WO2022210675A1 - 固体電解質及びその製造方法 - Google Patents
固体電解質及びその製造方法 Download PDFInfo
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- WO2022210675A1 WO2022210675A1 PCT/JP2022/015346 JP2022015346W WO2022210675A1 WO 2022210675 A1 WO2022210675 A1 WO 2022210675A1 JP 2022015346 W JP2022015346 W JP 2022015346W WO 2022210675 A1 WO2022210675 A1 WO 2022210675A1
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- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 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
- H01M2300/008—Halides
-
- 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 solid electrolytes and methods for producing the same.
- the present invention also relates to an electrode mixture containing a solid electrolyte, a solid electrolyte layer and a battery.
- Solid electrolytes have attracted attention as an alternative to the electrolyte solution used in many liquid-based batteries.
- Solid-state batteries using solid electrolytes are expected to be put into practical use as batteries having higher safety and higher energy density than liquid-based batteries using combustible organic solvents.
- a solid electrolyte for example, a sulfide solid electrolyte containing lithium (Li) element, phosphorus (P) element, sulfur (S) element and halogen element has been proposed (Patent Documents 1 and 2).
- an object of the present invention is to provide a solid electrolyte having excellent battery characteristics and a method for producing the same.
- the present invention includes lithium (Li) element, phosphorus (P) element, sulfur (S) element and halogen (X) element, including a crystalline phase having an aldirodite-type crystal structure,
- the crystallite size of the crystal phase having the aldirodite-type crystal structure is 40 nm or less
- XRD X-ray diffractometer
- the present invention provides a firing step of firing a raw material composition containing lithium (Li) element, phosphorus (P) element, sulfur (S) element and halogen (X) element at 200° C. or higher to obtain a fired product; and a pulverizing step of pulverizing the fired product by applying a pulverizing energy E represented by the following formula (1) of 200 J ⁇ sec/g or more to the fired product.
- E (J ⁇ sec/g) 1/2 ntmv 2 /s (1)
- n represents the number of grinding media
- t the grinding time (sec)
- m represents the mass (kg) of one grinding media
- v the speed of the grinding media (m/sec)
- s represents the mass (g) of the object to be ground.
- FIG. 1 is a diagram showing X-ray diffraction patterns of solid electrolytes obtained in Examples 1 to 3.
- FIG. 2 is a diagram showing X-ray diffraction patterns of solid electrolytes obtained in Comparative Examples 1 and 2.
- FIG. 1 is a diagram showing X-ray diffraction patterns of solid electrolytes obtained in Examples 1 to 3.
- FIG. 2 is a diagram showing X-ray diffraction patterns of solid electrolytes obtained in Comparative Examples 1 and 2.
- FIG. 1 is a diagram showing X-ray diffraction patterns of solid electrolytes obtained in Examples 1 to 3.
- FIG. 2 is a diagram showing X-ray diffraction patterns of solid electrolytes obtained in Comparative Examples 1 and 2.
- the present invention will be described below based on its preferred embodiments. First, the solid electrolyte of the present invention will be explained.
- the solid electrolyte of the present invention contains Li element, P element, S element and X element.
- the X element examples include fluorine (F) element, chlorine (Cl) element, bromine (Br) element, and iodine (I) element.
- the X element may be one of these elements, or may be a combination of two or more.
- the solid electrolyte preferably contains at least Cl element or Br element as the X element from the viewpoint that the later-described aldirodite-type crystal structure is easily generated by a solid-phase reaction and the lithium ion conductivity is increased, and the Cl element and the Br element It is more preferable to contain
- the ratio of the Br element to the sum of the number of moles of the Br element and the number of moles of the Cl element that is, the value of Br/(Br+Cl) is, for example, 0.2. It is preferably 0.3 or more, more preferably 0.3 or more, and still more preferably 0.4 or more. On the other hand, the value of Br/(Br+Cl) is, for example, preferably 0.8 or less, more preferably 0.7 or less, and even more preferably 0.6 or less.
- the solid electrolyte of the present invention it is preferable to set the molar ratio (X/P) of the X element to the P element to a relatively high value.
- X/P is preferably 1.1 or more, more preferably 1.5 or more, and even more preferably 1.8 or more.
- the X/P is preferably 4.0 or less, more preferably 3.5 or less, and even more preferably 2.4 or less.
- the solid electrolyte of the present invention exhibits superior lithium ion conductivity.
- the solid electrolyte of the present invention is used in a solid battery, the solid battery exhibits more excellent battery characteristics.
- the X/P can be measured, for example, by ICP emission spectrometry.
- the molar ratio (S/P) of the S element to the P element is, for example, preferably 4.9 or less, more preferably 4.5 or less, and 4.2 or less. is more preferable.
- the S/P is preferably 3.2 or more, more preferably 3.5 or more, and even more preferably 3.8 or more.
- the solid electrolyte of the present invention exhibits superior lithium ion conductivity.
- the solid electrolyte of the present invention when used in a solid battery, the solid battery exhibits better battery characteristics.
- the S/P can be measured, for example, by ICP emission spectroscopy.
- the solid electrolyte may contain elements other than Li element, P element, S element and X element.
- part of the Li element can be replaced with another alkali metal element
- part of the P element can be replaced with another pnictogen element
- part of the S element can be replaced with another chalcogen element.
- the solid electrolyte may contain materials containing other elements in addition to the Li element, P element, S element and X element as long as the effects of the present invention are not impaired.
- the content of other materials can be, for example, at most less than 5 mol %, preferably less than 3 mol %, particularly preferably less than 1 mol %.
- the solid electrolyte of the present invention is preferably a crystalline compound.
- a crystalline compound is a substance in which a diffraction peak attributed to a crystalline phase is observed when measured by an X-ray diffractometer (XRD). It is particularly preferable that the solid electrolyte contains a crystal phase having an aldirodite type crystal structure from the viewpoint of enhancing the lithium ion conductivity of the solid electrolyte.
- the solid electrolyte may or may not have a crystal phase other than the aldirodite crystal structure.
- the “main phase” refers to the phase having the largest ratio with respect to the total amount of all crystal phases constituting the present solid electrolyte. Therefore, the content of the crystal phase having an aldirodite-type crystal structure is preferably, for example, 60% by mass or more, preferably 70% by mass or more, 80% by mass or more, relative to the total crystal phases constituting the solid electrolyte. It is more preferably 90% by mass or more, more preferably 95% by mass or more.
- the ratio of the crystal phase can be confirmed by, for example, XRD.
- the solid electrolyte of the present invention preferably does not have a Li 2 S crystal phase, for example. Moreover, when it has the crystal phase of Li2S , it is preferable that the abundance ratio is as low as possible.
- the diffraction observed in the range of 2 ⁇ 25.5° ⁇ 1.0°
- the ratio Ia/Ib of Ia to Ib is preferably 0.20 or less, more preferably 0.17 or less, and even more preferably 0.15 or less.
- 0. Diffraction peak B is a diffraction peak derived from the aldirodite-type crystal structure.
- Ia/Ib When Ia/Ib is equal to or less than the above value, the movement of lithium ions at the interface between the active material and the solid electrolyte is improved, and as a result, the input/output characteristics of the battery can be improved.
- a method for measuring Ia and Ib will be described in detail in Examples described later.
- the intensity of a diffraction peak means the height of the peak.
- the solid electrolyte preferably does not have a crystal phase other than the Li 2 S crystal phase described above.
- This diffraction peak C is derived from a crystal phase other than the aldirodite-type crystal structure.
- the present inventor believes that this diffraction peak C is derived from the crystal phase disclosed in Patent Document 2 described in the background art section.
- the crystal phase derived from diffraction peak C is a phase that is thermodynamically more stable than the aldirodite crystal structure, it may be generated in the solid electrolyte depending on the manufacturing conditions of the solid electrolyte.
- the background intensity is I0
- the IC/I0 ratio to I0 is preferably 1.55 or less, more preferably 1.40 or less, and even more preferably 1.25 or less. . This is because the lithium ion conductivity can be more effectively improved.
- the count number of Ic is preferably 300 counts or less, and 200 It is more preferably 100 counts or less, more preferably 100 counts or less. This is because the lithium ion conductivity can be more effectively improved.
- a method for measuring the maximum count number IC and the count number Ic of the diffraction peaks C will be described in detail in Examples described later.
- the solid electrolyte has a crystal phase having an aldirodite crystal structure, and it is preferable that the crystal phase has low crystallinity from the viewpoint of improving the performance of a battery containing the solid electrolyte, particularly improving the output characteristics. .
- the inventors of the present invention believe that the lower crystallinity of the solid electrolyte makes it easier to undergo plastic deformation during the production of an all-solid-state battery, which leads to better contact with the active material.
- the crystallinity of a crystal phase having an aldirodite-type crystal structure can be evaluated using the crystallite size of the crystal phase as a scale.
- the crystallite size of the crystal phase having an algyrodite-type crystal structure is, for example, preferably 40 nm or less, more preferably 35 nm or less, and even more preferably 30 nm or less. Also, the crystallite size may be, for example, 1 nm or more, 5 nm or more, or 10 nm or more. A method for measuring the crystallite size will be described in detail in Examples described later.
- the volume cumulative particle size D50 at a cumulative volume of 50 % by volume measured by a laser diffraction scattering particle size distribution measurement method is preferably, for example, 5 ⁇ m or less, more preferably 3 ⁇ m or less. It is more preferably 5 ⁇ m or less, even more preferably 1.3 ⁇ m or less, and even more preferably 1.1 ⁇ m or less. This is because the contact points and contact areas between the solid electrolyte and the active material particles are increased, and the input/output characteristics of the battery can be effectively improved.
- the particle size D50 of the solid electrolyte is, for example, preferably 0.1 ⁇ m or more, more preferably 0.3 ⁇ m or more, and even more preferably 0.5 ⁇ m or more. This is because an excessive increase in the surface area of the solid electrolyte can be suppressed, and an increase in resistance can be suppressed. Moreover, it is because mixing with an active material becomes easy. A method for measuring the particle size D50 will be described in detail in the examples below.
- the solid electrolyte of the present invention preferably has lithium ion conductivity in a solid state.
- it preferably has a lithium ion conductivity of 0.1 mS/cm or more, especially 0.2 mS/cm or more, particularly 0.4 mS/cm or more at room temperature, that is, 25°C.
- Lithium ion conductivity can be measured using the method described in Examples below.
- This production method includes a firing step of firing the raw material composition of the solid electrolyte and a pulverizing step of strongly pulverizing the fired material obtained in the firing step.
- a method for producing a solid electrolyte for example, as described in the above-mentioned Patent Document 1, a method of manufacturing a target object by mechanical milling instead of firing the raw material composition, or a method of manufacturing the target object by mechanical milling, or the above-mentioned Patent Document 2, a method is known in which the raw material composition is fired, but the target product is produced without mechanical milling.
- the solid electrolyte when the solid electrolyte is produced by mechanical milling, lithium sulfide, which is a component contained in the raw material composition, may remain in the solid electrolyte even when the milling time is lengthened. Conceivable.
- Lithium sulfide is a substance that reduces the movement of lithium ions between the active material and the solid electrolyte when used as a solid-state battery, and is one of the factors that reduce the input/output characteristics of the battery.
- the crystal structure is thermodynamically A stable heterophasic crystalline phase is formed.
- the heterogeneous phase is a crystalline phase corresponding to the diffraction peak C described above, and contributes to a decrease in lithium ion conductivity.
- this production method employs a method in which firing of the raw material composition and strong pulverization by mechanical milling of the fired product are combined.
- lithium sulfide is less likely to remain, and an aldirodite-type crystal structure is likely to be generated as the main phase.
- the reasons for this are as follows.
- the crystal phase corresponding to the diffraction peak C described above is a crystal phase that undergoes a phase transition to an aldirodite crystal structure at high temperatures, but in the case of the conventional firing method, a stable crystal phase corresponding to the diffraction peak C is generated. There is a tendency.
- the metastable aldirodite-type crystal structure can be maintained even at room temperature by mechanical milling after sintering. That is, it is considered that the formation of the crystal phase corresponding to the diffraction peak C can be suppressed.
- the raw material composition can be obtained by mixing predetermined raw materials.
- the raw material is a substance containing elements constituting the solid electrolyte, and in detail, a compound containing Li element, a compound containing S element, a compound containing P element, and a compound containing X element. A chemical compound.
- Li element-containing compound examples include lithium compounds such as lithium sulfide (Li 2 S), lithium oxide (Li 2 O), lithium carbonate (Li 2 CO 3 ), and lithium metal alone.
- compounds containing element S include phosphorous sulfides such as niline trisulfide ( P2S3 ) and phosphorus pentasulfide ( P2S5 ).
- sulfur (S) alone can be used as the compound containing the sulfur (S) element.
- Examples of compounds containing the P element include phosphorous sulfides such as niline trisulfide (P 2 S 3 ) and phosphorus pentasulfide (P 2 S 5 ), phosphorus compounds such as sodium phosphate (Na 3 PO 4 ), and Phosphorus simple substance etc. can be mentioned.
- the compound containing element X includes one or more elements selected from the group consisting of fluorine (F) element, chlorine (Cl) element, bromine (Br) element and iodine (I) element, and sodium (Na) element, lithium (Li) element, boron (B) element, aluminum (Al) element, silicon (Si) element, phosphorus (P) element, sulfur (S) element, germanium (Ge) element, arsenic (As) ) element, selenium (Se) element, tin (Sn) element, antimony (Sb) element, tellurium (Te) element, lead (Pb) element and bismuth (Bi) element.
- lithium halides such as LiF, LiCl, LiBr and LiI, PF3, PF5 , PCl3, PCl5 , POCl3 , PBr3 , POBr3 , PI3 , P2Cl4 , P2 Phosphorus halides such as I4 , sulfur halides such as SF2 , SF4 , SF6 , S2F10 , SCl2 , S2Cl2 , S2Br2 , halogens such as NaI , NaF, NaCl and NaBr boron halides such as sodium chloride, BCl 3 , BBr 3 and BI 3 ; These compounds can be used individually by 1 type or in combination of 2 or more types. Among them, lithium halide (LiX (X represents halogen)) is preferably used.
- an attritor for example, an attritor, a paint shaker, a planetary ball mill, a ball mill, a bead mill, a homogenizer, or the like can be used as an apparatus for mixing the raw materials described above to prepare a raw material composition.
- the amount of each raw material to be added when mixing is appropriately adjusted so as to satisfy the desired composition of the solid electrolyte.
- the obtained raw material composition is subjected to firing to cause a solid-phase reaction to obtain a fired product containing a crystal phase having an aldirodite-type crystal structure.
- firing atmosphere for example, an inert gas atmosphere such as an argon atmosphere or a nitrogen atmosphere, or a hydrogen sulfide atmosphere can be used.
- the firing temperature is, for example, preferably 200° C. or higher, more preferably 300° C. or higher, even more preferably 350° C. or higher, from the viewpoint of ensuring solid-phase reaction of the raw material composition. °C or higher is even more preferred.
- the firing temperature is preferably, for example, 700° C. or lower, more preferably 600° C. or lower, and even more preferably 550° C. or lower, in consideration of industrial productivity and economic efficiency.
- the firing time is not critical, as long as it allows the firing of the desired composition to be obtained. Specifically, the firing time is preferably such that the raw material composition undergoes a sufficient solid-phase reaction.
- the firing time may be, for example, 30 minutes or longer, 2 hours or longer, or 3 hours or longer. On the other hand, the firing time may be, for example, 10 hours or less, or 5 hours or less.
- the fired product is subjected to a pulverization step for strong pulverization.
- strong pulverization for example, an attritor, a paint shaker, a planetary ball mill, a ball mill, a bead mill, a homogenizer, or the like can be used.
- an attritor, a paint shaker, a planetary ball mill, a ball mill, a bead mill, a homogenizer, or the like can be used.
- the energy given to the fired product is defined by the pulverization energy E represented by the following formula (1).
- n the number of grinding media
- t the grinding time (sec)
- m the mass (kg) of one grinding media
- v the speed of the grinding media (m/sec)
- s the mass (g) of the object to be ground.
- the speed v of the grinding media can be calculated from equation (2), for example, in the case of a planetary ball mill.
- v(m/sec) d ⁇ R ⁇ /60
- d is the diameter of the pot (m)
- R is the number of revolutions (rpm)
- ⁇ is the rotation/revolution ratio.
- the speed of the grinding media corresponds to the peripheral speed v (m/sec) of the stirring mechanism (disk or the like).
- the pulverization energy E defined by the above formula it is preferable to apply the pulverization energy E defined by the above formula to the fired product at 200 J ⁇ sec/g or more.
- Such high-energy pulverization is referred to herein as hard pulverization.
- the pulverization energy E applied to the fired product is more preferably 200 J ⁇ sec/g or more and 200000 J ⁇ sec/g or less, and more preferably 500 J ⁇ sec/g or more and 100000 J ⁇ sec/g.
- pulverization conditions for imparting the pulverization energy E within the range described above to the fired product is as follows.
- the pulverization step preferably includes a step in which the kinetic energy W defined by the above formula (3) is 0.0001 J or more.
- the kinetic energy W is more preferably 0.001 J or more and 1.0 J or less, even more preferably 0.005 J or more and 0.1 J or less, and even more preferably 0.01 J or more and 0.05 J or less. .
- a known pulverization treatment in which less energy than that of hard pulverization is applied can be performed for the purpose of adjusting the particle size.
- the pulverization treatment is preferably performed so that the particle diameter D50 of the solid electrolyte of the present invention is, for example, 5 ⁇ m or less, more preferably 3 ⁇ m or less, and preferably 1.5 ⁇ m or less. More preferably, it is carried out so that it becomes 1.3 ⁇ m or less, and even more preferably, it is carried out so that it becomes 1.1 ⁇ m or less. This is because the contact area between the solid electrolyte and the active material is increased, and the output characteristics of the battery are improved.
- the total pulverization energy of the above-described hard pulverization and known pulverization treatment is within the above range. This is because by applying such pulverization energy, it is easier to obtain a solid electrolyte containing a crystal phase having an aldirodite-type crystal structure in which no heterophase exists or the ratio of the heterophase existing is extremely low.
- the solid electrolyte of the present invention obtained by the above method is slightly blackish, unlike the solid electrolyte described in Patent Document 1, for example.
- the solid electrolyte described in Patent Document 1 is whitish unlike the solid electrolyte of the present invention.
- the inventor believes that this difference is due to the difference in manufacturing method. Specifically, the solid electrolyte of the present invention is obtained through the firing process as described above, and it is thought that the solid electrolyte becomes slightly blackish due to the firing process. On the other hand, the solid electrolyte described in Patent Literature 1 is thought to be whitish because it is obtained without the firing process.
- the color exhibited by the solid electrolyte of the present invention is preferably 90 or less, more preferably 50 or more and 90 or less, and still more preferably 60, in terms of lightness L * value in the L * a * b * color system. 85 or less, and more preferably 75 or more and 82 or less. A method for measuring the lightness L * value will be described in detail in Examples described later.
- the solid electrolyte obtained by the above method can be used as a material for forming a solid electrolyte layer, a positive electrode layer, or a negative electrode layer.
- the solid electrolyte of the present invention can be used in a battery having a positive electrode layer, a negative electrode layer, and a solid electrolyte layer between the positive electrode layer and the negative electrode layer.
- solid electrolytes can be used in so-called solid batteries. More specifically, it can be used in lithium solid state batteries.
- a lithium solid state battery may be a primary battery or a secondary battery. There is no particular limitation on the shape of the battery, and for example, shapes such as laminate, cylindrical and square can be adopted.
- Solid battery means a solid battery that does not contain any liquid or gel substance as an electrolyte, and also includes, for example, 50% by mass or less, 30% by mass or less, or 10% by mass or less of liquid or gel substance as an electrolyte. Aspects are also included.
- the solid electrolyte layer contains the solid electrolyte of the present invention
- the solid electrolyte layer can be formed, for example, by dropping a slurry comprising a solid electrolyte, a binder, and a solvent onto a substrate and scraping it off with a doctor blade or the like, or by separating the substrate and the slurry. It can be produced by a method of cutting with an air knife after contact, a method of forming a coating film by a screen printing method or the like, and a method of removing the solvent after drying by heating. Alternatively, a solid electrolyte in powder form may be press-formed into a powder compact, and then processed as appropriate.
- the thickness of the solid electrolyte layer is typically preferably 5 ⁇ m or more and 300 ⁇ m or less, more preferably 10 ⁇ m or more and 100 ⁇ m or less, from the viewpoint of the balance between short circuit prevention and volume capacity density.
- the solid electrolyte of the present invention is used together with an active material to constitute an electrode mixture.
- the ratio of the solid electrolyte in the electrode mixture is typically 10% by mass or more and 50% by mass or less.
- the electrode mixture may contain other materials such as a conductive aid and a binder as needed.
- An electrode layer such as a positive electrode layer and/or a negative electrode layer can be produced by mixing an electrode mixture and a solvent to prepare a paste, applying the paste onto a current collector such as an aluminum foil, and drying the paste.
- the positive electrode material used as the positive electrode active material for lithium ion batteries can be used as appropriate.
- positive electrode active materials containing lithium specifically, spinel-type lithium transition metal oxides and lithium metal oxides having a layered structure can be used.
- Energy density can be improved by using a high-voltage positive electrode material as the positive electrode material.
- the positive electrode material may contain a conductive material in addition to the positive electrode active material, or may contain other materials.
- a negative electrode material that is used as a negative electrode active material for lithium ion batteries can be appropriately used.
- the solid electrolyte of the present invention is electrochemically stable, graphite, artificial graphite, which is a material that charges and discharges at a base potential (about 0.1 V vs. Li + /Li) comparable to lithium metal or lithium metal, Carbon-based materials such as natural graphite and non-graphitizable carbon (hard carbon) can be used as the negative electrode material. This can greatly improve the energy density of solid-state batteries.
- silicon or tin which are promising as high-capacity materials, can also be used as an active material.
- the electrolytic solution reacts with the active material during charging and discharging, and corrosion occurs on the surface of the active material, resulting in significant degradation of battery characteristics.
- the solid electrolyte of the present invention is used instead of the electrolytic solution and silicon or tin is used as the negative electrode active material, the corrosion reaction described above does not occur, and the durability of the battery can be improved.
- the negative electrode material may also contain a conductive material in addition to the negative electrode active material, or may contain other materials.
- Example 1 (1) Preparation of raw material composition Lithium sulfide (Li 2 S) powder, diphosphorus pentasulfide (P 2 S 5 ) powder, and lithium chloride (LiCl) powder were mixed so as to obtain a composition of Li 5 PS 4 ClBr. , and lithium bromide (LiBr) powder were weighed so that the total amount was 5 g. A slurry was prepared by adding 10 mL of heptane to these powders. This slurry was placed in a zirconia container having a volume of 80 mL and set in a planetary ball mill (P-5 manufactured by Fritsch). 90 g of ZrO 2 balls with a diameter of 5 mm were used as grinding media. The operating condition of the ball mill device was 100 rpm, and grinding was performed for 10 hours. The resulting slurry was vacuum-dried at room temperature to remove the solvent and obtain a raw material composition.
- Li 2 S Lithium sulfide
- P 2 S 5
- Firing A fired product was obtained by firing the raw material composition. Firing was performed using a tubular electric furnace. During firing, 100% pure nitrogen gas was passed through the electric furnace. The firing temperature was set to 600° C. and firing was performed for 4 hours.
- Fine pulverization The powder obtained by strong pulverization was finely pulverized by a planetary ball mill. The powder was weighed to give a total weight of 2 g. A slurry was prepared by adding 10 mL of toluene and a dispersant to this powder. This slurry was placed in a zirconia container with a volume of 80 mL. 90 g of ZrO 2 balls with a diameter of 0.8 mm were used as grinding media. The operation condition of the ball mill device was 100 rpm, and grinding was performed for 3 hours. The solvent was removed by vacuum-drying the resulting slurry at 150°C. In this way, the desired solid electrolyte powder was obtained. The X/P molar ratio was 2 and the S/P molar ratio was 4 as determined by ICP emission spectroscopy.
- the pulverization energy E [J ⁇ sec/g] in this example was calculated as follows. First, the pulverization energy for strong pulverization and fine pulverization was calculated. (strong pulverization)
- the density of the ZrO 2 grinding media used in this example is 6.0 g/cm 2 .
- the number n of grinding media and the mass (kg) of one grinding media were calculated based on an input mass of 90 g on the assumption that the grinding media are spherical. As a result, the number n of balls was 28.6.
- the mass of one grinding media was 0.00314 kg.
- the speed (m/sec) of the grinding media when the planetary ball mill was operated at 370 rpm was calculated from the above equation (2).
- the rotation/revolution ratio ⁇ of the planetary ball mill used for pulverization was 2.19, and the inner diameter of the mill pot used for pulverization was 0.065 m, so the ball speed was calculated to be 2.76 (m/sec). .
- the pulverization energy E was calculated from the above formula (1) and found to be 493 J ⁇ sec/g. (fine pulverization)
- the pulverization energy during fine pulverization was calculated in the same manner as in the case of strong pulverization, it was 135 J ⁇ sec/g. Therefore, by adding the crushing energies in the strong crushing process and the fine crushing process, 628 J ⁇ sec/g, which is the crushing energy E shown in Table 1 below, was obtained.
- Example 2 and 3 In the strong pulverization process of Example 1, the pulverization time was set to 10 hours and 50 hours, respectively. A solid electrolyte powder was obtained in the same manner as in Example 1 except for the above.
- This comparative example corresponds to the example of Patent Document 2.
- a slurry was prepared by adding 10 mL of toluene and a dispersant to this powder.
- This slurry was placed in a zirconia container with a volume of 80 mL. 90 g of ZrO 2 balls with a diameter of 5 mm were used as grinding media. The operation condition of the ball mill device was 100 rpm, and weak pulverization was carried out for 3 hours. The resulting slurry was vacuum dried at room temperature to remove the solvent. (4) Fine pulverization It was carried out in the same manner as in Example 1.
- This comparative example corresponds to the example of Patent Document 1.
- (1) Preparation of raw material composition It was carried out in the same manner as in Example 1.
- (2) Mechanical Milling The raw material composition was subjected to mechanical milling using a planetary ball mill. Each raw material composition was weighed so that the total amount was 5 g.
- a slurry was prepared by adding 10 g of heptane to these powders. This slurry was placed in a zirconia container with a volume of 80 mL. 90 g of ZrO 2 balls with a diameter of 10 mm were used as grinding media.
- the operating conditions of the ball mill apparatus were 370 rpm, and the grinding time was 50 hours.
- the resulting slurry was vacuum dried at room temperature to remove the solvent.
- (3) Fine pulverization It was carried out in the same manner as in Example 1.
- a value obtained by subtracting the background I0 from IB was defined as the peak intensity Ib attributable to the aldirodite type crystal structure.
- the maximum count number of peak intensity in the range of 27.0° ⁇ 0.5° was defined as IA.
- a value obtained by subtracting the background I0 from IA was defined as the peak intensity Ia attributable to the Li 2 S crystal structure.
- the background I0 value was measured to be 400 to 800 counts.
- the maximum peak intensity in this XRD measurement was measured so as to be 1500 counts or more.
- the count number Ic of the diffraction peak C was obtained by subtracting the background I0 from the maximum count number IC. Furthermore, the obtained X-ray diffraction pattern was read into Smart Lab Studio II, and the WPPF method was used to determine the crystallite size of the crystal phase having an aldirodite crystal structure for the sulfide solid electrolytes obtained in Examples and Comparative Examples. Calculated. Device-derived parameters were corrected using standard samples. Table 1 shows the results. As a standard sample for angle correction, Si of SRM 640f manufactured by NIST was used. As a standard sample for width correction, LaB 6 of SRM 660c manufactured by NIST was used.
- An airtight holder for ASC (A00012149) manufactured by Rigaku Corporation was used for the cell not exposed to the air.
- the airtight cover was a transparent airtight film, and the atmosphere was Ar.
- the XRD measurement was performed using an X-ray diffractometer "Smart Lab SE” manufactured by Rigaku Corporation. The measurement conditions were non-exposure to air, scanning axis: 2 ⁇ / ⁇ , scanning range: 10° to 120°, step width of 0.02°, and scanning speed of 1°/min.
- the X-ray source was CuK ⁇ 1 rays.
- the tube voltage was 40 kV and the tube current was 80 mA. By measuring under these conditions, the number of counts of background I0 is within the range of 400 to 800, and the maximum peak intensity is 1500 counts or more.
- the cumulative volume was 10% by volume, 50% by volume, and 95% by volume.
- the particle sizes were determined to be D 10 , D 50 and D 95 respectively.
- the organic solvent was passed through a 60 ⁇ m filter.
- the solvent refractive index is set to 1.50
- the particle permeability condition is set to "transmission”
- the particle refractive index is set to 1.59
- the shape is set to "aspheric”
- the measurement range is set to 0.133 ⁇ m to 704.0 ⁇ m
- the measurement time is was set to 10 seconds. The measurement was performed twice, and the arithmetic mean values of the obtained measured values were defined as D 10 , D 50 and D 95 , respectively.
- a solid battery was produced using the solid electrolytes obtained in Examples and Comparative Examples, and the rate characteristics of the solid battery were measured by the following method. The results are shown in Table 1 below.
- material As the positive electrode active material, a LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM) powder, which is a layered compound, and a Li—Nb—O coating layer formed thereon were used. Graphite was used as the negative electrode active material.
- the solid electrolyte used for the positive electrode layer the solid electrolyte obtained in Examples or Comparative Examples was used.
- a general aldirodite-type sulfide solid electrolyte was used for the separator layer and the negative electrode layer.
- the positive electrode mixture was prepared by mixing the positive electrode active material, the solid electrolyte, and the conductive agent (acetylene black) powder in a mortar at a mass ratio of 60:37:3.
- the negative electrode mixture was prepared by mixing graphite and a solid electrolyte in a mass ratio of 64:36 in a mortar.
- a ceramic cylinder (opening diameter: 10.5 mm, height: 18 mm) with open top and bottom ends was closed with a SUS electrode, and 0.05 g of solid electrolyte was poured into the cylinder.
- An electrode was attached to the upper opening, and uniaxial press molding was performed at about 0.8 tf/cm 2 to produce an electrolyte layer.
- the upper electrode was temporarily removed, the positive electrode mixture was poured onto the electrolyte layer, the positive electrode mixture was smoothed, and then the upper electrode was attached again.
- the lower electrode was temporarily removed, and the negative electrode mixture was poured onto the electrolyte layer.
- the lower electrode was reattached and uniaxially pressed at about 4.6 tf/cm 2 . After that, the upper electrode and the lower electrode were sandwiched with a clamp and restrained with a torque pressure of 4 N ⁇ m to produce an all-solid-state battery equivalent to 1 mAh.
- the manufacturing process of the all-solid-state battery was performed in a glove box replaced with dry air having an average dew point of -70°C.
- the all-solid-state battery thus obtained was placed in an environmental tester maintained at 25° C. and connected to a charge/discharge measuring device to evaluate battery characteristics.
- the battery was charged and discharged with 1 mA as 1C.
- the battery was charged at 0.2C to 4.5V by CC-CV method to obtain the initial charge capacity.
- the discharge was performed at 0.2C to 2.5V by the CC method to obtain the initial discharge capacity.
- the battery was charged at 0.2C to 4.5V by CC-CV method, and then discharged at 5C to 2.5V by CC method to obtain discharge capacity at 5C.
- a rate characteristic (5C/0.2C [%]) was obtained by calculating the ratio of the 5C discharge capacity to the 0.2C discharge capacity as 100%.
- the solid batteries obtained using the solid electrolytes obtained in each example have higher rate characteristics than the comparative example. Moreover, as is clear from the XRD patterns shown in FIGS. 1 and 2, no diffraction peak of lithium sulfide was observed in the solid electrolyte obtained in the example.
- solid electrolyte of the present invention as described above in detail, excellent battery characteristics can be obtained. Moreover, according to the production method of the present invention, such a solid electrolyte can be easily produced.
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Abstract
Description
したがって本発明の課題は、電池特性に優れた固体電解質及びその製造方法を提供することにある。
アルジロダイト型結晶構造を有する結晶相を含み、
前記アルジロダイト型結晶構造を有する結晶相の結晶子サイズが40nm以下であり、
CuKα1線を用いたX線回折装置(XRD)により測定されるX線回折パターンにおいて、2θ=27.0°±0.5°の範囲に観察されるピークAの強度をIaとし、2θ=25.5°±1.0°の範囲に観察されるピークBの強度をIbとしたとき、前記Ibに対する前記Iaの比Ia/Ibが0.2以下である、固体電解質を提供するものである。
下記式(1)で表される粉砕エネルギーEを前記焼成物に200J・sec/g以上加えて該焼成物を粉砕する粉砕工程と、を有する固体電解質の製造方法を提供するものである。
E(J・sec/g)=1/2ntmv2/s (1)
式中、nは粉砕メディアの個数を表し、tは粉砕時間(sec)を表し、mは粉砕メディア1個の質量(kg)を表し、vは粉砕メディアの速度(m/sec)を表し、sは粉砕対象物の質量(g)を表す。
本発明の固体電解質は、Li元素、P元素、S元素及びX元素を含有するものである。
Ia及びIbの測定方法については後述する実施例において詳述する。
なお本明細書において回折ピークの強度とは、該ピークの高さのことである。
前記と同様の観点から、2θ=21.3°±0.3°の範囲に観測される回折ピークCの強度をIcとしたとき、Icのカウント数が300カウント以下であることが好ましく、200カウント以下であることが更に好ましく、100カウント以下であることが一層好ましい。リチウムイオン伝導性をより効果的に向上させることができるからである。
回折ピークCの最大カウント数IC、及びカウント数Icの測定方法については後述する実施例において詳述する。
結晶子サイズの測定方法は後述する実施例において詳述する。
また固体電解質の粒径D50は、例えば、0.1μm以上であることが好ましく、0.3μm以上であることが更に好ましく、特に0.5μm以上であることが一層好ましい。固体電解質の表面積が過度に増えることが抑制され、抵抗増大を抑制できるからである。また、活物質との混合が容易となるからである。
粒径D50の測定方法は後述する実施例において詳述する。
特許文献1に記載されている方法において、メカニカルミリングにて固体電解質を作製した場合には、ミリング時間を長くした場合等でも原料組成物に含まれる成分である硫化リチウムが固体電解質中に残留すると考えられる。硫化リチウムは、固体電池とした際に活物質と固体電解質のリチウムイオン移動を低下させ、電池の入出力特性を低下させる一因となる物質である。
一方、特許文献2に記載されている方法を採用した場合には、硫化リチウムの残存量は改善されるものの、焼成条件によっては、アルジロダイト型結晶構造に代えて、該結晶構造より熱力学的に安定な異相の結晶相が生成する。当該異相は、先に述べた回折ピークCに対応する結晶相であり、リチウムイオン伝導性を低下させる一因となる。
特許文献1及び2に記載の製造方法とは異なり、本製造方法では、原料組成物の焼成と、焼成物のメカニカルミリングによる強粉砕とを組み合わせた方法を採用している。これによって、硫化リチウムが残留しづらく、且つ、アルジロダイト型結晶構造が主相として生成されやすくなる。その理由としては、以下のようなことが考えられる。例えば、上述した回折ピークCに対応する結晶相は、高温においてアルジロダイト型結晶構造へ相転移する結晶相であるものの、従来の焼成方法の場合、回折ピークCに対応する安定な結晶相が生成する傾向にある。これに対し、本製造方法においては、焼成後にメカニカルミリング処理をすることによって、室温においても準安定相であるアルジロダイト型結晶構造を維持することができる。すなわち、回折ピークCに対応する結晶相の生成を抑制することができると考えられる。
S元素を含有する化合物としては、例えば三硫化ニリン(P2S3)、五硫化二リン(P2S5)等の硫化リン等を挙げることができる。また、硫黄(S)元素を含有する化合物として、硫黄(S)単体を用いることもできる。
P元素を含有する化合物としては、例えば三硫化ニリン(P2S3)、五硫化二リン(P2S5)等の硫化リン、リン酸ナトリウム(Na3PO4)等のリン化合物、及びリン単体等を挙げることができる。
E(J・sec/g)=1/2ntmv2/s (1)
式中、nは粉砕メディアの個数を表し、tは粉砕時間(sec)を表し、mは粉砕メディア1個の質量(kg)を表し、vは粉砕メディアの速度(m/sec)を表し、sは粉砕対象物の質量(g)を表す。
粉砕メディアの速度vは、例えば、遊星ボールミルの場合は式(2)から算出することができる。
v(m/sec)=dπRα/60 (2)
式中、dはポット容器の直径(m)、Rは回転数(rpm)、αは自公転比を表す。
また、ビーズミル等の撹拌機構を有する粉砕機においては、粉砕メディアの速度は、撹拌機構(ディスク等)の周速v(m/sec)に対応する。
・装置:遊星ボールミル
・回転数:100rpm以上1000rpm以下
・粉砕メディアの材質:ジルコニア又はアルミナ
・粉砕メディアの直径:2mm以上30mm以下
・粉砕時間:0.5時間以上100時間以下
W=1/2mv2(3)
で表すことができる。m及びvの定義は上述したとおりである。本数値は粉砕メディア1個の衝突エネルギーが大きいことを意味する。メカノケミカル反応を促進する観点から、粉砕工程は、前記の式(3)で定義される運動エネルギーWが0.0001J以上である工程を含むことが好ましい。運動エネルギーWは、0.001J以上1.0J以下であることが更に好ましく、0.005J以上0.1J以下であることが一層好ましく、0.01J以上0.05J以下であることが更に一層好ましい。
粉砕処理は、本発明の固体電解質の粒径D50が例えば5μm以下となるように行うことが好ましく、3μm以下となるように行うことがより好ましく、1.5μm以下となるように行うことが更に好ましく、1.3μm以下となるように行うことが一層好ましく、1.1μm以下となるように行うことがより一層好ましい。固体電解質と活物質との接触面積が増え、電池の出力特性が向上するからである。
本製造方法においては、上述した強粉砕及び公知の粉砕処理(強粉砕よりも低エネルギーの粉砕処理)の合計の粉砕エネルギーが上述の範囲であることも好ましい。このような粉砕エネルギーを付与することで、異相が存在しないか、又は異相の存在割合が非常に低いアルジロダイト型結晶構造を有する結晶相を含む固体電解質が一層得られやすいからである。
本発明の固体電解質が呈する色味は、L*a*b*表色系における明度L*値で表して、好ましくは90以下であり、更に好ましくは50以上90以下であり、一層好ましくは60以上85以下であり、更に一層好ましくは75以上82以下である。
明度L*値の測定方法は、後述する実施例において詳述する。
固体電解質層の厚さは、短絡防止と体積容量密度とのバランスから、典型的には5μm以上300μm以下であることが好ましく、中でも10μm以上100μm以下であることが更に好ましい。
(1)原料組成物の調製
Li5PS4ClBrの組成となるように、硫化リチウム(Li2S)粉末と、五硫化二リン(P2S5)粉末と、塩化リチウム(LiCl)粉末と、臭化リチウム(LiBr)粉末とを、全量で5gとなるようにそれぞれ秤量した。これらの粉末に10mLのヘプタンを加えてスラリーを調製した。このスラリーを容積80mLのジルコニア容器に入れ、遊星ボールミル装置(フリッチュ社製 P-5)にセットした。粉砕メディアとして直径5mmのZrO2製ボール90gを用いた。ボールミル装置の運転条件は100rpmとし、10時間にわたって粉砕した。得られたスラリーを室温真空乾燥することで溶剤を除去し、原料組成物を得た。
原料組成物を焼成して焼成物を得た。焼成は管状電気炉を用いて行った。焼成の間、電気炉内に純度100%の窒素ガスを流通させた。焼成温度は600℃に設定し4時間にわたり焼成を行った。
焼成物を遊星ボールミル装置(フリッチュ社製 P-5)によって強粉砕した。焼成物は全量で5gとなるように秤量した。この粉末に10mLのヘプタンを加えてスラリーを調製した。このスラリーを容積80mLのジルコニア容器に入れた。粉砕メディアとして直径10mmのZrO2製ボール90gを用いた。ボールミル装置の運転条件は370rpmとし、粉砕時間は2時間とした。強粉砕は、粉末の粒径D50が10μm程度になるまで行った。得られたスラリーを室温真空乾燥することで溶剤を除去した。
強粉砕によって得られた粉末を遊星ボールミル装置によって微粉砕した。粉末は全量で2gとなるように秤量した。この粉末に10mLのトルエンと分散剤を加えてスラリーを調製した。このスラリーを容積80mLのジルコニア容器に入れた。粉砕メディアとして直径0.8mmのZrO2製ボール90gを用いた。ボールミル装置の運転条件は100rpmとし、3時間にわたって粉砕した。得られたスラリーを150℃で真空乾燥することにより、溶剤を除去した。このようにして目的とする固体電解質の粉末を得た。ICP発光分光分析によって測定されたX/Pモル比は2であり、S/Pモル比は4であった。
まず、強粉砕と微粉砕における粉砕エネルギーをそれぞれ算出した。
(強粉砕)
本実施例で用いたZrO2製粉砕メディアの密度は6.0g/cm2である。粉砕メディアの個数n、粉砕メディア1個の質量(kg)は、粉砕メディアが真球であるとの仮定の上、投入質量90gに基づき算出した。その結果、ボールの個数nは28.6個となった。粉砕メディア1個の質量は0.00314kgとなった。
遊星ボールミル装置を370rpmで運転したときの粉砕メディアの速度(m/sec)は、上述した式(2)から算出した。粉砕に用いた遊星ボールミル装置の自公転比αは2.19であり、粉砕に用いたミルポット内径は0.065mであることから、ボールの速度は2.76(m/sec)と算出された。この値に基づき、上述した式(1)から粉砕エネルギーEを計算したところ、493J・sec/gであった。
(微粉砕)
強粉砕の場合と同様にして微粉砕時の粉砕エネルギーを算出したところ、135J・sec/gであった。
したがって、強粉砕工程と微粉砕工程による粉砕エネルギーを足し合わせることで、以下の表1に記載の粉砕エネルギーEである628J・sec/gを得た。
実施例1の強粉砕工程において粉砕時間をそれぞれ10時間及び50時間とした。それ以外は実施例1と同様にして固体電解質の粉末を得た。
本比較例は、特許文献2の実施例に相当するものである。
(1)原料組成物の調製
実施例1と同様に行った。
(2)焼成
原料組成物を焼成して焼成物を得た。焼成は管状電気炉を用いて行った。焼成の間、電気炉内に純度100%の窒素ガスを流通させた。焼成温度は600℃に設定し4時間にわたり焼成を行った。
(3)弱粉砕
焼成物を遊星ボールミル装置によって弱粉砕した。焼成物は全量で5gとなるように秤量した。この粉末に10mLのトルエンと分散剤を加えてスラリーを調製した。このスラリーを容積80mLのジルコニア容器に入れた。粉砕メディアとして直径5mmのZrO2製ボール90gを用いた。ボールミル装置の運転条件は100rpmとし、3時間にわたって弱粉砕した。得られたスラリーを室温真空乾燥し、溶剤を除去した。
(4)微粉砕
実施例1と同様に行った。
本比較例は、特許文献1の実施例に相当するものである。
(1)原料組成物の調製
実施例1と同様に行った。
(2)メカニカルミリング
原料組成物を遊星ボールミル装置によってメカニカルミリング法に付した。原料組成物は全量で5gとなるようにそれぞれ秤量した。これらの粉末に10gのヘプタンを加えてスラリーを調製した。このスラリーを容積80mLのジルコニア容器に入れた。粉砕メディアとして直径10mmのZrO2製ボール90gを用いた。ボールミル装置の運転条件は370rpmとし、粉砕時間は50時間とした。得られたスラリーを室温真空乾燥し、溶剤を除去した。
(3)微粉砕
実施例1と同様に行った。
実施例及び比較例で得られた固体電解質について、XRD測定を行い、Ia/Ibの値を算出した。その結果を表1に示す。また、XRDパターンを図1及び図2に示す。実施例1、2及び3並びに比較例1及び2は、測定値に対してそれぞれ+3000、+6000、+9000、+12000、+18000カウントオフセットしたグラフである。
Ia/Ibの算出方法は以下のとおりである。
2θ=23.5°±0.5°におけるピーク強度のカウント数の平均値をバックグラウンドI0とした。また、2θ=25.5°±1.0°の範囲におけるピーク強度の最大カウント数をIBとした。IBからバックグラウンドI0を引いた値をアルジロダイト型結晶構造に起因するピーク強度Ibとした。
また、27.0°±0.5°の範囲におけるピーク強度の最大カウント数をIAとした。IAからバックグラウンドI0を引いた値をLi2S結晶構造に起因するピーク強度Iaとした。
本XRD測定においては、バックグラウンドI0の値は400~800カウントとなるように測定を実施した。また、本XRD測定における最大ピーク強度は1500カウント以上となるように測定を実施した。
回折ピークCの最大カウント数ICは、2θ=21.3°±0.3°の範囲における最大カウント数とした。
回折ピークCのカウント数Icは、最大カウント数ICからバックグラウンドI0を引いた値とした。
更に得られたX線回折パターンをSmart Lab Studio IIに読み込み、WPPF法を用いて、実施例及び比較例で得られた硫化物固体電解質について、アルジロダイト型結晶構造を有する結晶相の結晶子サイズを算出した。装置由来パラメータは標準試料を用いて補正した。その結果を表1に示す。角度補正の標準試料としてはNIST製 SRM 640fのSiを用いた。幅補正の標準試料としては、NIST製 SRM 660cのLaB6を用いた。大気非曝露セルには株式会社リガク製ASC用気密ホルダー(A00012149)を用いた。気密カバーは透明気密フィルムであり、雰囲気はArとした。
XRD測定は、株式会社リガク製のX線回折装置「Smart Lab SE」を用いて行った。測定条件は、大気非曝露、走査軸:2θ/θ、走査範囲:10°以上120°以下、ステップ幅0.02°、走査速度1°/minとした。
X線源はCuKα1線とした。管電圧は40kV、管電流は80mAとした。この条件で測定することでバックグラウンドI0のカウント数は400~800の範囲内となり、最大ピーク強度は1500カウント以上となる。
実施例及び比較例で得られた固体電解質について、以下の方法で粒径D50を測定した。その結果を以下の表1に示す。
レーザー回折粒子径分布測定装置用自動試料供給機(日機装株式会社製「Microtorac SDC」)を用い、固体電解質を含む測定用試料の流速を50%に設定し、固体電解質を含む測定用試料に対して30Wの超音波を60秒間照射した。その後、日機装株式会社製レーザー回折粒度分布測定機「MT3000II」を用いて粒度分布を測定し、得られた体積基準粒度分布のチャートから、累積体積が10体積%、50体積%及び95体積%となる粒径を求め、それぞれ、D10、D50及びD95とした。なお、D10、D50及びD95の測定の際、有機溶媒を60μmのフィルターを通した。また、溶媒屈折率を1.50、粒子透過性条件を「透過」、粒子屈折率を1.59、形状を「非球形」に設定し、測定レンジを0.133μm~704.0μm、測定時間を10秒に設定した。測定は2回行い、得られた測定値の算術平均値をそれぞれD10、D50及びD95とした。
実施例及び比較例で得られた固体電解質について、以下の方法で明度L*を測定した。その結果を以下の表1に示す。
XRD測定で用いるガラスホルダーに固体電解質の粉末を充填し、分光測色計(コニカミノルタ製、CM-2600d)を用いて測定した。光源としてCIE標準光源D65を用いた。
実施例及び比較例で得られた固体電解質を用いて固体電池を作製し、該固体電池について、以下の方法でレート特性を測定した。その結果を以下の表1に示す。
(材料)
正極活物質として、層状化合物であるLiNi0.6Co0.2Mn0.2O2(NCM)粉末に、Li-Nb-Oからなる被覆層を形成したものを用いた。負極活物質としてグラファイトを用いた。正極層に使用する固体電解質として、実施例又は比較例で得られた固体電解質を用いた。セパレーター層及び負極層には、一般的なアルジロダイト型硫化物固体電解質を用いた。
(正極合剤及び負極合剤の調製)
正極合剤は、正極活物質、固体電解質及び導電助剤(アセチレンブラック)粉末を、質量比で60:37:3の割合で乳鉢混合することで調製した。
負極合剤は、グラファイトと固体電解質を質量比で64:36の割合で乳鉢混合することで調製した。
(固体電池セルの作製)
上下端が開口したセラミック製の円筒(開口径10.5mm、高さ18mm)の下側開口部をSUS製の電極で閉塞した状態下に円筒内に0.05gの固体電解質を注いだ。上側開口部に電極を装着し、約0.8tf/cm2で一軸プレス成型し、電解質層を作製した。上側の電極を一旦取り外し、電解質層上に正極合剤を注ぎ、該正極合剤を平滑にならした後、上側の電極を再度装着した。次いで下側の電極を一旦取り外し、電解質層上に負極合剤を注いだ。下側の電極を再度装着し、約4.6tf/cm2で一軸プレス成型した。然る後、上側電極と下側電極との間をクランプではさみ込み、4N・mのトルク圧で拘束し、1mAh相当の全固体電池を作製した。全固体電池の作製工程は、平均露点-70℃の乾燥空気で置換されたグローブボックス内で行った。
このようにして得られた全固体電池を、25℃に保たれた環境試験機内に載置し、充放電測定装置に接続して電池特性を評価した。
1mAを1Cとして電池の充放電を行った。0.2Cで4.5VまでCC-CV方式で充電し、初回充電容量を得た。放電は0.2Cで2.5VまでCC方式で行い初回放電容量を得た。
次に0.2Cで4.5VまでCC-CV方式で充電した後に、5Cで2.5VまでCC方式で放電し、5Cにおける放電容量を得た。0.2Cの放電容量を100%としたときの5Cの放電容量の割合を算出し、レート特性(5C/0.2C[%])を得た。
また図1及び図2に示すXRDパターンから明らかなとおり、実施例で得られた固体電解質には硫化リチウムの回折ピークが観察されなかった。
Claims (11)
- リチウム(Li)元素、リン(P)元素、硫黄(S)元素及びハロゲン(X)元素を含み、
アルジロダイト型結晶構造を有する結晶相を含み、
前記アルジロダイト型結晶構造を有する結晶相の結晶子サイズが40nm以下であり、
CuKα1線を用いたX線回折装置(XRD)により測定されるX線回折パターンにおいて、2θ=27.0°±0.5°の範囲に観察されるピークAの強度をIaとし、2θ=25.5°±1.0°の範囲に観察されるピークBの強度をIbとしたとき、前記Ibに対する前記Iaの比Ia/Ibが0.2以下である、固体電解質。 - 前記X線回折パターンにおいて、2θ=21.3°±0.3°の範囲に観測されるピークCの最大カウント数をICとし、2θ=23.5°±0.5°の範囲に観測されるバックグラウンドの強度をI0としたとき、前記I0に対する前記ICの比IC/I0が1.55以下である、請求項1に記載の固体電解質。
- L*a*b*表色系における明度L*値が90以下である、請求項1又は2に記載の固体電解質。
- レーザー回折散乱式粒度分布測定法による累積体積50容量%における体積累積粒径D50が5μm以下である、請求項1ないし3のいずれか一項に記載の固体電解質。
- 前記リン(P)元素に対する前記ハロゲン(X)元素のモル比が1.1以上であり、
前記リン(P)元素に対する前記硫黄(S)元素のモル比が4.9以下である、請求項1ないし4のいずれか一項に記載の固体電解質。 - 前記ハロゲン(X)元素が、塩素(Cl)元素及び臭素(Br)元素である、請求項1ないし5のいずれか一項に記載の固体電解質。
- リチウム(Li)元素、リン(P)元素、硫黄(S)元素及びハロゲン(X)元素を含む原料組成物を200℃以上で焼成して焼成物を得る焼成工程と、
下記式(1)で表される粉砕エネルギーEを前記焼成物に200J・sec/g以上加えて該焼成物を粉砕する粉砕工程と、を有する固体電解質の製造方法。
E(J・sec/g)=1/2ntmv2/s (1)
式中、nは粉砕メディアの個数を表し、tは粉砕時間(sec)を表し、mは粉砕メディア1個の質量(kg)を表し、vは粉砕メディアの速度(m/sec)を表し、sは粉砕対象物の質量(g)を表す。 - レーザー回折散乱式粒度分布測定法による累積体積50容量%における体積累積粒径D50が5μm以下となるまで粉砕する、請求項7に記載の製造方法。
- 請求項1ないし6のいずれか一項に記載の固体電解質と活物質とを含む、電極合剤。
- 請求項1ないし6のいずれか一項に記載の固体電解質を含有する、固体電解質層。
- 正極層と、負極層と、前記正極層及び前記負極層の間の固体電解質層とを有する電池であって、請求項1ないし6のいずれか一項に記載の固体電解質を含有する、電池。
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WO2024085070A1 (ja) * | 2022-10-17 | 2024-04-25 | Agc株式会社 | 硫化物固体電解質粉末及び全固体リチウムイオン二次電池 |
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