WO2012011179A1 - 硫化物固体電解質ガラス、硫化物固体電解質ガラスの製造方法およびリチウム固体電池 - Google Patents
硫化物固体電解質ガラス、硫化物固体電解質ガラスの製造方法およびリチウム固体電池 Download PDFInfo
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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
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
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- 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
- C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
- C03C14/006—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of microcrystallites, e.g. of optically or electrically active material
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- 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
- C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
- C03C3/321—Chalcogenide glasses, e.g. containing S, Se, Te
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- 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
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/80—Non-oxide glasses or glass-type compositions
- C03B2201/86—Chalcogenide glasses, i.e. S, Se or Te glasses
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- 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
- C03C2214/00—Nature of the non-vitreous component
- C03C2214/16—Microcrystallites, e.g. of optically or electrically active material
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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- 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 sulfide solid electrolyte glass that generates very little hydrogen sulfide.
- lithium batteries currently on the market use an electrolyte containing a flammable organic solvent, it is possible to install safety devices that suppress the temperature rise during short circuits and to improve the structure and materials to prevent short circuits. Necessary.
- a lithium battery in which the electrolyte is changed to a solid electrolyte layer to make the battery completely solid does not use a flammable organic solvent in the battery, so the safety device can be simplified, and manufacturing costs and productivity can be reduced. It is considered excellent.
- sulfide solid electrolyte glass is known as a solid electrolyte material used for such a solid electrolyte layer.
- Non-Patent Document 1 discloses a glassy Li ion conductive material in which Li 2 S in 75Li 2 S ⁇ 25P 2 S 5 is partially substituted with Li 2 O.
- the sulfide solid electrolyte glass has an advantage of high Li ion conductivity, but has a problem that hydrogen sulfide is generated when it comes into contact with water (including moisture, the same applies hereinafter).
- the present inventors have obtained the knowledge that the amount of hydrogen sulfide generated can be reduced by adjusting the composition of the sulfide solid electrolyte glass to the ortho composition.
- ortho generally refers to one having the highest degree of hydration among oxo acids obtained by hydrating the same oxide.
- the crystal composition to which Li 2 S is most added in sulfide is called an ortho composition.
- Li 3 PS 4 corresponds to the ortho composition
- the sulfide solid electrolyte glass is obtained.
- the sulfide solid electrolyte glass having such a composition of 75Li 2 S ⁇ 25P 2 S 5 is theoretically considered to have the least amount of hydrogen sulfide generated because no Li 2 S remains, Nevertheless, it has been confirmed that a small amount of hydrogen sulfide is generated. Therefore, in order to improve the stability of the sulfide solid electrolyte glass, it is necessary to further reduce the generation of hydrogen sulfide.
- the present invention has been made in view of the above circumstances, and has as its main object to provide a sulfide solid electrolyte glass with a very small amount of hydrogen sulfide generated.
- Li 2 S remains in sulfide solid electrolyte glass having a composition of 75Li 2 S ⁇ 25P 2 S 5 was obtained. It was. Specifically, Li 2 S remaining in the sulfide solid electrolyte glass having the above composition and not detectable by X-ray diffraction (XRD) measurement was detected by X-ray photoelectron spectroscopy (XPS) measurement.
- XRD X-ray diffraction
- XPS X-ray photoelectron spectroscopy
- the present inventors have based on the content of Li 2 S sulfide solid electrolyte glass by XPS measurement, the composition of the sulfide solid electrolyte glass, and more Li 2 S remaining amount is small composition
- the inventors have found that the amount of hydrogen sulfide generated can be reduced as compared with the sulfide solid electrolyte glass having the composition of 75Li 2 S ⁇ 25P 2 S 5 , and have reached the present invention.
- a sulfide solid electrolyte glass composed of Li 3 PS 4, 31 P NMR Li 4 P 2 S 7 is not detected by the measurement, and the content of Li 2 S by XPS measurement
- a sulfide solid electrolyte glass characterized in that the amount is 3 mol% or less.
- a sulfide solid electrolyte glass with a small amount of remaining Li 2 S can be obtained.
- Li 4 P 2 S 7 is not detected by 31 P NMR measurement can be a sulfide solid electrolyte glass S 3 PS-PS 3 unit (P 2 S 7 unit) is not formed. Therefore, the amount of hydrogen sulfide generated is extremely small, and a highly safe sulfide solid electrolyte glass can be obtained.
- the content of Li 2 S by the XPS measurement is less than 1 mol%. It is because it can be set as the sulfide solid electrolyte glass with less hydrogen sulfide generation amount.
- a method for producing an electrolyte glass is provided.
- the raw material composition contains Li 2 S and P 2 S 5 in a predetermined ratio, the remaining amount of Li 2 S is small, and the S 3 P—S—PS 3 unit (P 2 S 7 unit) is not formed can be obtained sulfide solid electrolyte glass. Therefore, it is possible to obtain a sulfide solid electrolyte glass with a very low hydrogen sulfide generation amount and high safety.
- the content of Li 2 S by the XPS measurement is less than 1 mol%. This is because a sulfide solid electrolyte glass with less hydrogen sulfide generation can be obtained.
- the present invention also relates to a method for producing a sulfide solid electrolyte glass composed of Li 3 PS 4 , wherein Li 2 S and P 2 S 5 are replaced with xLi 2 S ⁇ (100 ⁇ x) P 2 S 5.
- a method for producing a sulfide solid electrolyte glass is provided.
- the present invention by using the raw material composition containing Li 2 S and P 2 S 5 in a predetermined ratio, the remaining amount of Li 2 S is small, and the S 3 P—S—PS 3 unit (P 2 S 7 unit) is not formed can be obtained sulfide solid electrolyte glass. Therefore, it is possible to obtain a sulfide solid electrolyte glass with a very low hydrogen sulfide generation amount and high safety.
- the amorphization treatment is preferably mechanical milling. This is because processing at room temperature is possible, and the manufacturing process can be simplified.
- a positive electrode active material layer containing a positive electrode active material, a negative electrode active material layer containing a negative electrode active material, and a solid electrolyte formed between the positive electrode active material layer and the negative electrode active material layer A lithium solid state battery, wherein at least one of the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer contains the sulfide solid electrolyte glass described above.
- FIG. 1 is a graph showing the Li 2 S content by XPS measurement for the sulfide solid electrolyte glasses obtained in Examples 1 to 3 and Comparative Examples 1 to 3.
- 2 is an XPS spectrum of the sulfide solid electrolyte glass obtained in Example 2 and Comparative Example 1.
- 6 is a graph showing the content of Li 4 P 2 S 7 by 31 P NMR measurement for the sulfide solid electrolyte glasses obtained in Examples 1 to 3 and Comparative Examples 1 to 3.
- 3 is a 31 P NMR spectrum of the sulfide solid electrolyte glass obtained in Comparative Example 1.
- 3 is a graph showing the results of hydrogen sulfide generation amount measurement for sulfide solid electrolyte glasses obtained in Examples 1 to 3 and Comparative Examples 1 to 3.
- 6 is a graph showing the results of Li ion conductivity measurement for the sulfide solid electrolyte glasses obtained in Examples 1 to 3 and Comparative Examples 1 to 3. 6 is a graph showing the results of XRD measurement for the sulfide solid electrolyte glass obtained in Comparative Example 1.
- the sulfide solid electrolyte glass of the present invention is a sulfide solid electrolyte glass composed of Li 3 PS 4 , Li 4 P 2 S 7 is not detected by 31 P NMR measurement, and Li 2 by XPS measurement is used.
- the S content is 3 mol% or less.
- a sulfide solid electrolyte glass with a small amount of remaining Li 2 S can be obtained.
- a sulfide solid electrolyte glass in which no S 3 P—S—PS 3 unit (P 2 S 7 unit) is formed by detecting no Li 4 P 2 S 7 by 31 P NMR (nuclear magnetic resonance) measurement. be able to. Therefore, the amount of hydrogen sulfide generated is extremely small, and a highly safe sulfide solid electrolyte glass can be obtained.
- the bridging sulfur present in the Li 2 S and S 3 PS—PS 3 units is highly reactive and generates hydrogen sulfide by reacting with water.
- the sulfide solid electrolyte glass of the present invention has the above-described composition, it is possible to reduce the content of Li 2 S and bridged sulfur in the sulfide solid electrolyte glass that generate a large amount of hydrogen sulfide. The amount of hydrogen sulfide generated can be extremely reduced.
- the sulfide solid electrolyte glass of the present invention is composed of Li 3 PS 4 .
- being composed of Li 3 PS 4 has a peak in the range of 415 cm ⁇ 1 to 420 cm ⁇ 1 in the Raman spectroscopic measurement, and a peak in the range of 80 ppm to 90 ppm in the 31 P NMR measurement. It means having. In 31 P NMR measurement, it is preferable to use the MAS (Magic Angle Spinning) method.
- the sulfide solid electrolyte glass of the present invention is composed of Li 3 PS 4 which is an ortho composition, the amount of hydrogen sulfide generated is reduced, and further, Li 4 P 2 S 7 is not detected by 31 P NMR measurement, Moreover, the amount of hydrogen sulfide generated can be extremely reduced by having a composition in which the content of Li 2 S by XPS measurement is 3 mol% or less.
- Li 4 P 2 S 7 is not detected by 31 P NMR measurement.
- the content of Li 2 S by XPS measurement is 3 mol% or less. As shown in the examples described later, when the content of Li 2 S is 3 mol% or less, the content of Li 2 S is significantly reduced. On the other hand, in the sulfide solid electrolyte glass having an ortho composition (75Li 2 S ⁇ 25P 2 S 5 ) in which no Li 2 S remains theoretically, the content of Li 2 S is 5 mol% or more. This is considered to be because it is difficult to prepare the suspension solid electrolyte glass from the raw material composition completely homogeneously.
- the content of Li 2 S is, for example, by using Quantera SXM manufactured by PHI Co., Ltd., excitation X-ray monochromatic AlK ⁇ 1, 2 line (1486.6 eV), X-ray diameter 100 ⁇ m, photoelectron escape angle 45 °, Ar ion etching ( It can be determined as follows by XPS measurement performed under measurement conditions measured at an etching rate of 30 nm in terms of SiO 2 with an ion acceleration voltage of 2 kV and an etching rate of 4 nm / min (SiO 2 equivalent). . That is, three sulfur states are assumed and fitting is performed.
- the peak positions of the three sulfur states are variable, and the peak position with the best fit is selected and the peak fit is performed. At that time, the sulfur state having a peak in most low-energy Li as 2 S, it is possible to determine the S fraction of Li 2 S than the area ratio of each state (the content of Li 2 S).
- the three sulfur states are presumed to be SP, Li-SP, and Li 2 S (S 2 ⁇ ) from the high energy side.
- the content of Li 2 S may be 3 mol% or less, but is preferably 1 mol% or less. It is because it can be set as the sulfide solid electrolyte glass with less hydrogen sulfide generation amount. In particular, when the content of Li 2 S is 1 mol% or less, it is close to the measurement limit and almost no Li 2 S remains.
- the sulfide solid electrolyte glass of the present invention can be obtained, for example, by subjecting a raw material composition to be described later to an amorphization treatment.
- the amorphization treatment include a mechanical milling method and a melt quenching method, and among them, the mechanical milling method is preferable. This is because processing at room temperature is possible, and the manufacturing process can be simplified.
- the raw material composition used in the present invention contains at least Li element, P element and S element.
- the composition of the raw material composition is a sulfide composed of Li 3 PS 4 , Li 4 P 2 S 7 is not detected by 31 P NMR measurement, and the content of Li 2 S by XPS measurement is 3 mol% or less is not particularly limited as long as the composition can be obtained a solid electrolyte glass. for example, there may be mentioned those containing Li 2 S and P 2 S 5.
- the raw material composition may contain only Li 2 S and P 2 S 5 , and may further contain other raw materials. Further, Li 2 S contained in the raw material composition is preferably less impurities. This is because side reactions can be suppressed.
- Examples of the method for synthesizing Li 2 S include the method described in JP-A-7-330312. Furthermore, Li 2 S is preferably purified using the method described in WO2005 / 040039. Similarly, it is preferable that P 2 S 5 contained in the raw material composition is also low in impurities.
- the ratio of Li 2 S and P 2 S 5 in the raw material composition is composed of Li 3 PS 4 , Li 4 P 2 S 7 is not detected by 31 P NMR measurement, and Li 2 S is contained by XPS measurement
- the amount is not particularly limited as long as it is a ratio capable of obtaining a sulfide solid electrolyte glass having an amount of 3 mol% or less.
- the lower limit of the ratio of Li 2 S to the total of Li 2 S and P 2 S 5 in the raw material composition is the composition of the sulfide solid electrolyte glass in which Li 4 P 2 S 7 is not detected by 31 P NMR measurement. , It can be determined from the composition with the least Li 2 S.
- the upper limit of the ratio of Li 2 S to the total of Li 2 S and P 2 S 5 in the raw material composition, in the composition of the sulfide solid electrolyte glass in which the content of Li 2 S by XPS measurement is 3 mol% or less It can be determined from the composition with the most Li 2 S.
- the Li 2 S content is determined by the XPS measurement described above.
- the other raw materials added to the raw material composition include at least one orthooxo selected from the group consisting of Li 3 PO 4 , Li 4 SiO 4 , Li 4 GeO 4 , Li 3 BO 3 and Li 3 AlO 3. Mention may be made of lithium acid. By adding lithium orthooxoate, a more stable sulfide solid electrolyte glass can be obtained.
- a crystallized sulfide solid electrolyte glass can be obtained. That is, a crystallized sulfide solid electrolyte glass can be obtained by sequentially performing an amorphization process and a heat treatment on the raw material composition.
- the temperature of the heat treatment is, for example, preferably 270 ° C. or higher, more preferably 280 ° C. or higher, and further preferably 285 ° C. or higher.
- the temperature of the heat treatment is preferably, for example, 310 ° C. or less, more preferably 300 ° C. or less, and further preferably 295 ° C. or less.
- the heat treatment time is, for example, in the range of 1 minute to 2 hours, and more preferably in the range of 30 minutes to 1 hour.
- the hydrogen sulfide concentration in 5 minutes from the start of measurement is preferably 10 ppm or less, more preferably 5 ppm or less, and 1 ppm or less. More preferably it is. This is because the hydrogen sulfide concentration is low, that is, the amount of hydrogen sulfide generated is small, so that a safer sulfide solid electrolyte glass can be obtained.
- the hydrogen sulfide amount measurement test refers to the following test.
- a sulfide solid electrolyte glass was weighed under an Ar atmosphere and left in a closed container (humidity state of 1750 cc volume, humidity 50%, temperature 20 ° C.), and hydrogen sulfide generated in the first 5 minutes The amount generated is measured using a hydrogen sulfide sensor.
- the sealed container is stirred with a fan.
- the sulfide solid electrolyte glass of the present invention preferably has a high Li ion conductivity value.
- the Li ion conductivity at room temperature is preferably 10 ⁇ 5 S / cm or more, and more preferably 10 ⁇ 4 S / cm or more.
- the sulfide solid electrolyte glass of the present invention is usually in the form of powder, and the average diameter thereof is, for example, in the range of 0.1 ⁇ m to 50 ⁇ m.
- a lithium battery can be used, and among them, it is preferable to be used for a lithium solid battery. This is because it is useful as a solid electrolyte material constituting the solid electrolyte layer of a lithium solid state battery.
- the lithium battery may be a primary battery or a secondary battery, but is preferably a secondary battery. This is because it can be repeatedly charged and discharged and is useful, for example, as a vehicle-mounted battery.
- the method for producing a sulfide solid electrolyte glass according to the first embodiment includes a preparation step of preparing a raw material composition containing Li 2 S and P 2 S 5 , and an amorphous treatment of the raw material composition by an amorphization treatment.
- An amorphization step wherein the raw material composition is Li 2 S and P 2 S 5 , Li 4 P 2 S 7 is not detected by 31 P NMR measurement, and XPS
- the content of Li 2 S by measurement is such that it is contained in a proportion capable of obtaining a sulfide solid electrolyte glass having a content of 3 mol% or less.
- the raw material composition contains Li 2 S and P 2 S 5 in a predetermined ratio, the remaining amount of Li 2 S is small, and the S 3 PS—PS 3 unit A sulfide solid electrolyte glass in which (P 2 S 7 unit) is not formed can be obtained. Therefore, it is possible to obtain a sulfide solid electrolyte glass with a very low hydrogen sulfide generation amount and high safety.
- FIG. 1 is a flowchart for explaining an example of a method for producing a sulfide solid electrolyte glass of the first embodiment.
- a raw material composition is prepared (preparation process).
- the ratio of Li 2 S and P 2 S 5 is a sulfide solid in which Li 4 P 2 S 7 is not detected by 31 P NMR measurement and the content of Li 2 S by XPS measurement is 3 mol% or less. It is the ratio which can obtain electrolyte glass.
- the raw material composition is made amorphous by performing mechanical milling (amorphization process).
- the preparation step in the first embodiment is a method for producing a sulfide solid electrolyte glass composed of Li 3 PS 4 , and prepares a raw material composition containing Li 2 S and P 2 S 5. It is a process to do. Furthermore, in the raw material composition, Li 2 S and P 2 S 5 are Li 4 P 2 S 7 not detected by 31 P NMR measurement, and the content of Li 2 S by XPS measurement is 3 mol% or less. The sulfide solid electrolyte glass is contained in such a ratio that it can be obtained. In addition, about the raw material composition in a 1st embodiment, since it is the same as that of the content described in said "A. sulfide solid electrolyte glass", description here is abbreviate
- the amorphization step in the first embodiment is a step of amorphizing the raw material composition by an amorphization process.
- the amorphization treatment in the present invention is not particularly limited as long as it is a treatment capable of obtaining a sulfide solid electrolyte glass, and examples thereof include mechanical milling and melt quenching methods. Mechanical milling is preferred. This is because processing at room temperature is possible, and the manufacturing process can be simplified.
- Mechanical milling is not particularly limited as long as the raw material composition is mixed while imparting mechanical energy, and examples thereof include a ball mill, a vibration mill, a turbo mill, a mechanofusion, and a disk mill. Among them, a ball mill is preferable, and a planetary ball mill is particularly preferable. This is because the desired sulfide solid electrolyte glass can be obtained efficiently.
- the various conditions of mechanical milling are set so that a sufficiently solid amorphous sulfide solid electrolyte glass can be obtained.
- a planetary ball mill when a planetary ball mill is used, a raw material composition and grinding balls are added, and the treatment is performed at a predetermined number of revolutions and time.
- the number of rotations when performing the planetary ball mill is, for example, preferably in the range of 200 rpm to 500 rpm, and more preferably in the range of 250 rpm to 400 rpm.
- the processing time when performing the planetary ball mill is preferably in the range of 1 hour to 100 hours, and more preferably in the range of 1 hour to 50 hours.
- Heat treatment step In the first embodiment, a heat treatment step of heat treating the sulfide solid electrolyte glass obtained in the amorphization treatment step may be performed. Thereby, a crystallized sulfide solid electrolyte glass is usually obtained.
- description here is abbreviate
- the sulfide solid electrolyte glass obtained according to the first embodiment is the same as the content described in the above-mentioned “A. Sulfide solid electrolyte glass”, and the description here is omitted. .
- a sulfide solid electrolyte glass characterized by being obtained by the preparation step and the amorphization step described above can be provided.
- the method for producing a sulfide solid electrolyte glass according to the second embodiment is a method for producing a sulfide solid electrolyte glass composed of Li 3 PS 4 , wherein Li 2 S and P 2 S 5 are replaced with xLi 2 S ⁇ ( 100-x) a preparation step of preparing a raw material composition containing a molar ratio of P 2 S 5 (x is 73 ⁇ x ⁇ 75), and the raw material composition is made amorphous by an amorphization treatment And an amorphization step.
- the second embodiment by using a raw material composition containing Li 2 S and P 2 S 5 in a predetermined ratio, the remaining amount of Li 2 S is small, and the S 3 P—S—PS 3 unit ( A sulfide solid electrolyte glass in which (P 2 S 7 unit) is not formed can be obtained. Therefore, it is possible to obtain a sulfide solid electrolyte glass with a very low hydrogen sulfide generation amount and high safety.
- the preparation step in the second embodiment includes a raw material containing Li 2 S and P 2 S 5 in a molar ratio of xLi 2 S ⁇ (100 ⁇ x) P 2 S 5 (x is 73 ⁇ x ⁇ 75). It is a process of preparing a composition.
- the above x may be 73 ⁇ x ⁇ 75, but among them, 73.5 ⁇ x ⁇ 74 is preferable, and 73.5 ⁇ x ⁇ 73.8 is more preferable. This is because a sulfide solid electrolyte glass with less hydrogen sulfide generation can be obtained.
- description here is abbreviate
- each component is preferably dispersed uniformly.
- the lithium solid state battery of the present invention includes a positive electrode active material layer containing a positive electrode active material, a negative electrode active material layer containing a negative electrode active material, and a solid formed between the positive electrode active material layer and the negative electrode active material layer.
- FIG. 2 is a schematic cross-sectional view showing an example of the lithium solid state battery of the present invention.
- a lithium solid battery 10 shown in FIG. 2 includes a positive electrode active material layer 1 containing a positive electrode active material, a negative electrode active material layer 2 containing a negative electrode active material, and between the positive electrode active material layer 1 and the negative electrode active material layer 2.
- the solid electrolyte layer 3 formed on the cathode, the positive electrode current collector 4 for collecting current of the positive electrode active material layer 1, the negative electrode current collector 5 for collecting current of the negative electrode active material layer 2, and these members are housed.
- a battery case 6 is provided.
- At least one of the positive electrode active material layer 1, the negative electrode active material layer 2, and the solid electrolyte layer 3 contains the sulfide solid electrolyte glass described in “A. Sulfide solid electrolyte glass”.
- the solid electrolyte layer in the present invention is a layer formed between the positive electrode active material layer and the negative electrode active material layer, and is a layer composed of a solid electrolyte material.
- the solid electrolyte material contained in the solid electrolyte layer is not particularly limited as long as it has Li ion conductivity.
- the solid electrolyte material contained in the solid electrolyte layer is preferably the sulfide solid electrolyte glass described in the above “A. Sulfide solid electrolyte glass”. This is because a lithium solid battery having a very low hydrogen sulfide generation amount and high safety can be obtained.
- the content of the solid electrolyte material in the solid electrolyte layer is not particularly limited as long as a desired insulating property can be obtained.
- the content is in the range of 10% to 100% by volume, especially 50% by volume. It is preferably in the range of ⁇ 100% by volume.
- the solid electrolyte layer is preferably composed only of the sulfide solid electrolyte glass. This is because it is possible to obtain a lithium solid state battery with less hydrogen sulfide generation and higher safety.
- the solid electrolyte layer may contain a binder. This is because a solid electrolyte layer having flexibility can be obtained by containing a binder.
- the binder include fluorine-containing binders such as PTFE.
- the thickness of the solid electrolyte layer is, for example, preferably in the range of 0.1 ⁇ m to 1000 ⁇ m, and more preferably in the range of 0.1 ⁇ m to 300 ⁇ m.
- the method of compression-molding the material which comprises a solid electrolyte layer, etc. can be mentioned, for example.
- the positive electrode active material layer in the present invention is a layer containing at least a positive electrode active material, and may further contain at least one of a solid electrolyte material, a conductive material and a binder as necessary.
- the solid electrolyte material contained in the positive electrode active material layer is preferably the sulfide solid electrolyte glass described in the above “A. Sulfide solid electrolyte glass”. This is because a lithium solid battery having a very low hydrogen sulfide generation amount and high safety can be obtained.
- the content of the solid electrolyte material in the positive electrode active material layer is, for example, in the range of 0.1% by volume to 80% by volume, especially in the range of 1% by volume to 60% by volume, in particular, 10% by volume to 50% by volume. It is preferable to be within the range.
- the positive electrode active material it is not particularly limited, for example, LiCoO 2, LiMnO 2, Li 2 NiMn 3 O 8, LiVO 2, LiCrO 2, LiFePO 4, LiCoPO 4, LiNiO 2, LiNi 1/3 Co 1/3 Mn 1/3 O 2 and the like.
- the conductive material include acetylene black, ketjen black, and carbon fiber.
- the binder include fluorine-containing binders such as PTFE.
- the thickness of the positive electrode active material layer is preferably in the range of 0.1 ⁇ m to 1000 ⁇ m, for example.
- the method etc. which compression-mold the material which comprises a positive electrode active material layer can be mentioned, for example.
- the negative electrode active material layer in the present invention is a layer containing at least a negative electrode active material, and may further contain at least one of a solid electrolyte material, a conductive material, and a binder as necessary.
- the solid electrolyte material contained in the negative electrode active material layer is preferably the sulfide solid electrolyte glass described in the above “A. Sulfide solid electrolyte glass”. This is because a lithium solid battery having a very low hydrogen sulfide generation amount and high safety can be obtained.
- the content of the solid electrolyte material in the negative electrode active material layer is, for example, in the range of 0.1% by volume to 80% by volume, especially in the range of 1% by volume to 60% by volume, in particular, 10% by volume to 50% by volume. It is preferable to be within the range.
- Examples of the negative electrode active material include a metal active material and a carbon active material.
- Examples of the metal active material include In, Al, Si, and Sn.
- examples of the carbon active material include mesocarbon microbeads (MCMB), highly oriented graphite (HOPG), hard carbon, and soft carbon. Note that the conductive material and the binder used in the negative electrode active material layer are the same as those in the positive electrode active material layer described above.
- the thickness of the negative electrode active material layer is preferably in the range of 0.1 ⁇ m to 1000 ⁇ m, for example.
- the method etc. which compression-mold the material which comprises a negative electrode active material layer can be mentioned, for example.
- the lithium solid state battery of the present invention has at least the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer described above. Furthermore, it usually has a positive electrode current collector for collecting current of the positive electrode active material layer and a negative electrode current collector for collecting current of the negative electrode active material layer.
- Examples of the material for the positive electrode current collector include SUS, aluminum, nickel, iron, titanium, and carbon. Among them, SUS is preferable.
- examples of the material for the negative electrode current collector include SUS, copper, nickel, and carbon. Among them, SUS is preferable.
- the thickness and shape of the positive electrode current collector and the negative electrode current collector are preferably appropriately selected according to the use of the lithium solid state battery.
- the battery case of a general lithium solid battery can be used for the battery case used for this invention.
- the battery case include a SUS battery case.
- the power generation element may be formed inside the insulating ring.
- Lithium solid battery The lithium solid battery of the present invention may be a primary battery or a secondary battery, and among these, a secondary battery is preferable. This is because it can be repeatedly charged and discharged and is useful, for example, as a vehicle-mounted battery.
- Examples of the shape of the lithium solid state battery of the present invention include a coin type, a laminate type, a cylindrical type, and a square type.
- the manufacturing method of the lithium solid state battery of the present invention is not particularly limited as long as it is a method capable of obtaining the above-described lithium solid state battery, and the same method as a general lithium solid state battery manufacturing method is used. be able to.
- a method for producing a lithium solid state battery a power generation element is manufactured by sequentially pressing a material constituting the positive electrode active material layer, a material constituting the solid electrolyte layer, and a material constituting the negative electrode active material layer, A method of storing the power generation element in the battery case and caulking the battery case can be exemplified.
- the present invention also provides a positive electrode active material layer, a negative electrode active material layer, and a solid electrolyte layer each containing the sulfide solid electrolyte glass described in “A. Sulfide solid electrolyte glass”. You can also
- the present invention is not limited to the above embodiment.
- the above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.
- the amount of hydrogen sulfide generated was measured for the sulfide solid electrolyte glasses obtained in Examples 1 to 3 and Comparative Examples 1 to 3.
- the amount of hydrogen sulfide generated was measured as follows. 100 mg of the sulfide solid electrolyte glass was weighed under an Ar atmosphere and left in a sealed container (humidified state of 1750 cc volume, humidity 50%, temperature 20 ° C.). The sealed container was stirred with a fan, and a hydrogen sulfide sensor was used for the measurement.
- Example 7 shows the hydrogen sulfide concentration in the sealed container 5 minutes after exposure to the atmosphere of the sulfide solid electrolyte glass obtained in Examples 1 to 3 and Comparative Examples 1 to 3. As shown in FIG. 7, it was confirmed that Examples 1 to 3 produced significantly lower amounts of hydrogen sulfide than Comparative Example 1. From the results of the XPS measurement and 31 P NMR measurement, the contents of Li 2 S and Li 4 P 2 S 7 were minimized in Example 1, but from the results of hydrogen sulfide generation amount measurement, The amount of hydrogen sulfide generated was minimized in Example 2. This is probably because Li 4 P 2 S 7 below the detection lower limit of 31 P NMR measurement is contained in Example 1.
- Li ion conductivity was measured for the sulfide solid electrolyte glasses obtained in Examples 1 to 3 and Comparative Examples 1 to 3. Li ion conductivity was measured as follows. 100 mg of sulfide solid electrolyte glass added to a support tube (made by Macor) was sandwiched between electrodes made of SKD. Thereafter, the sulfide solid electrolyte glass was compacted at a pressure of 4.3 ton / cm 2 , and impedance measurement was performed while restraining the sulfide solid electrolyte glass at 6 Ncm.
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Abstract
Description
まず、本発明の硫化物固体電解質ガラスについて説明する。本発明の硫化物固体電解質ガラスは、Li3PS4から構成される硫化物固体電解質ガラスであって、31P NMR測定によりLi4P2S7が検出されず、かつ、XPS測定によるLi2Sの含有量が3mol%以下であることを特徴とするものである。
Li2SおよびS3P-S-PS3ユニット中に存在する架橋硫黄は、反応性が高く、水と反応することで硫化水素を発生する。これに対して、本発明の硫化物固体電解質ガラスは、上述した組成を有するため、硫化水素発生量の多いLi2Sおよび架橋硫黄の硫化物固体電解質ガラス中における含有量を低減することができ、硫化水素発生量を極めて少なくすることができる。
次に、本発明の硫化物固体電解質ガラスの製造方法について説明する。本発明の硫化物固体電解質ガラスの製造方法は、2つの実施態様に大別することができる。以下、本発明の硫化物固体電解質ガラスの製造方法について、第一実施態様および第二実施態様に分けて説明する。
まず、本発明の硫化物固体電解質ガラスの製造方法の第一実施態様について説明する。第一実施態様の硫化物固体電解質ガラスの製造方法は、Li2SおよびP2S5を含有する原料組成物を調製する調製工程と、上記原料組成物を非晶質化処理により非晶質化する非晶質化工程と、を有し、上記原料組成物が、上記Li2Sおよび上記P2S5を、31P NMR測定によりLi4P2S7が検出されず、かつ、XPS測定によるLi2Sの含有量が3mol%以下である硫化物固体電解質ガラスを得ることができる割合で含有していることを特徴とするものである。
以下、本発明の硫化物固体電解質ガラスの製造方法について、工程ごとに説明する。
第一実施態様における調製工程は、Li3PS4から構成される硫化物固体電解質ガラスの製造方法であって、Li2SおよびP2S5を含有する原料組成物を調製する工程である。さらに、原料組成物は、Li2SおよびP2S5を、31P NMR測定によりLi4P2S7が検出されず、かつ、XPS測定によるLi2Sの含有量が3mol%以下である硫化物固体電解質ガラスを得ることができる割合で含有する。なお、第一実施態様における原料組成物については、上記「A.硫化物固体電解質ガラス」に記載した内容と同様であるので、ここでの記載は省略する。また、原料組成物は、各成分が均一に分散していることが好ましい。
第一実施態様における非晶質化工程は、上記原料組成物を非晶質化処理により非晶質化する工程である。
第一実施態様においては、非晶質化処理工程で得られた硫化物固体電解質ガラスを熱処理する熱処理工程を行っても良い。これにより、通常、結晶化硫化物固体電解質ガラスが得られる。なお、熱処理の条件については、上記「A.硫化物固体電解質ガラス」に記載した内容と同様であるので、ここでの記載は省略する。
第一実施態様により得られる硫化物固体電解質ガラスについては、上記「A.硫化物固体電解質ガラス」に記載した内容と同様であるので、ここでの記載は省略する。また、第一実施態様においては、上述した調製工程および非晶質化工程により得られたことを特徴とする硫化物固体電解質ガラスを提供することができる。同様に、本発明においては、上述した調製工程、非晶質化工程および熱処理工程により得られたことを特徴とする結晶化硫化物固体電解質ガラスを提供することができる。
次に、本発明の硫化物固体電解質ガラスの製造方法の第二実施態様について説明する。第二実施態様の硫化物固体電解質ガラスの製造方法は、Li3PS4から構成される硫化物固体電解質ガラスの製造方法であって、Li2SおよびP2S5を、xLi2S・(100-x)P2S5(xは73<x<75である)のモル比で含有する原料組成物を調製する調製工程と、上記原料組成物を非晶質化処理により非晶質化する非晶質化工程と、を有することを特徴とするものである。
次に、本発明のリチウム固体電池について説明する。本発明のリチウム固体電池は、正極活物質を含有する正極活物質層と、負極活物質を含有する負極活物質層と、上記正極活物質層および上記負極活物質層の間に形成された固体電解質層と、を有するリチウム固体電池であって、上記正極活物質層、上記負極活物質層および上記固体電解質層の少なくとも一つが、上述した硫化物固体電解質ガラスを含有することを特徴とするものである。
以下、本発明のリチウム固体電池について、構成ごとに説明する。
まず、本発明における固体電解質層について説明する。本発明における固体電解質層は、正極活物質層および負極活物質層の間に形成される層であり、固体電解質材料から構成される層である。固体電解質層に含まれる固体電解質材料は、Liイオン伝導性を有するものであれば特に限定されるものではない。
次に、本発明における正極活物質層について説明する。本発明における正極活物質層は、少なくとも正極活物質を含有する層であり、必要に応じて、固体電解質材料、導電化材および結着材の少なくとも一つをさらに含有していても良い。
次に、本発明における負極活物質層について説明する。本発明における負極活物質層は、少なくとも負極活物質を含有する層であり、必要に応じて、固体電解質材料、導電化材および結着材の少なくとも一つをさらに含有していても良い。
本発明のリチウム固体電池は、上述した正極活物質層、負極活物質層および固体電解質層を少なくとも有するものである。さらに通常は、正極活物質層の集電を行う正極集電体、および負極活物質層の集電を行う負極集電体を有する。正極集電体の材料としては、例えば、SUS、アルミニウム、ニッケル、鉄、チタンおよびカーボン等を挙げることができ、中でも、SUSが好ましい。一方、負極集電体の材料としては、例えば、SUS、銅、ニッケルおよびカーボン等を挙げることができ、中でも、SUSが好ましい。また、正極集電体および負極集電体の厚さや形状等については、リチウム固体電池の用途等に応じて適宜選択することが好ましい。また、本発明に用いられる電池ケースには、一般的なリチウム固体電池の電池ケースを用いることができる。電池ケースとしては、例えば、SUS製電池ケース等を挙げることができる。また、本発明のリチウム固体電池は、発電要素を絶縁リングの内部に形成しても良い。
本発明のリチウム固体電池は、一次電池であっても良く、二次電池であっても良いが、中でも、二次電池であることが好ましい。繰り返し充放電でき、例えば、車載用電池として有用だからである。本発明のリチウム固体電池の形状としては、例えば、コイン型、ラミネート型、円筒型および角型等を挙げることができる。
出発原料として、硫化リチウム(Li2S)および五硫化リン(P2S5)を用いた。これらの粉末をAr雰囲気下(露点-70℃)のグローブボックス内で、73.5Li2S・26.5P2S5のモル比となるように秤量し、メノウ乳鉢で混合し、原料組成物1g(Li2S=0.3644g、P2S5=0.6356g)を得た。次に、得られた原料組成物1gを45mlのジルコニアポットに投入し、さらにジルコニアボール(Φ10mm、10個)を投入し、ポットを完全に密閉した(Ar雰囲気)。このポットを遊星型ボールミル機(フリッチュ製P7)に取り付け、台盤回転数370rpmで40時間メカニカルミリングを行い、硫化物固体電解質ガラスを得た。
73.8Li2S・26.2P2S5のモル比とし、原料組成物1g(Li2S=0.3680g、P2S5=0.6320g)を得たこと以外は、実施例1と同様にして、硫化物固体電解質ガラスを得た。
74Li2S・26P2S5のモル比とし、原料組成物1g(Li2S=0.3704g、P2S5=0.6296g)を得たこと以外は、実施例1と同様にして、硫化物固体電解質ガラスを得た。
75Li2S・25P2S5のモル比とし、原料組成物1g(Li2S=0.3827g、P2S5=0.6173g)を得たこと以外は、実施例1と同様にして、硫化物固体電解質ガラスを得た。
76Li2S・24P2S5のモル比とし、原料組成物1g(Li2S=0.3956g、P2S5=0.6044g)を得たこと以外は、実施例1と同様にして、硫化物固体電解質ガラスを得た。
73Li2S・27P2S5のモル比とし、原料組成物1g(Li2S=0.3585g、P2S5=0.6415g)を得たこと以外は、実施例1と同様にして、硫化物固体電解質ガラスを得た。
(XPS測定)
実施例1~3および比較例1~3で得られた硫化物固体電解質ガラスに対して、XPS(X線光電子分光)測定を行った。得られたXPSスペクトルを用いて、上述した方法により、Li2Sの含有量を決定した。その結果を図3に示す。また、実施例2および比較例1で得られた硫化物固体電解質ガラスのXPSスペクトルを図4に示す。
図3に示されるように、実施例1~3および比較例3では、Li2Sの含有量(Li2S分率)が3mol%以下であることが確認された。一方、比較例1および2では、Li2Sの含有量が5mol%以上であることが確認された。Li2Sの含有量が3mol%以下の場合に、Li2Sの含有量が顕著に減少していた。
実施例1~3および比較例1~3で得られた硫化物固体電解質ガラスに対して、31P NMR(核磁気共鳴)測定を行った。得られた31P NMRスペクトルを用いて、上述した方法により、Li4P2S7の含有量を決定した。その結果を図5に示す。また、比較例1で得られた硫化物固体電解質ガラスの31P NMRスペクトルを図6に示す。
図5に示されるように、実施例1~3および比較例1~2では、Li4P2S7が検出されないことが確認された。一方、比較例3では、Li4P2S7の含有量が4mol%以上であることが確認された。
実施例1~3および比較例1~3で得られた硫化物固体電解質ガラスに対して、硫化水素発生量の測定を行った。硫化水素発生量の測定は以下のように行った。Ar雰囲気下で硫化物固体電解質ガラスを100mg秤量し、密閉容器(1750ccの容積、湿度50%、温度20℃の加湿状態)内に静置した。密閉容器内はファンにより撹拌し、測定には硫化水素センサーを用いた。実施例1~3および比較例1~3で得られた硫化物固体電解質ガラスの大気暴露5分後の密閉容器内の硫化水素濃度を図7に示す。
図7に示されるように、実施例1~3は、比較例1に比べて硫化水素発生量が大幅に低いことが確認された。なお、上記XPS測定および31P NMR測定の結果から、Li2SおよびLi4P2S7の含有量は、実施例1で最小となったが、硫化水素発生量測定の結果から、実際の硫化水素発生量は、実施例2で最小となった。これは、31P NMR測定の検出下限以下のLi4P2S7が、実施例1に含まれているためと考えられる。
実施例1~3および比較例1~3で得られた硫化物固体電解質ガラスに対して、Liイオン伝導度の測定を行った。Liイオン伝導度の測定は以下のように行った。支持筒(マコール製)に添加された硫化物固体電解質ガラス100mgを、SKD製の電極で挟んだ。その後、4.3ton/cm2の圧力で硫化物固体電解質ガラスを圧粉し、6Ncmで硫化物固体電解質ガラスを拘束しながらインピーダンス測定を行った。測定にはソーラトロン1260を用い、測定条件は、印加電圧5mV、測定周波数域0.01MHz~1MHzとした。その結果を図8に示す。
図8に示されるように、実施例1~3および比較例1~3のイオン伝導度は、同程度であり、硫化物固体電解質ガラスの組成を変化させても、Liイオン伝導度は大きく変化しないことが確認された。
比較例1で得られた硫化物固体電解質ガラスに対して、XRD(X線回折)測定を行った。その結果を図9に示す。
図9に示されるように、比較例1においては、Li2Sのピーク(2θ=27.0°、31.2°、44.8°、53.1°)が検出されないことが確認された。これに対して、上記XPS測定の結果では、Li2Sの存在を確認することができた。
2 … 負極活物質層
3 … 固体電解質層
4 … 正極集電体
5 … 負極集電体
6 … 電池ケース
10 … リチウム固体電池
Claims (7)
- Li3PS4から構成される硫化物固体電解質ガラスであって、
31P NMR測定によりLi4P2S7が検出されず、かつ、XPS測定によるLi2Sの含有量が3mol%以下であることを特徴とする硫化物固体電解質ガラス。 - 前記XPS測定によるLi2Sの含有量が1mol%以下であることを特徴とする請求の範囲第1項に記載の硫化物固体電解質ガラス。
- Li3PS4から構成される硫化物固体電解質ガラスの製造方法であって、
Li2SおよびP2S5を含有する原料組成物を調製する調製工程と、
前記原料組成物を非晶質化処理により非晶質化する非晶質化工程と、を有し、
前記原料組成物が、前記Li2Sおよび前記P2S5を、31P NMR測定によりLi4P2S7が検出されず、かつ、XPS測定によるLi2Sの含有量が3mol%以下である硫化物固体電解質ガラスを得ることができる割合で含有していることを特徴とする硫化物固体電解質ガラスの製造方法。 - 前記XPS測定によるLi2Sの含有量が1mol%以下であることを特徴とする請求の範囲第3項に記載の硫化物固体電解質ガラスの製造方法。
- Li3PS4から構成される硫化物固体電解質ガラスの製造方法であって、
Li2SおよびP2S5を、xLi2S・(100-x)P2S5(xは73<x<75である)のモル比で含有する原料組成物を調製する調製工程と、
前記原料組成物を非晶質化処理により非晶質化する非晶質化工程と、
を有することを特徴とする硫化物固体電解質ガラスの製造方法。 - 前記非晶質化処理が、メカニカルミリングであることを特徴とする請求の範囲第3項から第5項までのいずれかに記載の硫化物固体電解質ガラスの製造方法。
- 正極活物質を含有する正極活物質層と、負極活物質を含有する負極活物質層と、前記正極活物質層および前記負極活物質層の間に形成された固体電解質層と、を有するリチウム固体電池であって、
前記正極活物質層、前記負極活物質層および前記固体電解質層の少なくとも一つが、請求の範囲第1項または第2項に記載の硫化物固体電解質ガラスを含有することを特徴とするリチウム固体電池。
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US20130164632A1 (en) | 2013-06-27 |
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US8993176B2 (en) | 2015-03-31 |
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JPWO2012011179A1 (ja) | 2013-09-09 |
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