WO2014136650A1 - Procédé de fabrication de verre-céramique conducteur des ions de lithium, verre-céramique conducteur des ions de lithium et cellule secondaire au lithium-ion - Google Patents

Procédé de fabrication de verre-céramique conducteur des ions de lithium, verre-céramique conducteur des ions de lithium et cellule secondaire au lithium-ion Download PDF

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WO2014136650A1
WO2014136650A1 PCT/JP2014/054902 JP2014054902W WO2014136650A1 WO 2014136650 A1 WO2014136650 A1 WO 2014136650A1 JP 2014054902 W JP2014054902 W JP 2014054902W WO 2014136650 A1 WO2014136650 A1 WO 2014136650A1
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lithium ion
conductive glass
raw material
ion conductive
material mixture
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PCT/JP2014/054902
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English (en)
Japanese (ja)
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知之 ▲辻▼村
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旭硝子株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/18—Compositions for glass with special properties for ion-sensitive glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • 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
    • 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

Definitions

  • the present invention relates to a method for producing a lithium ion conductive glass ceramic, a lithium ion conductive glass ceramic, and a lithium ion secondary battery.
  • Lithium ion secondary batteries are used as small and high capacity drive power sources in various fields such as automobiles, personal computers, and mobile phones.
  • organic solvent-based liquid electrolytes such as diethyl carbonate and ethyl methyl carbonate are used as electrolytes for lithium ion secondary batteries.
  • organic solvent-based liquid electrolyte may be decomposed or deteriorated when a high voltage is applied.
  • an inorganic solid electrolyte that is nonflammable and has high stability against voltage application is expected as an electrolyte for the next-generation lithium ion secondary battery.
  • inorganic solid electrolytes made of ceramics and inorganic solid electrolytes made of glass ceramics (glass containing crystals, also called crystallized glass) have been proposed.
  • an inorganic solid electrolyte made of glass ceramics for example, Li 1 + x + y (Al, Ga) x (Ti, Ge) 2-x Si y P 3-y O 12 (where 0 ⁇ a ⁇ 1, 0 ⁇ y ⁇ 1 There is proposed a material composed of (A).
  • the inorganic solid electrolyte made of glass ceramics of Patent Document 1 has titanium and germanium. Titanium and germanium ions can have multiple valence states. Therefore, at the time of charge / discharge of the lithium ion secondary battery, the valence state of titanium ions and germanium ions may change, and battery characteristics such as cycle characteristics may become unstable. In particular, titanium and germanium are likely to change in valence state due to a reduction reaction when metallic lithium is used for the negative electrode, and the potential window becomes narrow and unstable.
  • an object of the present invention is to provide a method for producing a lithium ion conductive glass ceramic that is relatively stable with respect to metallic lithium and has improved ion conductivity.
  • Another object of the present invention is to provide a lithium ion secondary battery having a lithium ion conductive glass ceramic produced by such a method and a solid electrolyte containing the lithium ion conductive glass ceramic.
  • the raw material mixture is 25% or more and 50% or less of SiO 2 , 10% or more and 45% or less of ZrO 2 , and more than 0% and 30% or less in terms of mol% converted to oxide.
  • raw materials were blended to obtain a raw material mixture, the raw material mixture to be treated made of glass ceramics in the process of solidifying melted cooled to include a P 2 O 5, and 5% to 40% of Na 2 O
  • a method for producing a lithium ion conductive glass ceramic comprising: a step of obtaining a body; and (b) a step of subjecting the object to be treated to an ion exchange treatment in a molten salt containing lithium ions.
  • the object to be processed may have a NASICON type crystal structure.
  • the step (c) may include a step of processing the thickness of the treatment body to 1 mm or less between the steps (a) and (b).
  • the melting may be performed by heating the raw material mixture at a temperature of 1400 ° C. or higher and 1700 ° C. or lower.
  • the cooling may be performed at a cooling rate of 0.2 ° C./min to 2 ° C./min.
  • the ion exchange treatment is performed at a temperature of 200 ° C. or more and 500 ° C. or less and the object to be treated is held in the molten salt containing lithium ions for 24 hours to 120 hours. May be implemented.
  • a lithium ion conductive glass ceramic manufactured by the method as described above.
  • a lithium ion secondary battery having a positive electrode, a negative electrode, and a solid electrolyte disposed between the two electrodes, wherein the solid electrolyte is manufactured by the method as described above.
  • a lithium ion secondary battery that is a solid electrolyte containing conductive glass ceramics.
  • the present invention can provide a method for producing a lithium ion conductive glass ceramic that is relatively stable with respect to metallic lithium and has improved ion conductivity. Moreover, in this invention, the lithium ion secondary battery which has a solid electrolyte containing the lithium ion conductive glass ceramics manufactured by such a method and this lithium ion conductive glass ceramics can be provided.
  • FIG. 6 is a diagram showing an X-ray diffraction pattern of an evaluation sample of Example 2.
  • FIG. 6 is a diagram showing an X-ray diffraction pattern of an evaluation sample of Example 3.
  • FIG. 6 is a diagram showing an X-ray diffraction pattern of an evaluation sample of Example 4.
  • FIG. 6 is a diagram showing an X-ray diffraction pattern of an evaluation sample of Example 5.
  • the production method of lithium ion conductive glass ceramics and the content of each component in the lithium ion conductive glass ceramics obtained thereby are in mol% units converted to oxides. It expresses by. This is a unit when the content of each component converted to oxide is expressed as a percentage when the total content of each component converted to oxide is 100 mol%.
  • the method for producing the lithium ion conductive glass ceramic of the present embodiment is as follows: (A) The raw material mixture is in mol% unit converted to oxide, 25% or more and 50% or less of SiO 2 , 10% or more and 45% or less of ZrO 2 , more than 0% and 30% or less of P 2 O 5 , and Preparing a raw material mixture by preparing a raw material so as to contain 5% or more and 40% or less Na 2 O, and obtaining an object to be processed made of glass ceramics in the process of melting, cooling and solidifying the raw material mixture; (B) performing an ion exchange process on the object to be processed in a molten salt containing lithium ions.
  • the manufacturing method of the present embodiment may include a step of processing the object to be processed to 1 mm or less between the step (a) and the step (b).
  • the manufacturing method of the present embodiment does not have to have a heat treatment step after the step (a) and before the step (b). That is, the glass ceramic obtained in the process of melting and cooling the raw material mixture in the step (a) is once cooled to a predetermined temperature (for example, room temperature), and then is not heat-treated in the step (b). Ion exchange treatment may be performed.
  • the object to be processed made of glass ceramics preferably has a clear diffraction peak in an X-ray diffraction pattern by X-ray diffraction measurement using CuK ⁇ rays, and has a diffraction peak with a half-value width of 3 ° or less. More preferably.
  • the object to be processed made of glass ceramics preferably has a NASICON type crystal structure.
  • the identification of the “crystal structure” is performed by performing X-ray diffraction measurement of an object, and collating the obtained X-ray diffraction pattern based on a JCPDS (Joint of Committee on Powder Standards) card, Can be easily identified.
  • JCPDS Joint of Committee on Powder Standards
  • SiO 2 is an essential component for expanding the composition range (hereinafter also referred to as vitrification range) to become glass and obtaining glass ceramics having a NASICON type crystal structure. If the content of SiO 2 is too small, it becomes difficult to obtain glass ceramics having a NASICON type crystal structure. Therefore, SiO 2 is set to 25% or more. Further, since glass ceramics having a NASICON type crystal structure can be obtained more stably, SiO 2 is preferably 30% or more, and more preferably 32% or more.
  • SiO 2 is set to 50% or less. Further, since it becomes easy to lower the viscosity at the time of melting of the raw material mixture, and it becomes easy to precipitate crystals having a NASICON type crystal structure in the obtained glass ceramic, SiO 2 is preferably 45% or less, and 43% or less. More preferably.
  • ZrO 2 is an essential component for obtaining glass ceramics having a NASICON type crystal structure. If the content of ZrO 2 is too small, it becomes difficult to obtain glass ceramics having a NASICON type crystal structure, so ZrO 2 is made 10% or more. Further, it becomes easier to precipitate crystals having a crystal structure of the NASICON type, ZrO 2 is preferably 15% or more, and more preferably 17% or more.
  • ZrO 2 is set to 45% or less.
  • ZrO 2 is preferably set to 40% or less, and 38% or less. More preferably.
  • P 2 O 5 is an essential component for expanding the vitrification range and obtaining glass ceramics having a NASICON type crystal structure. If P 2 O 5 is not contained, glass ceramics having a NASICON type crystal structure cannot be obtained. Therefore, P 2 O 5 is set to exceed 0%. Further, since glass ceramics having a NASICON type crystal structure can be obtained more stably, P 2 O 5 is preferably 2% or more, and more preferably 5% or more.
  • P 2 O 5 is set to 30% or less. Further, it becomes easier to precipitate crystals only having a crystal structure of the NASICON type obtained glass ceramic, it is preferred that the P 2 O 5 is 25% or less, and more preferably 20% or less.
  • Na 2 O is an essential component for obtaining glass ceramics having a NASICON type crystal structure. If the content of Na 2 O is too small, the ion conductivity of the lithium ion conductive glass ceramic obtained later by ion exchange treatment will be low, so Na 2 O is made 5% or more. Further, since glass ceramics having a NASICON type crystal structure can be obtained more stably, Na 2 O is preferably 10% or more, and more preferably 15% or more.
  • Na 2 O is 40% or less.
  • Na 2 O is preferably 35% or less, and more preferably 30% or less, because an objective glass ceramic having a NASICON crystal structure can be obtained more stably.
  • lithium ion conductivity which is relatively stable with respect to metallic lithium, is prevented by substantially not including an element whose valence state changes due to a reduction reaction, such as titanium or germanium. Glass ceramics can be obtained.
  • the raw material mixture is SiO 2 of 25% to 50%, ZrO 2 of 10% to 45%, P 2 O 5 of more than 0% to 30% and Na of 5% to 40%. It is preferable to prepare the raw material so as to contain 2 O.
  • the raw material mixture contains 30% to 45% SiO 2 , 15% to 40% ZrO 2 , 2% to 25% P 2 O 5 , and 10% to 35% Na 2 O. It is more preferable to prepare the raw materials so as to include them.
  • the raw material mixture contains SiO 2 of 32% to 43%, ZrO 2 of 17% to 38%, P 2 O 5 of 5% to 20%, and Na 2 O of 15% to 30%. It is more preferable to prepare the raw materials so as to include them.
  • the raw material mixture is prepared such that each component is included in the above range to obtain the raw material mixture, and the raw material mixture is melted, cooled and solidified to precipitate crystals in the amorphous state.
  • Raw materials are prepared by a general method to obtain a raw material mixture, and the raw material mixture is melted to obtain a melt. Specifically, a raw material mixture prepared by mixing raw materials so as to include each component in the above range is heated and melted by a general method to obtain a melt.
  • the raw material is not particularly limited as long as it is a raw material used for production of ordinary glass ceramics.
  • raw materials include silica sand, sodium carbonate, diphosphorus pentoxide, zirconium oxide, sodium silicate, trisodium phosphate, ammonium phosphate, sodium metasilicate, sodium disilicate ⁇ n hydrate, sodium diphosphate Hydrates, sodium metaphosphate, sodium hexametaphosphate, zirconium hydroxide, and the like can be used.
  • the melting temperature is preferably from 1400 ° C to 1700 ° C, more preferably from 1450 ° C to 1650 ° C.
  • the melt is preferably solidified by slow cooling.
  • the melt is poured on a carbon plate.
  • the melt poured out on the carbon plate is heated at a glass transition temperature + 20 ° C. (for example, 750 ° C.) for 1 hour and then cooled to room temperature.
  • the cooling rate in cooling from the glass transition temperature + 20 ° C. to room temperature is preferably 2 ° C./min or less, and more preferably 1 ° C./min or less. It is preferable to make the cooling rate slower because crystals are easily precipitated. Moreover, this cooling rate can be 0.2 degree-C / min or more.
  • an object to be processed made of glass ceramics is directly obtained in the process of heating and melting the raw material mixture to obtain a melt, and cooling and solidifying the melt. Therefore, the reheating process in the normal method for producing glass ceramics can be omitted. That is, it is not necessary to have a step of further heat-treating (for example, 800 ° C. or higher) the solidified product (glass ceramic) that has been melted and then cooled to room temperature.
  • the object to be processed may be in any form.
  • the object to be processed may be, for example, a block shape, a plate shape, or a disk shape.
  • the ion exchange treatment replaces part or all of the sodium ions in the object to be treated with lithium ions.
  • the ion-exchanged lithium ions are considered to be introduced into the sites occupied by sodium ions.
  • Lithium ions introduced to the site occupied by sodium ions are easy to move, and therefore the degree of freedom is increased. This is because lithium ions have a smaller ionic radius than sodium ions. That is, lithium ion conductive glass ceramics having a large ion conductivity can be formed by ion exchange treatment.
  • the object to be processed has a NASICON type crystal structure
  • lithium ion conductive glass ceramics having higher ion conductivity can be obtained.
  • the NASICON type crystal structure originally has a characteristic that the ionic conductivity of sodium ions is relatively high. Therefore, when an object to be processed having a NASICON type crystal structure is subjected to ion exchange treatment with lithium ions, two steps of ionic conductivity, ie, good ion conductivity derived from the crystal structure and improvement of ion conductivity by the ion exchange treatment. Improvement effect is obtained. For this reason, it becomes possible to provide lithium ion conductive glass-ceramics with improved ion conductivity compared to the prior art.
  • the conditions for the ion exchange treatment are not particularly limited as long as lithium ions can be introduced into some or all of the sites occupied by sodium ions in the object to be treated.
  • the ion exchange treatment may be performed by immersing the object to be processed in a molten salt containing lithium ions for a predetermined time.
  • the molten salt containing lithium ions for example, lithium nitrate, lithium nitrite, lithium sulfate, lithium chloride, lithium fluoride, and a mixed salt thereof may be used.
  • the temperature condition of the ion exchange treatment varies depending on the molten salt to be used, but may be, for example, 200 ° C. or more and 500 ° C. or less, preferably 300 ° C. or more and 400 ° C. or less.
  • the treatment time of the ion exchange treatment varies depending on temperature conditions, but may be, for example, 24 hours or more and 120 hours or less, preferably 24 hours or more and 80 hours or less.
  • the manufacturing method of the present embodiment may include a step (c) of thinning the thickness of the object to be processed before the ion exchange treatment in the step (b).
  • Process (c) The object to be processed obtained in the step (a) is thinned. Polishing etc. are mentioned as a processing method which makes a to-be-processed object thin.
  • the thickness of the object to be processed is preferably 1 mm or less, more preferably 0.6 mm or less, and further preferably 0.25 mm or less.
  • the thickness of the object to be processed is preferably 0.1 mm or more.
  • the manufacturing method of this embodiment prepares the to-be-processed object which consists of glass ceramics at a process (a), Then, the process to thin the to-be-processed object of a process (c) is performed, and the to-be-processed object of a process (b) Can be performed in the order of ion exchange treatment.
  • the thin target object is only subjected to a temperature load of about 200 to 500 ° C. during the ion exchange process. Therefore, the manufacturing method of the present embodiment can prevent defects such as warpage that are likely to occur on a thin glass substrate or the like.
  • the lithium ion conductive glass ceramic produced according to the present embodiment includes 25% to 50% SiO 2 , 10% to 45% ZrO 2 , more than 0% to 30% P 2 O 5 , and 5%. It is preferable to contain Na 2 O of 40% or less, 30% or more and 45% or less of SiO 2 , 15% or more and 40% or less of ZrO 2 , 2% or more and 25% or less of P 2 O 5 , and 10% or more.
  • it contains 35% or less Na 2 O, 32% or more and 43% or less SiO 2 , 17% or more and 38% or less ZrO 2 , 5% or more and 20% or less P 2 O 5 , and 15% or more More preferably, it contains 30% or less of Na 2 O.
  • the lithium ion conductive glass ceramic preferably has a clear diffraction peak in an X-ray diffraction pattern by X-ray diffraction measurement using CuK ⁇ rays, and has a diffraction peak with a half-value width of 3 ° or less. It is more preferable.
  • the lithium ion conductive glass ceramics preferably has a NASICON type crystal structure.
  • the ion conductivity of the lithium ion conductive glass ceramic is preferably 1.0 ⁇ 10 ⁇ 7 (S / cm) or more.
  • the ionic conductivity means a value obtained by AC impedance measurement at room temperature (20 ° C. or more and 25 ° C. or less; the same applies hereinafter).
  • the ionic conductivity is obtained by measurement by an alternating current impedance method using a sample having electrodes formed on both sides.
  • the ion conductivity of the lithium ion conductive glass ceramic in the present embodiment is calculated from the arc diameter of the colle-core plot obtained by AC impedance measurement under the measurement conditions of an applied voltage of 50 mV and a measurement frequency range of 1 Hz to 1 MHz.
  • the lithium ion conductive glass ceramic produced according to this embodiment can be applied to an inorganic solid electrolyte for a lithium ion secondary battery.
  • the solid electrolyte according to the present embodiment can be applied to a solid electrolyte for a metal-air battery or an all-solid battery.
  • the lithium ion conductive glass ceramic produced by the production method of the present embodiment can be used, for example, as a solid electrolyte of a lithium ion secondary battery, a metal-air battery, or an all-solid battery.
  • FIG. 1 schematically shows an example of the configuration of a lithium ion secondary battery.
  • a lithium ion secondary battery 100 has a cathode electrode 110, an anode electrode 150, and an electrolyte 120 between the electrodes.
  • cathode electrode 110 for example, LiCoO 2 , LiMn 2 O 4 , LiFePO 4 or the like is used.
  • anode electrode 150 for example, metallic lithium, graphite, Li 4 Ti 5 O 12 or the like is used. However, this is merely an example, and it will be apparent to those skilled in the art that other electrode materials may be used for both electrodes.
  • the electrolyte 120 a solid electrolyte containing the lithium ion conductive glass ceramic in the present embodiment is used.
  • the lithium ion conductive glass ceramic according to the present embodiment is used as the electrolyte 120, higher safety can be provided to the lithium ion secondary battery than when a conventional organic solvent-based liquid electrolyte is used.
  • the lithium ion conductive glass ceramic in the present embodiment has higher stability against voltage application than a conventional organic solvent-based liquid electrolyte. For this reason, when a large voltage is applied to the lithium ion secondary battery, the conventional problem that the electrolyte is decomposed or deteriorated is reduced.
  • the lithium ion conductive glass ceramic in this embodiment has high lithium ion conductivity. Therefore, the lithium ion secondary battery 100 having the electrolyte 120 made of the lithium ion conductive glass ceramic according to the present embodiment exhibits better characteristics than a conventional lithium ion secondary battery using a solid electrolyte. be able to.
  • Examples and comparative examples of this embodiment are shown below.
  • Examples 1 to 4 are examples, and example 5 is a comparative example.
  • Table 1 shows the composition (mol% unit) of the raw material mixture and the ionic conductivity of the sample for evaluation obtained after the ion exchange treatment.
  • Example 1 preparation of sample for evaluation
  • the sample for evaluation was produced in the following procedures, and the characteristics were evaluated.
  • the raw material powder is weighed and mixed so that the raw material mixture contains each component in the composition shown in the column of “raw material mixture composition” of Example 1 in Table 1 below (indicated as the raw material mixture composition (mol%) in Table 1).
  • a raw material mixture was obtained.
  • the raw material mixture was put in a platinum crucible, heated at 1650 ° C. for 120 minutes, and melted to obtain a melt of the raw material mixture.
  • the molten material was poured onto a carbon plate. In order to remove the distortion in the sample, the sample was heated at 830 ° C.
  • a sample obtained by heating and melting the raw material mixture to obtain a melt, and cooling and solidifying the melt is referred to as a sample before ion exchange treatment.
  • the sample before ion exchange treatment was pulverized, and X-ray diffraction measurement using CuK ⁇ rays was performed. Since a clear diffraction peak was observed in the obtained X-ray diffraction pattern, it was confirmed that the sample before the ion exchange treatment was glass ceramics. As a result of peak analysis of the X-ray diffraction pattern, it was confirmed that the sample before the ion exchange treatment had a NASICON type crystal structure.
  • ion exchange treatment was performed using the sample before ion exchange treatment after polishing.
  • the ion exchange treatment was performed by immersing the sample before the ion exchange treatment in a 400 ° C. lithium nitrate molten salt.
  • the processing time was 72 hours. Thereby, the sample for evaluation was obtained.
  • FIG. 2 shows an X-ray diffraction pattern of the evaluation sample.
  • the sample for evaluation of Example 1 was the same glass ceramics as before the ion exchange treatment.
  • the sample for evaluation of Example 1 has the same crystal structure as that before the ion exchange treatment, that is, the NASICON type crystal structure.
  • the composition of the sample for evaluation was measured by ICP analysis. As a result, SiO 2 was 30%, ZrO 2 was 35%, P 2 O 5 was 15%, Li 2 O was 20%, and Na 2 O was the detection limit. It was the following. It was confirmed that the sample for evaluation in which most of the sodium ions in the sample before the ion exchange treatment were replaced with lithium ions was obtained by the ion exchange treatment.
  • the ionic conductivity was 5.5 ⁇ 10 ⁇ 5 S / cm.
  • Example 2 In Example 2, the raw material powder was weighed and mixed so that the raw material mixture contained each component with the composition shown in the column of “Raw material mixture composition” in Example 2 in Table 1 above to obtain a raw material mixture. In Example 2, the sample before the ion exchange treatment was polished until the thickness became 0.6 mm. The other production conditions were the same as in Example 1.
  • the X-ray diffraction measurement using CuK ⁇ rays was performed on the sample before ion exchange treatment and the sample for evaluation.
  • FIG. 3 the X-ray-diffraction result of the sample for evaluation is shown.
  • the X-ray diffraction patterns of the sample before and after the ion exchange treatment that is, the sample before the ion exchange treatment and the sample for evaluation were hardly changed. Since the clear diffraction peak was recognized in the X-ray diffraction pattern, the sample before the ion exchange treatment and the evaluation sample were confirmed to be glass ceramics. Further, as a result of peak analysis of the X-ray diffraction pattern, it was confirmed that it had a NASICON type crystal structure.
  • SiO 2 was 42.5%
  • ZrO 2 was 22.5%
  • P 2 O 5 was 15%
  • Li 2 O was 20%
  • Na 2 O was below the detection limit. It was confirmed that the sample for evaluation in which most of the sodium ions in the sample before the ion exchange treatment were replaced with lithium ions was obtained by the ion exchange treatment.
  • the ionic conductivity of the sample for evaluation was 1.6 ⁇ 10 ⁇ 5 S / cm.
  • Example 3 the raw material powder was weighed and mixed so as to include each component in the composition shown in the column of “Raw material mixture composition” in Example 3 in Table 1 above to obtain a raw material mixture.
  • Other manufacturing conditions were the same as in Example 2.
  • the X-ray diffraction measurement using CuK ⁇ rays was performed on the sample before ion exchange treatment and the sample for evaluation.
  • FIG. 4 the X-ray-diffraction result of the sample for evaluation is shown.
  • the X-ray diffraction patterns of the sample before and after the ion exchange treatment that is, the sample before the ion exchange treatment and the sample for evaluation were hardly changed. Since the clear diffraction peak was recognized in the X-ray diffraction pattern, the sample before the ion exchange treatment and the evaluation sample were confirmed to be glass ceramics. Further, as a result of peak analysis of the X-ray diffraction pattern, it was confirmed that it had a NASICON type crystal structure.
  • the composition of the sample for evaluation was measured by ICP analysis. As a result, SiO 2 was 40%, ZrO 2 was 20%, P 2 O 5 was 10%, Li 2 O was 30%, and Na 2 O was the detection limit. It was the following. It was confirmed that the sample for evaluation in which most of the sodium ions in the sample before the ion exchange treatment were replaced with lithium ions was obtained by the ion exchange treatment.
  • the ionic conductivity of the sample for evaluation was 4.1 ⁇ 10 ⁇ 6 S / cm.
  • Example 4 the raw material powder was weighed and mixed so that the raw material mixture contained each component with the composition shown in the column of “Raw material mixture composition” in Example 4 in Table 1 above to obtain a raw material mixture.
  • Other manufacturing conditions were the same as in Example 2.
  • the X-ray diffraction measurement using CuK ⁇ rays was performed on the sample before ion exchange treatment and the sample for evaluation.
  • FIG. 5 the X-ray-diffraction result of the sample for evaluation is shown.
  • the X-ray diffraction patterns of the sample before and after the ion exchange treatment that is, the sample before the ion exchange treatment and the sample for evaluation were hardly changed. Since the clear diffraction peak was recognized in the X-ray diffraction pattern, the sample before the ion exchange treatment and the evaluation sample were confirmed to be glass ceramics. Further, as a result of peak analysis of the X-ray diffraction pattern, it was confirmed that it had a NASICON type crystal structure.
  • the composition of the sample for evaluation was measured by ICP analysis. As a result, SiO 2 was 32.5%, ZrO 2 was 22.5%, P 2 O 5 was 15%, Li 2 O was 30%, Na 2 O was below the detection limit. It was confirmed that the sample for evaluation in which most of the sodium ions in the sample before the ion exchange treatment were replaced with lithium ions was obtained by the ion exchange treatment.
  • the ionic conductivity was measured by the method described above. As a result of the measurement, the ionic conductivity of the sample for evaluation was 3.4 ⁇ 10 ⁇ 7 S / cm.
  • Example 5 the raw material powder was weighed and mixed so as to include each component in the composition shown in the column of “Raw material mixture composition” in Example 5 in Table 1 to obtain a raw material mixture.
  • Other manufacturing conditions were the same as in Example 2.
  • the X-ray diffraction measurement using CuK ⁇ rays was performed on the sample before ion exchange treatment and the sample for evaluation.
  • FIG. 6 the X-ray-diffraction result of the sample for evaluation is shown.
  • the sample before ion exchange treatment and the sample for evaluation were hardly changed.
  • the sample before ion exchange treatment and the sample for evaluation are ZrSiO 4 (h mark), Li 3 PO 4 (i mark), SiO 2 (j mark), and ZrO 2 (k mark). ). Further, it did not contain a NASICON type crystal structure.
  • ZrO (m mark) is an internal standard substance put in the case of X-ray diffraction measurement.
  • the ionic conductivity of the sample for evaluation was as low as 2.9 ⁇ 10 ⁇ 8 S / cm.

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Abstract

L'invention concerne un procédé de fabrication d'un verre-céramique conducteur des ions de lithium qui est caractérisé par la mise en jeu (a) d'une étape de mélange de matériaux bruts pour obtenir un mélange de matériaux bruts qui contient, exprimé en % molaire en termes d'oxydes, de 25 à 50% de SiO2, de 10 à 45% de ZrO2, plus de 0% et moins de 30% de P2O5, et de 5 à 40% de Na2O, et d'obtention, par l'intermédiaire d'un processus de fusion, refroidissement et solidification du mélange de matériaux bruts, d'une pièce de travail consistant en un verre-céramique, et (b) une étape dans laquelle la pièce de travail subit un traitement d'échange ionique dans un sel fondu contenant des ions de lithium.
PCT/JP2014/054902 2013-03-05 2014-02-27 Procédé de fabrication de verre-céramique conducteur des ions de lithium, verre-céramique conducteur des ions de lithium et cellule secondaire au lithium-ion WO2014136650A1 (fr)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9487441B2 (en) 2011-10-28 2016-11-08 Corning Incorporated Glass articles with infrared reflectivity and methods for making the same
US10116035B2 (en) 2015-04-30 2018-10-30 Corning Incorporated Electrically conductive articles with discrete metallic silver layers and methods for making same
GB2568613A (en) * 2018-02-01 2019-05-22 Thermal Ceram Uk Ltd Energy storage device and ionic conducting composition for use therein
CN112397774A (zh) * 2020-10-19 2021-02-23 上海空间电源研究所 一种固态电解质膜、制备方法及固态电池
CN112563564A (zh) * 2020-11-13 2021-03-26 上海空间电源研究所 一种制备钠离子固体电解质的软化学合成方法
CN112563565A (zh) * 2020-11-13 2021-03-26 上海空间电源研究所 一种锂钠离子混合固态电解质的制备方法及固态混合电池
US11264614B2 (en) 2018-02-01 2022-03-01 Thermal Ceramics Uk Limited Energy storage device and ionic conducting composition for use therein
JP2022530939A (ja) * 2019-06-26 2022-07-05 上海空間電源研究所 リチウムイオン固体電解質及びその製造方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52156200A (en) * 1976-06-21 1977-12-26 Massachusetts Inst Technology Composition for transporting alkali metal ion rapidly
JPS59107942A (ja) * 1982-11-30 1984-06-22 アメリカ合衆国 イオン伝導性ガラス
JP2002519836A (ja) * 1998-06-26 2002-07-02 ヴァレンス テクノロジー、 インク． リチウム含有リン酸ケイ素塩と、その製造方法および使用方法
JP2010275130A (ja) * 2009-05-27 2010-12-09 Hoya Corp リチウムイオン伝導性ガラスの製造方法
JP2012531709A (ja) * 2009-06-26 2012-12-10 セラマテック インコーポレイテッド アルカリ金属超イオン伝導セラミック
WO2013031507A1 (fr) * 2011-08-31 2013-03-07 旭硝子株式会社 Procédé permettant de fabriquer un électrolyte solide conducteur au lithium-ion, et batterie rechargeable au lithium-ion

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52156200A (en) * 1976-06-21 1977-12-26 Massachusetts Inst Technology Composition for transporting alkali metal ion rapidly
JPS59107942A (ja) * 1982-11-30 1984-06-22 アメリカ合衆国 イオン伝導性ガラス
JP2002519836A (ja) * 1998-06-26 2002-07-02 ヴァレンス テクノロジー、 インク． リチウム含有リン酸ケイ素塩と、その製造方法および使用方法
JP2010275130A (ja) * 2009-05-27 2010-12-09 Hoya Corp リチウムイオン伝導性ガラスの製造方法
JP2012531709A (ja) * 2009-06-26 2012-12-10 セラマテック インコーポレイテッド アルカリ金属超イオン伝導セラミック
WO2013031507A1 (fr) * 2011-08-31 2013-03-07 旭硝子株式会社 Procédé permettant de fabriquer un électrolyte solide conducteur au lithium-ion, et batterie rechargeable au lithium-ion
WO2013031508A1 (fr) * 2011-08-31 2013-03-07 旭硝子株式会社 Vitrocéramique conductrice au lithium-ion et son procédé de fabrication

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9586861B2 (en) 2011-10-28 2017-03-07 Corning Incorporated Glass articles with discrete metallic silver layers and methods for making the same
US9975805B2 (en) 2011-10-28 2018-05-22 Corning Incorporated Glass articles with infrared reflectivity and methods for making the same
US9487441B2 (en) 2011-10-28 2016-11-08 Corning Incorporated Glass articles with infrared reflectivity and methods for making the same
US11535555B2 (en) 2011-10-28 2022-12-27 Corning Incorporated Glass articles with infrared reflectivity and methods for making the same
US10116035B2 (en) 2015-04-30 2018-10-30 Corning Incorporated Electrically conductive articles with discrete metallic silver layers and methods for making same
US11264614B2 (en) 2018-02-01 2022-03-01 Thermal Ceramics Uk Limited Energy storage device and ionic conducting composition for use therein
GB2568613A (en) * 2018-02-01 2019-05-22 Thermal Ceram Uk Ltd Energy storage device and ionic conducting composition for use therein
GB2568613B (en) * 2018-02-01 2020-06-24 Thermal Ceram Uk Ltd Energy storage device and ionic conducting composition for use therein
JP7253075B2 (ja) 2019-06-26 2023-04-05 上海空間電源研究所 リチウムイオン固体電解質及びその製造方法
JP2022530939A (ja) * 2019-06-26 2022-07-05 上海空間電源研究所 リチウムイオン固体電解質及びその製造方法
CN112397774A (zh) * 2020-10-19 2021-02-23 上海空间电源研究所 一种固态电解质膜、制备方法及固态电池
CN112563565B (zh) * 2020-11-13 2022-03-25 上海空间电源研究所 一种锂钠离子混合固态电解质的制备方法及固态混合电池
CN112563564B (zh) * 2020-11-13 2021-11-09 上海空间电源研究所 一种制备钠离子固体电解质的软化学合成方法
CN112563565A (zh) * 2020-11-13 2021-03-26 上海空间电源研究所 一种锂钠离子混合固态电解质的制备方法及固态混合电池
CN112563564A (zh) * 2020-11-13 2021-03-26 上海空间电源研究所 一种制备钠离子固体电解质的软化学合成方法

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