WO2013100000A1 - Batterie entièrement à l'état solide, et procédé de fabrication de celle-ci - Google Patents

Batterie entièrement à l'état solide, et procédé de fabrication de celle-ci Download PDF

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Publication number
WO2013100000A1
WO2013100000A1 PCT/JP2012/083767 JP2012083767W WO2013100000A1 WO 2013100000 A1 WO2013100000 A1 WO 2013100000A1 JP 2012083767 W JP2012083767 W JP 2012083767W WO 2013100000 A1 WO2013100000 A1 WO 2013100000A1
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solid
component
solid electrolyte
electrolyte layer
state battery
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PCT/JP2012/083767
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English (en)
Japanese (ja)
Inventor
彰佑 伊藤
倍太 尾内
充 吉岡
武郎 石倉
剛司 林
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株式会社 村田製作所
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Priority to JP2013551764A priority Critical patent/JP5811191B2/ja
Publication of WO2013100000A1 publication Critical patent/WO2013100000A1/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
    • H01M10/056—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
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • 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
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • 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 is made of a general formula Li 1 + X M III X Ti IV 2-X (PO 4 ) 3 (where M III is Al, Y, Ga, In And La is at least one metal ion selected from the group consisting of La, and X is a compound represented by the formula: LiMPO 4 (wherein M Is at least one selected from the group consisting of Mn, Fe, Co, and Ni).
  • Patent Document 1 as an all-solid battery manufacturing method, an active material containing a phosphoric acid compound and a solid electrolyte are dispersed in a solution containing a binder and a plasticizer, respectively.
  • An active material green sheet and a solid electrolyte green sheet obtained by molding the slurry are laminated, and the binder and the plasticizer are thermally decomposed and removed, followed by firing to produce a laminate of an all-solid battery. It is described.
  • Patent Document 1 describes that at least one of the active material layer and the solid electrolyte layer preferably contains an amorphous oxide.
  • the amorphous oxide include SiO 2 , Al 2 O 3 , Na 2 O, MgO, CaO and the like.
  • an object of the present invention is to provide an all solid state battery capable of improving the density of the solid electrolyte layer after firing and improving the ionic conductivity, and a method for manufacturing the same.
  • a component containing at least one element of magnesium, calcium, barium, and strontium is added to the component that functions as a solid electrolyte. It has been found that by configuring the solid electrolyte layer, the density of the solid electrolyte layer after firing can be improved and the ionic conductivity can be improved. Based on such knowledge of the inventors, the present invention has the following features.
  • the all solid state battery according to the present invention includes at least one of the positive electrode layer and the negative electrode layer and a solid electrolyte layer laminated on the electrode layer.
  • the solid electrolyte layer includes a first component made of a lithium-containing oxide and a second component made of a compound containing at least one element selected from the group consisting of magnesium, calcium, barium, and strontium.
  • the second component is preferably made of an oxide.
  • the second component is made of a phosphoric acid compound.
  • the second component contains M- (PO 4 ) n (where M contains at least one element selected from the group consisting of Mg, Ca, Ba and Sr, and n Is preferably an integer of 1 or more).
  • the second component is Mg 3 (PO 4 ) 2 , Ca 3 (PO 4 ) 2 , Ba 3 (PO 4 ) 2 , Sr 3 (PO 4 ) 2 , LiMgPO 4. It is preferably made of one compound selected from the group consisting of LiCaPO 4 , LiBaPO 4 , and LiSrPO 4 .
  • the first component includes a lithium-containing phosphate compound having a NASICON type structure.
  • the first component in Li x M y (PO 4) 3 ( Formula, x is 1 ⁇ x ⁇ 2, y is a numerical value in the 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, Ga and Zr.
  • the first component is Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 , Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 , and Li 1.2 Al 0.2 Ti 1.8 (PO 4 ) It is preferable to contain at least one compound selected from the group consisting of 3 .
  • the solid electrolyte layer contains 1 mol part or more and 75 mol parts or less of the second component with respect to 100 mol parts of the first component.
  • the solid electrolyte layer includes 1 mol part or more and 32 mol parts or less of the second component with respect to 100 mol parts of the first component.
  • the solid electrolyte layer contains 2 mol parts or more and 8 mol parts or less of the second component with respect to 100 mol parts of the first component.
  • the manufacturing method of the all-solid-state battery according to the present invention includes the following steps.
  • a second component comprising a first component comprising a lithium-containing oxide and a compound comprising at least one element selected from the group consisting of magnesium, calcium, barium, and strontium.
  • An unsintered solid electrolyte layer is prepared from the mixture containing the components.
  • a 2nd component consists of a phosphoric acid compound, and a mixture contains 1 mol part or more and 75 mol part or less of 2nd component with respect to 100 mol part of 1st components. preferable.
  • the first component includes a lithium-containing phosphate compound having a NASICON structure.
  • the unsintered electrode layer and the unsintered solid electrolyte layer may be in the form of a green sheet or a printed layer.
  • the overvoltage during charging and discharging can be reduced.
  • the all-solid battery stack 10 of the present invention includes a positive electrode layer 11, a solid electrolyte layer 13, and a negative electrode layer 12.
  • the all-solid battery stack 10 is formed in a rectangular parallelepiped shape, and is configured by a stack including a plurality of flat layers having a rectangular plane.
  • the all-solid-state battery stack 10 is formed in a cylindrical shape and is formed of a stack made of a plurality of disk-shaped layers.
  • Each of the positive electrode layer 11 and the negative electrode layer 12 includes a solid electrolyte and an electrode active material, and the solid electrolyte layer 13 includes 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 solid electrolyte layer 13 is selected from the group consisting of a first component as a solid electrolyte made of a lithium-containing oxide, and magnesium, calcium, barium, and strontium. And a second component made of a compound containing at least one element.
  • the firing density of the solid electrolyte layer 13 is improved and the ion conductivity of the solid electrolyte layer 13 is improved.
  • the degree is improved. It can be assumed that the following phenomenon occurs during firing and charge / discharge.
  • the second component particles having lower ionic conductivity than the first component particles segregate between the first component particles, thereby connecting the first component particles functioning as a solid electrolyte to each other. Conceivable. Since the particles of the second component absorb the expansion or contraction that occurs in the firing step when forming the solid electrolyte layer 13, the firing property can be improved and the firing density of the solid electrolyte layer 13 can be improved.
  • the second component particles absorb expansion or contraction caused by the entry and exit of ions during charging and discharging, it is considered that the ionic conductivity of the solid electrolyte layer 13 can be improved. Thereby, the overvoltage at the time of charging / discharging can be reduced. Therefore, the all solid state battery of the present invention exhibits higher battery characteristics.
  • the second component is preferably made of an oxide, more preferably a phosphate compound.
  • the second component particles more effectively absorb the expansion or contraction that occurs in the firing step when the solid electrolyte layer 13 is formed. It is considered that the firing density of the solid electrolyte layer 13 can be improved.
  • the second component particles absorb more effectively the expansion or contraction caused by the entry and exit of ions during charge and discharge, so that the ionic conductivity of the solid electrolyte layer 13 is improved. It is thought that it can be made to. Therefore, the firing density and ionic conductivity of the solid electrolyte layer 13 can be further increased.
  • the second component is M- (PO 4 ) n (where M includes at least one element selected from the group consisting of Mg, Ca, Ba and Sr, and n is an integer of 1 or more) It is preferable to consist of the phosphoric acid compound represented by these. In this case, the firing density and ionic conductivity of the solid electrolyte layer 13 can be improved more effectively.
  • the second component is Mg 3 (PO 4 ) 2 , Ca 3 (PO 4 ) 2 , Ba 3 (PO 4 ) 2 , Sr 3 (PO 4 ) 2 , LiMgPO 4. It is preferably made of one compound selected from the group consisting of LiCaPO 4 , LiBaPO 4 , and LiSrPO 4 .
  • the firing density and ionic conductivity of the solid electrolyte layer 13 can be further improved by forming the second component from the specified phosphoric acid compound.
  • the second component is not limited to the phosphoric acid compound represented by M- (PO 4 ) n .
  • M m- (P 2 O 7 ) n (where m and n are 1 or more)
  • m and n are 1 or more
  • the solid electrolyte layer 13 preferably contains 1 mol part or more and 75 mol parts or less of the second component with respect to 100 mol parts of the first component.
  • the firing density and ionic conductivity of the solid electrolyte layer 13 can be improved.
  • the solid electrolyte layer 13 includes 1 mol part or more and 32 mol parts or less of the second component with respect to 100 mol parts of the first component.
  • the firing density and ionic conductivity of the solid electrolyte layer 13 can be further improved.
  • the solid electrolyte layer 13 includes 2 mol parts or more and 8 mol parts or less of the second component with respect to 100 mol parts of the first component.
  • the firing density and ionic conductivity of the solid electrolyte layer 13 can be further remarkably improved.
  • a lithium-containing phosphate compound having a NASICON structure can be used as the solid electrolyte as the first component or the solid electrolyte included in the positive electrode layer 11 or the negative electrode layer 12.
  • 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), for example, Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 .
  • part of P in the above chemical formula may be substituted with B, Si, or the like.
  • 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 lithium-containing phosphate compound having a NASICON structure used in the above solid electrolyte includes a crystal phase of a lithium-containing phosphate compound having a NASICON structure, or a lithium-containing phosphate having a NASICON structure by heat treatment You may use the glass which precipitates the crystal phase of a phosphoric acid compound.
  • a material used for said solid electrolyte it is possible to use the material which has ion conductivity and is so small that electronic conductivity can be disregarded other than the lithium-containing phosphate compound which has a NASICON structure.
  • Examples of such a material include lithium oxyacid salts and derivatives thereof.
  • Li-PO system compounds such as lithium phosphate (Li 3 PO 4 ), LIPON (LiPO 4 ⁇ x N x ) in which nitrogen is mixed with lithium phosphate, and Li—Si—O such as Li 4 SiO 4
  • Li—Si—O such as Li 4 SiO 4
  • Examples thereof include compounds having a lobskite structure, compounds having a garnet structure having Li, La, and Zr.
  • the positive electrode active material examples include a lithium-containing phosphate compound having a NASICON structure such as Li 3 V 2 (PO 4 ) 3 , a lithium-containing phosphate compound having an olivine structure such as LiFePO 4 and LiMnPO 4 , LiCoO 2 , and LiCo. It is possible to use a layered compound such as 1/3 Ni 1/3 Mn 1/3 O 2 or a lithium-containing compound having a spinel type structure such as LiMn 2 O 4 , LiNi 0.5 Mn 1.5 O 4 , Li 4 Ti 5 O 12. it can.
  • MOx (M includes at least one element selected from the group consisting of Ti, Si, Sn, Cr, Fe, Nb and Mo, x is 0.9 ⁇ x ⁇ 2.0.
  • a compound having a composition represented by the following formula can be used.
  • a mixture in which two or more active materials having a composition represented by MOx containing different elements M such as TiO 2 and SiO 2 may be used.
  • graphite-lithium compounds, lithium alloys such as Li-Al, oxidation of Li 3 V 2 (PO 4 ) 3 , Li 3 Fe 2 (PO 4 ) 3 , Li 4 Ti 5 O 12, etc. Thing, etc. can be used.
  • the negative electrode layer 12 may be formed from metallic lithium.
  • the solid electrolyte layer 13 includes a first component as a solid electrolyte composed of a lithium-containing phosphate compound having a NASICON structure, and at least one of the positive electrode layer 11 or the negative electrode layer 12 is It is preferable to include a solid electrolyte composed of a lithium-containing phosphate compound having a NASICON structure.
  • An unsintered solid electrolyte layer that is an unsintered body of the electrolyte layer 13 is fabricated (unsintered layer fabrication step).
  • an unsintered solid electrolyte layer that is an unsintered body of the solid electrolyte layer 13 is produced from the mixture including the first component and the second component.
  • the produced unfired electrode layer and the unfired solid electrolyte layer are laminated to form a laminate (laminated body forming step). And the obtained laminated body is baked (baking process).
  • the positive electrode layer 11 and / or the negative electrode layer 12 and the solid electrolyte layer 13 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.
  • 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.
  • a plurality of laminates having a single battery structure may be laminated electrically in series or in parallel.
  • the method for forming the unfired electrode layer and the unfired solid electrolyte layer is not particularly limited, but a doctor blade method, a die coater, a comma coater, etc. for forming a green sheet, or a screen for forming a printing layer. Printing or the like can be used.
  • the method for laminating the unfired electrode layer and the unfired solid electrolyte layer is not particularly limited, but hot isostatic pressing (HIP), cold isostatic pressing (CIP), isostatic pressing (WIP), etc.
  • HIP hot isostatic pressing
  • CIP cold isostatic pressing
  • WIP isostatic pressing
  • the green electrode layer and the green solid electrolyte layer can be laminated by using.
  • 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, a positive electrode active material and a solid electrolyte, a negative electrode active material and a solid electrolyte, a first component and a second component, or a collection. It can be produced by wet-mixing the electrical material. 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.
  • a positive electrode sheet and a solid electrolyte sheet were produced as follows.
  • LATP Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3
  • Mg 3 Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3
  • LATP Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3
  • Slurries A1 to A5 and solid electrolyte slurries B1 and B2 used in Comparative Examples 1 and 2 were prepared.
  • the mixing ratio of the mixture powder and polyvinyl alcohol was 70:30 by weight.
  • a positive electrode slurry was prepared by mixing the positive electrode active material slurry obtained above and the solid electrolyte slurry B1 so that the blending ratio of LVP and LATP was 50:50 by weight.
  • Each of the obtained positive electrode slurry and solid electrolyte slurries A1 to A5, B1, and B2 is formed into a thickness of 50 ⁇ m by a doctor blade method, thereby forming a positive electrode sheet and solid electrolyte sheets A1 to A5, B1, and B2 compacts ( Green sheet) was prepared.
  • FIG. 4 shows the measured X-ray diffraction patterns of the solid electrolyte sheets A2, B1, and B2.
  • FIG. 4 shows an X-ray diffraction pattern of a JCPDS (Joint Committee on Powder Diffraction Standards) card (card number: 35-0754) of LiTi 2 (PO 4 ) 3 which is a Nasicon type lithium-containing phosphate compound, and MgTi 4
  • JCPDS Joint Committee on Powder Diffraction Standards
  • LiTi 2 (PO 4 ) 3 LiTi 2 (PO 4 ) 3 which is a Nasicon type lithium-containing phosphate compound
  • MgTi 4 MgTi 4
  • the X-ray diffraction pattern (card number: 43-0073) of the JCPDS card of (PO 4 ) 6 and the X-ray diffraction pattern of the JCPDS card of LiMgPO 4 (card number: 32-0574) are shown together.
  • the X-ray diffraction pattern of the solid electrolyte sheet A2 as the fired body almost coincides with the X-ray diffraction pattern of LiTi 2 (PO 4 ) 3 , and in the solid electrolyte sheet A2 as the fired body, the solid electrolyte layer is It was confirmed that LATP as the first component and Mg 3 (PO 4 ) 2 as the second component can be maintained in the skeleton without disappearing in the solid phase reaction. Although not shown, similar results were obtained with the solid electrolyte sheets A1, A3 to A5 as the fired bodies.
  • the X-ray diffraction pattern of the solid electrolyte sheet B2 as a fired body is LATP and Mg 3 (PO 4 ) 2.
  • X-ray diffraction patterns of MgTi 4 (PO 4 ) 6 and LiMgPO 4 which are the reaction phases of the above, were confirmed, and LATP and Mg 3 (PO 4 ) 2 reacted in a solid phase in the solid electrolyte sheet B2 as a fired body. It was confirmed that
  • the solid electrolyte layer has 1 Mg 3 (PO 4 ) 2 as the second component with respect to 100 mol parts of LATP as the first component. It can be seen that the ionic conductivity can be made higher than that of the solid electrolyte layers B1 and B2 of Comparative Examples 1 and 2 by including the molar part to 75 parts by mole.
  • the solid electrolyte layer is Mg 3 (PO 4 ) 2 as the second component with respect to 100 parts by mole of LATP as the first component. It can be seen that the ionic conductivity can be further increased by containing 1 mol part or more and 32 mol parts or less.
  • the solid electrolyte layer is Mg 3 (PO 4 ) 2 as the second component with respect to 100 mol parts of LATP as the first component. It can be seen that the ionic conductivity can be further remarkably increased by containing 2 mol parts or more and 8 mol parts or less.
  • a positive electrode sheet cut into a circular shape with a diameter of 12 mm is laminated on one side of the solid electrolyte sheets A1 to A5, B1, B2 cut into a circular shape with a diameter of 12 mm, and 1 ton at a temperature of 80 ° C.
  • positive electrode-electrolyte laminates A1 to A5, B1, and B2 were produced as molded bodies.
  • Firing is performed for 2 hours at a temperature of 500 ° C. in an oxygen gas atmosphere in a state where the positive electrode-electrolyte laminates A1 to A5, B1 and B2 are sandwiched between two alumina ceramic plates as a molded body (firing step 1). ), After removing the polyvinyl alcohol, the positive electrode layer and the solid electrolyte layer were joined by firing at a temperature of 900 ° C. for 2 hours in a nitrogen gas atmosphere (firing step 2). In this way, positive electrode-electrolyte laminates A1 to A5, B1, and B2 were produced as fired bodies.
  • the positive electrode-electrolyte laminates A1 to A5, B1, and B2 as the fired bodies are dried at a temperature of 100 ° C. to remove moisture, and then polymethyl methacrylate resin (PMMA) is placed on the metal lithium plate as the negative electrode.
  • PMMA polymethyl methacrylate resin
  • a gel electrolyte is applied, and positive electrode-electrolyte laminates A1 to A5, B1, B2 as fired bodies and a metal lithium plate are laminated so that the surface on the electrolyte side is in contact with the applied surface, and a 2032 type coin cell is used. Sealed to produce all solid state batteries A1 to A5, B1, and B2 of Examples 1 to 5 and Comparative Examples 1 and 2.
  • Cyclic voltammetry was measured for all solid state batteries A1 to A5, B1, and B2. The measurement was performed as follows. First, a voltage range of 3.0 V to 4.5 V was swept at 0.1 mV / sec and then held at 4.5 V for 5 hours. Then, after resting for 3 hours, it was swept from the potential after the rest to 3.0 V at 0.1 mV / sec, and then maintained at 3.0 V for 5 hours. The above series of operations was repeated.
  • FIG. 5 shows the results of cyclic voltammetry measurement for the all solid state battery A2 of Example 2 (solid line) and the all solid state battery B1 of Comparative Example 1 (broken line).
  • the charge / discharge capacity of the all solid state battery A2 was about 120 to 130 mAh / g
  • the charge / discharge capacity of the all solid state battery B1 was about 80 to 90 mAh / g.
  • the charge / discharge capacities of all solid state batteries A1, A3 to A5 were also about 120 to 130 mAh / g.
  • the charge / discharge capacity was a value obtained by integrating the current value observed by cyclic voltammetry in the voltage range.
  • the all solid state battery B2 operates as a battery. It can be assumed that the following phenomenon occurs during firing. In the solid electrolyte layer of the all-solid-state battery B2, LATP as the first component constituting the solid electrolyte layer and Mg 3 (PO 4 ) 2 as the second component undergo a solid phase reaction, and a part of LATP is decomposed. Yes. Thereby, it is guessed that the ionic conductivity of a solid electrolyte layer fell and became lower than the ionic conductivity required for battery operation.
  • the solid electrolyte layer contains 1 mol part or more and 75 mol parts or less of Mg 3 (PO 4 ) 2 as the second component with respect to 100 mol parts of LATP as the first component. It can be estimated that the density of the solid electrolyte layer can be improved and the ionic conductivity can be improved, and the overvoltage during charge / discharge can be reduced.
  • Mg 3 (PO 4 ) 2 is used as the second component
  • a group consisting of magnesium, calcium, barium, and strontium Even when a compound containing at least one element selected from the above is used, the same effect as described above can be obtained.
  • the present invention is particularly useful for the production of an all-solid battery. .

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Abstract

L'invention concerne une batterie entièrement à l'état solide et un procédé de fabrication de celle-ci, dans laquelle la densité d'une couche d'électrolyte à l'état solide après calcination et la conductance ionique peuvent être améliorées. Un empilement de batterie entièrement à l'état solide (10) est équipé d'au moins une couche d'électrode comprenant une couche d'électrode positive (11) ou une couche d'électrode négative (12), et une couche d'électrolyte solide (13) empilée sur la couche d'électrode. La couche d'électrolyte solide (13) comprend : un premier composant comprenant un oxyde contenant du lithium ; et un second composant comprenant un composé comprenant au moins un élément choisi dans le groupe constitué par le magnésium, le calcium, le baryum, et le strontium.
PCT/JP2012/083767 2011-12-28 2012-12-27 Batterie entièrement à l'état solide, et procédé de fabrication de celle-ci WO2013100000A1 (fr)

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JP2013551764A JP5811191B2 (ja) 2011-12-28 2012-12-27 全固体電池およびその製造方法

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015064992A (ja) * 2013-09-25 2015-04-09 株式会社村田製作所 全固体電池
JP2016001596A (ja) * 2014-05-19 2016-01-07 Tdk株式会社 リチウムイオン二次電池
JP2016001598A (ja) * 2014-05-19 2016-01-07 Tdk株式会社 リチウムイオン二次電池
JP2016001595A (ja) * 2014-05-19 2016-01-07 Tdk株式会社 リチウムイオン二次電池
CN105406114A (zh) * 2015-11-24 2016-03-16 青岛能迅新能源科技有限公司 一种全固态锂电池电解质的制备方法
JP2017168373A (ja) * 2016-03-17 2017-09-21 株式会社Ｇｓユアサ 非水電解質二次電池用非水電解質
DE112017004915T5 (de) 2016-09-29 2019-06-13 Tdk Corporation Lithiumionenleitender Festelektrolyt und wiederaufladbare Lithiumionen-Feststoffbatterie
WO2021049360A1 (fr) * 2019-09-13 2021-03-18 Tdk株式会社 Couche d'électrolyte solide, batterie secondaire entièrement solide et son procédé de fabrication
CN113073357A (zh) * 2021-03-19 2021-07-06 西南石油大学 一种基于固态电解质隔膜材料的电解装置及利用该电解装置制钠的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004537834A (ja) * 2001-08-01 2004-12-16 カリフォルニア・インスティテュート・オブ・テクノロジー 電気化学デバイスのための固体酸電解質
JP2007005279A (ja) * 2004-12-13 2007-01-11 Matsushita Electric Ind Co Ltd 活物質層と固体電解質層とを含む積層体およびこれを用いた全固体リチウム二次電池
JP2007528108A (ja) * 2004-03-06 2007-10-04 ヴェップナー ヴェルナー 化学的に安定な固体のリチウムイオン伝導体
JP2009181807A (ja) * 2008-01-30 2009-08-13 Sony Corp 固体電解質、および固体電解質電池、並びにリチウムイオン伝導体の製造方法、固体電解質の製造方法、および固体電解質電池の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004537834A (ja) * 2001-08-01 2004-12-16 カリフォルニア・インスティテュート・オブ・テクノロジー 電気化学デバイスのための固体酸電解質
JP2007528108A (ja) * 2004-03-06 2007-10-04 ヴェップナー ヴェルナー 化学的に安定な固体のリチウムイオン伝導体
JP2007005279A (ja) * 2004-12-13 2007-01-11 Matsushita Electric Ind Co Ltd 活物質層と固体電解質層とを含む積層体およびこれを用いた全固体リチウム二次電池
JP2009181807A (ja) * 2008-01-30 2009-08-13 Sony Corp 固体電解質、および固体電解質電池、並びにリチウムイオン伝導体の製造方法、固体電解質の製造方法、および固体電解質電池の製造方法

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015064992A (ja) * 2013-09-25 2015-04-09 株式会社村田製作所 全固体電池
JP2016001596A (ja) * 2014-05-19 2016-01-07 Tdk株式会社 リチウムイオン二次電池
JP2016001598A (ja) * 2014-05-19 2016-01-07 Tdk株式会社 リチウムイオン二次電池
JP2016001595A (ja) * 2014-05-19 2016-01-07 Tdk株式会社 リチウムイオン二次電池
CN105406114A (zh) * 2015-11-24 2016-03-16 青岛能迅新能源科技有限公司 一种全固态锂电池电解质的制备方法
JP2017168373A (ja) * 2016-03-17 2017-09-21 株式会社Ｇｓユアサ 非水電解質二次電池用非水電解質
DE112017004915T5 (de) 2016-09-29 2019-06-13 Tdk Corporation Lithiumionenleitender Festelektrolyt und wiederaufladbare Lithiumionen-Feststoffbatterie
US11254573B2 (en) 2016-09-29 2022-02-22 Tdk Corporation Lithium ion-conducting solid electrolyte and solid-state lithium ion rechargeable battery
WO2021049360A1 (fr) * 2019-09-13 2021-03-18 Tdk株式会社 Couche d'électrolyte solide, batterie secondaire entièrement solide et son procédé de fabrication
CN113073357A (zh) * 2021-03-19 2021-07-06 西南石油大学 一种基于固态电解质隔膜材料的电解装置及利用该电解装置制钠的方法

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