperature of the second solid electrolyte material is preferably 1000 ° C. or lower.
  • the firing temperature of the second solid electrolyte material it becomes possible to perform firing below the volatilization temperature of lithium, so that a dense all-solid battery can be obtained.
  • the first solid electrolyte material and the second solid electrolyte material contain a lithium-containing phosphate compound.
  • a lithium-containing phosphate compound having a NASICON structure can be used as the lithium-containing phosphate compound contained in the first solid electrolyte material and the second solid electrolyte material.
  • the negative electrode layer 12 includes a third solid electrolyte material, and the second solid electrolyte material included in the intervening layer 14 is the same as the third solid electrolyte material. . By doing in this way, the lifetime of an all-solid-state battery can be improved.
  • the first solid electrolyte material included in the solid electrolyte layer 13 or the solid electrolyte material included in the positive electrode layer 11 or the negative electrode layer 12 includes lithium having a NASICON structure.
  • Phosphoric acid compounds can be used.
  • Lithium-containing phosphoric acid compound having a NASICON-type structure the chemical formula Li x M y (PO 4) 3 ( Formula, x 1 ⁇ x ⁇ 2, y is a number in the range of 1 ⁇ y ⁇ 2, M Includes one or more elements selected from the group consisting of Ti, Ge, Al, Ga and Zr).
  • Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 , Li 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 and the like.
  • part of P in the above chemical formula may be substituted with B, Si, or the like.
  • two or more compounds having different compositions of lithium-containing phosphate compounds having a NASICON type structure such as Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 and Li 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 are mixed. You may use the mixture.
  • the second solid electrolyte material contained in the intervening layer 14 is Li x M1 y M2 z M3 w (PO 4 ) 3 (wherein x is 0.5 ⁇ x ⁇ 4, y is 0 ⁇ y ⁇ 1, z is 0 ⁇ z ⁇ 2, w is a numerical value within the range of 0 ⁇ w ⁇ 2, and M1 is selected from the group consisting of Mg, Ca, Ba and Sr One or more elements are included, M2 includes one or more elements selected from the group consisting of Al, Cr, In, Sc and Y, and M3 is selected from the group consisting of Zr, Hf, Nb and Ta A lithium-containing phosphoric acid compound having a NASICON structure represented by the formula (including one or more elements). For example, Li 1.0 Al 1.0 Ta 1.0 (PO 4 ) 3 , Li 1.0 Zr 2.0 (PO 4 ) 3 and the like. In this case, part of P
  • the negative electrode layer 12 includes a negative electrode active material, and a compound or alloy capable of inserting and extracting lithium ions can be used as the negative electrode active material.
  • the negative electrode active material contains a compound
  • the negative electrode active material is one or more selected from the group consisting of TiO 2 , Cr 2 O 3 , Fe 2 O 3 , Fe 3 O 4 , MoO 2, and Nb 2 O 5 . It is preferable that an oxide is included.
  • the laminate of the negative electrode layer 12 and the intervening layer 14 can be produced by integral firing without causing a solid phase reaction with the lithium-containing phosphate compound having a NASICON structure contained in the intervening layer 14.
  • the negative electrode active material preferably contains silicon or tin.
  • the negative electrode active material preferably contains one or more selected from the group consisting of silicon, silicon oxide, silicon-containing alloy, silicon-containing compound, tin, tin oxide, tin-containing alloy and tin-containing compound. . By doing so, it is possible to realize high voltage and high capacity of the all solid state battery.
  • Examples of the lithium-containing phosphate compound having a NASICON structure used in the first solid electrolyte material and the second solid electrolyte material include a crystal phase of a lithium-containing phosphate compound having a NASICON structure, or You may use the glass which precipitates the crystal phase of the lithium containing phosphoric acid compound which has a NASICON structure by heat processing.
  • the type of the positive electrode active material included in the positive electrode layer 11 is not limited, but examples of the positive electrode active material include lithium-containing phosphate compounds having a Nasicon type structure such as Li 3 V 2 (PO 4 ) 3 , LiFePO 4 , LiMnPO 4 .
  • a lithium-containing compound having a spinel structure such as Ti 5 O 12 can be used.
  • an unfired positive electrode layer that is an unfired body of the positive electrode layer 11 and an unfired body that is an unfired body of the negative electrode layer 12 are used.
  • a sintered negative electrode layer, an unsintered solid electrolyte layer that is an unsintered body of the solid electrolyte layer 13 that includes the first solid electrolyte material, and an unsintered intermediate that is an unsintered body of the intervening layer 14 that includes the second solid electrolyte material A layer is produced (unfired layer production process).
  • an unfired intervening layer containing a second solid electrolyte material having a potential window wider than that of the first solid electrolyte material is produced. Thereafter, the produced unfired positive electrode layer, unfired solid electrolyte layer, and unfired negative electrode layer are laminated with an unfired intervening layer interposed between the unfired negative electrode layer and the unfired solid electrolyte layer. A body is formed (laminated body forming step). And the obtained laminated body is baked (baking process). The positive electrode layer 11, the solid electrolyte layer 13, the intervening layer 14, and the negative electrode layer 12 are joined by firing. Finally, the fired laminate is sealed, for example, in a coin cell.
  • the sealing method is not particularly limited. For example, you may seal the laminated body after baking with resin. Alternatively, an insulating paste having an insulating property such as Al 2 O 3 may be applied or dipped around the laminate, and the insulating paste may be heat-treated for sealing.
  • a current collector layer such as a carbon layer, a metal layer, or an oxide layer may be formed on the positive electrode layer 11 and the negative electrode layer 12.
  • Examples of the method for forming the current collector layer include a sputtering method.
  • the metal paste may be applied or dipped and heat-treated.
  • the green body of the single battery structure can be formed by laminating the green body of the positive electrode layer 11, the solid electrolyte layer 13, the intervening layer 14, and the negative electrode layer 12. Furthermore, in the laminated body forming step, a laminated body may be formed by laminating a plurality of laminated bodies having the above single cell structure with an unfired body of the current collector interposed therebetween. In this case, a plurality of laminates having a single battery structure may be laminated electrically in series or in parallel.
  • the method for forming the unfired positive electrode layer, the unfired negative electrode layer, the unfired solid electrolyte layer, and the unfired intervening layer is not particularly limited, but a doctor blade method, a die coater, a comma coater, etc. to form a green sheet, Or screen printing etc. can be used in order to form a printing layer.
  • the method for laminating the above-mentioned unfired positive electrode layer, unfired solid electrolyte layer, unfired intervening layer, and unfired negative electrode layer is not particularly limited, but hot isostatic pressing, cold isostatic pressing, isostatic pressing Etc. can be used to laminate the unfired positive electrode layer, unfired solid electrolyte layer, unfired intervening layer, and unfired negative electrode layer.
  • the slurry for forming the green sheet or the printing layer includes an organic vehicle in which an organic material is dissolved in a solvent, and a positive electrode active material and a solid electrolyte, a negative electrode active material and a solid electrolyte, a first solid electrolyte material, and a second solid.
  • Electrolyte material or current collector material can be prepared by wet mixing. Media can be used in wet mixing, and specifically, a ball mill method, a viscomill method, or the like can be used. On the other hand, a wet mixing method that does not use media may be used, and a sand mill method, a high-pressure homogenizer method, a kneader dispersion method, or the like can be used.
  • the organic material contained in the slurry for forming the green sheet or the printing layer is not particularly limited, and polyvinyl acetal resin, cellulose resin, acrylic resin, urethane resin, and the like can be used.
  • the slurry may contain a plasticizer.
  • plasticizer is not particularly limited, phthalic acid esters such as dioctyl phthalate and diisononyl phthalate may be used.
  • the atmosphere is not particularly limited, but it is preferably performed under conditions that do not change the valence of the transition metal contained in the electrode active material.
  • the firing temperature is preferably 400 ° C. or higher and 1000 ° C. or lower.
  • Example shown below is an example and this invention is not limited to the following Example.
  • Example 1 As a first solid electrolyte material included in the solid electrolyte layer, Li 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 which is a lithium-containing titanium phosphate compound having a NASICON structure, a second solid electrolyte material included in the intervening layer (hereinafter, Li 1.2 Ca 0.1 Zr 1.9 (PO 4 ) 3 , which is a lithium-containing zirconium phosphate compound having a NASICON structure, was used as the solid electrolyte A), and Nb 2 O 5 was used as the electrode active material contained in the negative electrode layer.
  • Li 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 which is a lithium-containing titanium phosphate compound having a NASICON structure
  • a second solid electrolyte material included in the intervening layer hereinafter, Li 1.2 Ca 0.1 Zr 1.9 (PO 4 ) 3 , which is a lithium-containing zirconium phosphate compound having a NASICON structure, was used as
  • a solid electrolyte A was produced as follows.
  • Lithium carbonate (Li 2 CO 3 ), zirconium oxide (ZrO 2 ), calcium hydroxide (Ca (OH) 2 ), diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ) are used as raw materials, and these are in a molar ratio. 10.7% -Li 2 CO 3 , 1.8% -Ca (OH) 2 , 33.9% -ZrO 2 , 53.6%-(NH 4 ) 2 HPO 4 and weighed 500 ml
  • a raw material mixed powder was prepared by enclosing the container in a polyethylene container and rotating the container at a rotation speed of 150 rpm for 6 hours.
  • the fired powder A was produced by firing the mixed powder of the raw material obtained above in an air atmosphere at a temperature of 400 ° C. for 2 hours (firing step 1).
  • the obtained pulverized powder A was fired in an air atmosphere at a temperature of 800 ° C. for 2 hours (firing step 2) to produce a solid electrolyte powder A.
  • the X-ray diffraction pattern of the solid electrolyte powder A obtained above was measured using an X-ray diffractometer (XRD) at a scanning speed of 1.0 ° / min and an angle measurement range of 10 ° to 60 °. .
  • the measured X-ray diffraction pattern of the solid electrolyte powder A is shown in FIG.
  • FIG. 2 shows the X-ray diffraction pattern of a JCPDS (Joint Committee on Powder Diffraction Standards) card (card number: 84-0998) of LiZr 2 (PO 4 ) 3 which is a NASICON type lithium-containing zirconium phosphate compound. Show.
  • the X-ray diffraction pattern of the solid electrolyte powder A almost matches the X-ray diffraction pattern of LiZr 2 (PO 4 ) 3 , and the solid electrolyte powder A is a lithium-containing zirconium phosphate compound having a NASICON structure. It was confirmed.
  • a solid electrolyte slurry is prepared by mixing the binder solution and glass powder of Li 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 which is an example of a NASICON type lithium-containing phosphate compound as a first solid electrolyte material. 1 was produced. The mixing ratio of the above glass powder and polyvinyl alcohol was 70:30 by weight.
  • the solid electrolyte slurry 2 was produced by mixing the binder solution and the solid electrolyte powder A obtained above as the second solid electrolyte material.
  • the mixing ratio of the solid electrolyte powder A and polyvinyl alcohol was 70:30 by weight.
  • the negative electrode active material slurry 1 and the solid electrolyte slurry 2 obtained above are mixed so that the mixing ratio of Nb 2 O 5 and the solid electrolyte powder A is 50:50 by weight, thereby preparing the negative electrode slurry 1. did.
  • Each of the obtained negative electrode slurry 1, solid electrolyte slurry 1, and solid electrolyte slurry 2 is formed into a thickness of 50 ⁇ m by a doctor blade method, thereby forming a negative electrode layer sheet 1 as a green sheet, a solid electrolyte layer sheet 1, And the intervening layer sheet
  • cyclic voltammetry was measured. The measurement was performed as follows. First, after sweeping from the open circuit voltage to 0 V at 0.1 mV / sec, the voltage was held at 0 V for 5 hours. Thereafter, it was rested for 3 hours, swept from the rest potential to 3V at 0.1 mV / sec, and then held at 3V for 5 hours.
  • FIG. 3 shows a cyclic voltammetry measurement result of the reduction resistance evaluation cell 1 as an example. From FIG. 3, it was confirmed that the solid electrolyte A was electrochemically stable up to the potential of lithium.
  • the intervening layer sheet 1 cut into a circular shape with a diameter of 12 mm is laminated on one side of the solid electrolyte layer sheet 1 cut into a circular shape with a diameter of 12 mm, and a pressure of 1 ton is applied at a temperature of 80 ° C. Then, the negative electrode layer sheet 1 cut into a circular shape having a diameter of 12 mm was laminated thereon, and thermocompression bonding was performed by applying a pressure of 1 ton at a temperature of 80 ° C.
  • a negative electrode-electrolyte laminate A as a molded body constituting the all-solid battery was prepared.
  • the negative electrode layer sheet 1 cut into a circular shape with a diameter of 12 mm is laminated on one side of the solid electrolyte layer sheet 1 cut into a circular shape with a diameter of 12 mm, and a pressure of 1 ton at a temperature of 80 ° C. was added and thermocompression bonded to produce a negative electrode-electrolyte laminate B as a molded body constituting the all-solid-state battery of Comparative Example 1.
  • Cyclic voltammetry was measured using all solid state batteries A and B. As a result, the current-voltage curve of the obtained all-solid battery A is shown in FIG. 4, and the current-voltage curve of the all-solid battery B is shown in FIG.
  • the measurement was performed as follows. First, after sweeping from an open circuit voltage to 1.2 V at 0.1 mV / sec, the voltage was held at 1.2 V for 5 hours. Thereafter, it was rested for 3 hours, swept from the rest potential to 3V at 0.1 mV / sec, and then held at 3V for 5 hours.
  • the all solid state batteries A and B were charged and discharged at a constant current and a constant voltage at a current density of 20 ⁇ A / cm 2 in a voltage range of 1.2 to 3V.
  • the charge / discharge curve of the obtained all-solid battery A is shown in FIG. 6, and the charge / discharge curve of the all-solid battery B is shown in FIG.
  • the discharge capacity of the all-solid-state battery B includes Li 1.2 Al 0.2 Ti 1.8 (PO), which is a lithium-containing titanium phosphate compound having a NASICON type structure contained in the solid electrolyte layer, in addition to the capacity of Nb 2 O 5 as the negative electrode active material. 4 ) It can be seen that the reduction capacity of 3 is included.
  • Example 2 As a first solid electrolyte material included in the solid electrolyte layer, Li 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 which is a lithium-containing titanium phosphate compound having a NASICON structure, a second solid electrolyte material included in the intervening layer (hereinafter, As a solid electrolyte B), Li 1.0 Zr 2.0 (PO 4 ) 3 , which is a lithium-containing zirconium phosphate compound having a NASICON structure, and Nb 2 O 5 as an electrode active material contained in the negative electrode layer were used.
  • a solid electrolyte B Li 1.0 Zr 2.0 (PO 4 ) 3 , which is a lithium-containing zirconium phosphate compound having a NASICON structure, and Nb 2 O 5 as an electrode active material contained in the negative electrode layer were used.
  • a solid electrolyte B was produced as follows.
  • Lithium carbonate (Li 2 CO 3 ), zirconium oxide (ZrO 2 ), diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ) were used as raw materials, and these were in a molar ratio of 9.1% -Li 2 CO 3 , By weighing to 36.4% -ZrO 2 , 54.5%-(NH 4 ) 2 HPO 4 , sealing in a 500 ml polyethylene container, and rotating the container at 150 rpm for 6 hours A mixed powder of raw materials was prepared.
  • the fired powder B was produced by firing the mixed powder of the raw materials obtained above in an air atmosphere at a temperature of 400 ° C. for 2 hours (firing step 1).
  • the obtained pulverized powder B was fired in an air atmosphere at a temperature of 800 ° C. for 2 hours (firing step 2) to produce a solid electrolyte powder B.
  • the X-ray diffraction pattern of the solid electrolyte powder B obtained above was measured using an X-ray diffractometer (XRD) at a scan rate of 1.0 ° / min and an angle measurement range of 10 ° to 60 °. .
  • the measured X-ray diffraction pattern of the solid electrolyte powder B is shown in FIG.
  • FIG. 8 shows the X-ray diffraction pattern of a JCPDS (Joint Committee on Powder Diffraction Standards) card (card number: 84-0998) of LiZr 2 (PO 4 ) 3 which is a NASICON type lithium-containing zirconium phosphate compound. Show.
  • the X-ray diffraction pattern of the solid electrolyte powder B almost coincides with the X-ray diffraction pattern of LiZr 2 (PO 4 ) 3 , and the solid electrolyte powder B is a lithium-containing zirconium phosphate compound having a NASICON type structure. It was confirmed.
  • a solid electrolyte slurry is prepared by mixing the binder solution and glass powder of Li 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 which is an example of a NASICON type lithium-containing phosphate compound as a first solid electrolyte material. 1 was produced. The mixing ratio of the above glass powder and polyvinyl alcohol was 70:30 by weight.
  • a solid electrolyte slurry 3 was prepared by mixing the binder solution and the solid electrolyte powder B obtained above as the second solid electrolyte material.
  • the mixing ratio of the solid electrolyte powder B and polyvinyl alcohol was 70:30 by weight.
  • the negative electrode active material slurry 1 and the solid electrolyte slurry 3 obtained above are mixed so that the mixing ratio of Nb 2 O 5 and the solid electrolyte powder B is 50:50 by weight, thereby preparing the negative electrode slurry 2. did.
  • Each of the obtained negative electrode slurry 2, solid electrolyte slurry 1, and solid electrolyte slurry 3 was formed into a thickness of 50 ⁇ m by a doctor blade method, thereby forming a negative electrode layer sheet 2, a solid electrolyte layer sheet 1, as a green sheet, And the intervening layer sheet
  • seat 2 was produced.
  • a plurality of intervening layer sheets 2 cut into a circular shape having a diameter of 12 mm are stacked, and subjected to thermocompression bonding by applying a pressure of 1 ton at a temperature of 80 ° C.
  • the laminated body 2 was produced. After firing the laminate 2 in an oxygen gas atmosphere at a temperature of 500 ° C. for 2 hours, the laminate 2 is fired in a nitrogen gas atmosphere for 2 hours at a temperature of 900 ° C. Produced.
  • Cyclic voltammetry was measured using the reduction resistance evaluation cell 2. The measurement was performed as follows. First, after sweeping from the open circuit voltage to 0 V at 0.1 mV / sec, the voltage was held at 0 V for 5 hours. Thereafter, it was rested for 3 hours, swept from the rest potential to 3V at 0.1 mV / sec, and then held at 3V for 5 hours.
  • FIG. 9 shows a cyclic voltammetry measurement result for the reduction resistance evaluation cell 2 as an example. From FIG. 9, it was confirmed that the solid electrolyte B was electrochemically stable up to the potential of lithium.
  • the intervening layer sheet 2 cut into a circular shape with a diameter of 12 mm is laminated on one side of the solid electrolyte layer sheet 1 cut into a circular shape with a diameter of 12 mm, and a pressure of 1 ton is applied at a temperature of 80 ° C. Then, the negative electrode layer sheet 2 cut into a circular shape having a diameter of 12 mm was laminated thereon, and thermocompression bonded by applying a pressure of 1 ton at a temperature of 80 ° C.,
  • Example 2 A negative electrode-electrolyte laminate C as a molded body constituting the all solid state battery was prepared.
  • the all solid state battery C was charged and discharged at a constant current and a constant voltage at a current density of 20 ⁇ A / cm 2 in a voltage range of 1.2 to 3V. As a result, the charge / discharge curve of the obtained all-solid-state battery C is shown in FIG.
  • the discharge capacity of the all-solid-state battery B includes Li 1.2 Al 0.2 Ti 1.8 (PO), which is a lithium-containing titanium phosphate compound having a NASICON type structure contained in the solid electrolyte layer, in addition to the capacity of Nb 2 O 5 as the negative electrode active material. 4 ) It can be seen that the reduction capacity of 3 is included.
  • Example 3 As a first solid electrolyte material included in the solid electrolyte layer, Li 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 which is a lithium-containing titanium phosphate compound having a NASICON structure, a second solid electrolyte material included in the intervening layer (hereinafter, As the solid electrolyte C), Li 1.0 Al 1.0 Ta 1.0 (PO 4 ) 3 , which is a lithium-containing tantalum phosphate compound having a NASICON structure, and Nb 2 O 5 as an electrode active material contained in the negative electrode layer were used.
  • a solid electrolyte C was produced as follows.
  • Lithium carbonate (Li 2 CO 3 ), aluminum oxide (Al 2 O 3 ), tantalum oxide (Ta 2 O 5 ), diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ) are used as raw materials, and these are in a molar ratio.
  • NH 4 ) 2 HPO 4 diammonium hydrogen phosphate
  • 11.1% -Li 2 CO 3 , 11.1% -Al 2 O 3 , 11.1% -Ta 2 O 5 , 66.7%-(NH 4 ) 2 HPO 4 The mixture powder of the raw material was produced by enclosing in a 500 ml polyethylene container, and rotating the container for 6 hours at the rotation speed of 150 rpm.
  • the fired powder C was produced by firing the mixed powder of the raw material obtained above in an air atmosphere at a temperature of 800 ° C. for 2 hours (firing step 1).
  • the obtained pulverized powder C was fired in an air atmosphere at a temperature of 800 ° C. for 2 hours (firing step 2) to produce a solid electrolyte powder C.
  • the X-ray diffraction pattern of the solid electrolyte powder C obtained above was measured using an X-ray diffractometer (XRD) at a scanning speed of 1.0 ° / min and an angle measurement range of 10 ° to 60 °. .
  • the measured X-ray diffraction pattern of the solid electrolyte powder C is shown in FIG. FIG. 11 also shows an X-ray diffraction pattern of a JCPDS (Joint Committee on Powder Diffraction Standards) card (card number: 25-0986) of TiTa (PO 4 ) 3 which is a NASICON type tantalum phosphate compound.
  • JCPDS Joint Committee on Powder Diffraction Standards
  • the X-ray diffraction pattern of the solid electrolyte powder C almost coincides with the X-ray diffraction pattern of TiTa (PO 4 ) 3 , and the solid electrolyte powder C is a lithium-containing tantalum phosphate compound having a NASICON structure.
  • a solid electrolyte slurry is prepared by mixing the binder solution and glass powder of Li 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 which is an example of a NASICON type lithium-containing phosphate compound as a first solid electrolyte material. 1 was produced. The mixing ratio of the above glass powder and polyvinyl alcohol was 70:30 by weight.
  • the solid electrolyte slurry 4 was prepared by mixing the binder solution and the solid electrolyte powder C obtained above as the second solid electrolyte material.
  • the preparation ratio of the solid electrolyte powder C and polyvinyl alcohol was 70:30 by weight.
  • the negative electrode active material slurry 1 and the solid electrolyte slurry 4 obtained above are mixed so that the mixing ratio of Nb 2 O 5 and the solid electrolyte powder C is 50:50 by weight, thereby preparing the negative electrode slurry 3. did.
  • Each of the obtained negative electrode slurry 3, solid electrolyte slurry 1, and solid electrolyte slurry 4 is formed into a thickness of 50 ⁇ m by a doctor blade method, thereby forming a negative electrode layer sheet 3 as a green sheet, a solid electrolyte layer sheet 1, And the intervening layer sheet
  • a plurality of intervening layer sheets 3 cut into a circular shape having a diameter of 12 mm are laminated, and subjected to thermocompression bonding by applying a pressure of 1 ton at a temperature of 80 ° C.
  • the laminated body 1 was produced. After firing the laminate 1 in an oxygen gas atmosphere at a temperature of 500 ° C. for 2 hours, the laminate 1 is fired in a nitrogen gas atmosphere at a temperature of 900 ° C. for 2 hours to obtain a sintered body 3 for evaluation of reduction resistance. Produced.
  • Cyclic voltammetry was measured using the reduction resistance evaluation cell 3. The measurement was performed as follows. First, after sweeping from the open circuit voltage to 0 V at 0.1 mV / sec, the voltage was held at 0 V for 5 hours. Thereafter, it was rested for 3 hours, swept from the rest potential to 3V at 0.1 mV / sec, and then held at 3V for 5 hours.
  • FIG. 12 shows the cyclic voltammetry measurement results for the reduction resistance evaluation cell 3 as an example. From FIG. 12, it was confirmed that the solid electrolyte C was electrochemically stable up to the potential of lithium.
  • the intervening layer sheet 3 cut into a circular shape with a diameter of 12 mm is laminated on one side of the solid electrolyte layer sheet 1 cut into a circular shape with a diameter of 12 mm, and a pressure of 1 ton is applied at a temperature of 80 ° C. Then, the negative electrode layer sheet 3 cut into a circular shape having a diameter of 12 mm was laminated thereon, and thermocompression bonded by applying a pressure of 1 ton at a temperature of 80 ° C.,
  • Example 3 A negative electrode-electrolyte laminate D as a molded body constituting the all solid state battery was prepared.
  • a polymethyl methacrylate resin (PMMA) gel electrolyte was applied on the metal lithium plate as the positive electrode, The negative electrode-electrolyte laminate D as a fired body and a metal lithium plate are laminated so that the surface on the electrolyte side is in contact with the coated surface, and sealed with a 2032 type coin cell. D was produced.
  • PMMA polymethyl methacrylate resin
  • the all solid state battery D was charged and discharged at a constant current and a constant voltage at a current density of 20 ⁇ A / cm 2 in a voltage range of 1.2 to 3V.
  • the charge / discharge curve of the obtained all-solid-state battery A is shown in FIG.
  • the discharge capacity of the all-solid-state battery B includes Li 1.2 Al 0.2 Ti 1.8 (PO), which is a lithium-containing titanium phosphate compound having a NASICON type structure contained in the solid electrolyte layer, in addition to the capacity of Nb 2 O 5 as the negative electrode active material. 4 ) It can be seen that the reduction capacity of 3 is included.
  • the present invention is particularly useful for the production of an all-solid battery.

Abstract

L'invention concerne une cellule entièrement électronique avec laquelle il est possible de contrôler une réduction de l'efficacité de charge/décharge de la cellule, et son procédé de fabrication. Un stratifié (10) de cellule entièrement électronique comprend une couche d'électrode négative (12), une couche d'électrolyte solide (13) stratifiée sur la couche d'électrode négative (12) et une couche intercalée (14) intercalée entre la couche d'électrode négative (12) et la couche d'électrolyte solide (13). La couche d'électrolyte solide (13) comprend un premier matériau d'électrolyte solide et la couche intercalée (14) comprend un second matériau d'électrolyte solide qui est différent du premier matériau d'électrolyte solide. Le second matériau d'électrolyte solide a une fenêtre potentielle plus large que le premier matériau d'électrolyte solide.
PCT/JP2013/056729 2012-03-15 2013-03-12 Cellule entièrement électronique et son procédé de fabrication WO2013137224A1 (fr)

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JP2015065021A (ja) * 2013-09-25 2015-04-09 株式会社村田製作所 全固体電池
JP2015065022A (ja) * 2013-09-25 2015-04-09 株式会社村田製作所 固体電解質材料、及び全固体電池
JP2015076324A (ja) * 2013-10-10 2015-04-20 株式会社村田製作所 固体電解質材料およびそれを用いた全固体電池
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JP2015216220A (ja) * 2014-05-09 2015-12-03 日本特殊陶業株式会社 キャパシタ及びその製造方法
JP2015216222A (ja) * 2014-05-09 2015-12-03 日本特殊陶業株式会社 キャパシタ及びその製造方法
JP2015216221A (ja) * 2014-05-09 2015-12-03 日本特殊陶業株式会社 キャパシタ及びその製造方法
WO2016031942A1 (fr) * 2014-08-29 2016-03-03 国立研究開発法人産業技術総合研究所 Feuille d'électrolyte et son procédé de fabrication
JP2016051539A (ja) * 2014-08-29 2016-04-11 株式会社村田製作所 固体電解質材料、及び全固体電池
JP2016066550A (ja) * 2014-09-25 2016-04-28 太陽誘電株式会社 全固体二次電池
WO2016063607A1 (fr) * 2014-10-20 2016-04-28 アルプス電気株式会社 Poudre d'électrolyte solide, batterie rechargeable lithium-ion tout solide, et procédé de préparation de poudre d'électrolyte solide
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JP2019510349A (ja) * 2016-03-28 2019-04-11 セブン キング エナージー カンパニー リミテッドＳｅｖｅｎ Ｋｉｎｇ Ｅｎｅｒｇｙ Ｃｏ．，Ｌｔｄ． 多層構造を有する二次電池用複合電解質
WO2019102762A1 (fr) * 2017-11-22 2019-05-31 株式会社 オハラ Matériau actif d'électrode négative, électrode négative et batterie
CN110521026A (zh) * 2017-04-18 2019-11-29 丰田自动车株式会社 全固体锂离子二次电池
WO2020091435A1 (fr) * 2018-10-31 2020-05-07 주식회사 엘지화학 Électrolyte présentant une conductivité ionique différentielle, et batterie secondaire au lithium le comprenant
EP3745518A4 (fr) * 2018-01-26 2021-03-10 Panasonic Intellectual Property Management Co., Ltd. Batterie
CN112510253A (zh) * 2019-09-13 2021-03-16 丰田自动车工程及制造北美公司 作为锂超离子导体的钽酸锂钾化合物、固体电解质以及用于锂金属电池和锂离子电池的涂层
CN112510252A (zh) * 2019-09-13 2021-03-16 丰田自动车工程及制造北美公司 作为锂电池用的Li超级离子导体、固体电解质和涂层的锂钾元素氧化物化合物
CN113745649A (zh) * 2020-05-29 2021-12-03 太阳诱电株式会社 固体电解质及其制造方法、以及全固体电池及其制造方法
WO2022209193A1 (fr) * 2021-03-31 2022-10-06 パナソニックＩｐマネジメント株式会社 Batterie
US11705578B2 (en) 2018-10-31 2023-07-18 Lg Energy Solution, Ltd. Electrolyte having differential ion conductivity and lithium secondary battery comprising same
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JP2015065022A (ja) * 2013-09-25 2015-04-09 株式会社村田製作所 固体電解質材料、及び全固体電池
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