WO2021065228A1 - 硫化物系無機固体電解質材料用の硫化リン組成物 - Google Patents
硫化物系無機固体電解質材料用の硫化リン組成物 Download PDFInfo
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- H01B1/10—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances sulfides
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- 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
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- 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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- C03C4/18—Compositions for glass with special properties for ion-sensitive glass
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
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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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Definitions
- the present invention relates to a phosphorus sulfide composition for a sulfide-based inorganic solid electrolyte material.
- Lithium-ion batteries are generally used as a power source for small portable devices such as mobile phones and laptop computers. Recently, in addition to small portable devices, lithium-ion batteries have begun to be used as power sources for electric vehicles and electric power storage.
- lithium-ion batteries use an electrolytic solution containing a flammable organic solvent.
- a lithium-ion battery in which the electrolyte is replaced with a solid electrolyte and the battery is completely solidified (hereinafter, also referred to as an all-solid-state lithium-ion battery) does not use a flammable organic solvent in the battery, and thus is a safety device. It is considered that the manufacturing cost and productivity are excellent because of the simplification of the battery.
- solid electrolyte material used for such a solid electrolyte for example, a sulfide-based inorganic solid electrolyte material is known.
- Patent Document 1 Japanese Unexamined Patent Publication No. 2016-27545
- Patent Document 1 Japanese Unexamined Patent Publication No. 2016-27545
- has a peak at the position of 2 ⁇ 29.86 ° ⁇ 1.00 ° in X-ray diffraction measurement using CuK ⁇ ray, and Li 2y + 3 PS 4 (0).
- a sulfide-based solid electrolyte material having a composition of .1 ⁇ y ⁇ 0.175) is described.
- Patent Document 2 International Publication No. 2016/067631 describes a method for producing sulfide glass using phosphorus sulfide according to the following formula (1) as a raw material. 100 ⁇ A / B ⁇ 37 ... (1) (In the formula, A indicates the peak area of the peak appearing in the range of 57.2 ppm or more and 58.3 ppm or less and 63.0 ppm or more and 64.5 ppm or less in the 31 PNMR spectrum analysis, and B is measured. Shows the sum of the peak areas of all peaks.)
- the sulfide-based inorganic solid electrolyte material was excellent in electrochemical stability and lithium ion conductivity, it was inferior in lithium ion conductivity to the electrolytic solution. From the above, the sulfide-based inorganic solid electrolyte material used for the lithium ion battery is required to further improve the lithium ion conductivity while having electrochemical stability.
- the present invention has been made in view of the above circumstances, and provides a phosphorus sulfide composition capable of improving the lithium ion conductivity of the obtained sulfide-based inorganic solid electrolyte material.
- the present inventors have diligently studied to provide a sulfide-based inorganic solid electrolyte material having improved lithium ion conductivity.
- the use of phosphorus sulfide composition content of a specific range of P 4 S 10 calculated from the solid 31 P-NMR spectrum obtained We have found that the lithium ion conductivity of the sulfide-based inorganic solid electrolyte material can be improved, and have reached the present invention.
- a phosphorus sulfide composition for sulfide-based inorganic solid electrolyte materials Including P 4 S 10 and P 4 S 9
- Phosphorus sulfide composition content is 99 wt% or less than 70 wt% of the P 4 S 10 calculated from the solid 31 P-NMR spectrum is provided.
- a raw material composition of a sulfide-based inorganic solid electrolyte material containing the above phosphorus sulfide composition and lithium sulfide is provided.
- a method for producing a sulfide-based inorganic solid electrolyte material which comprises a step of mechanically treating the raw material composition of the sulfide-based inorganic solid electrolyte material.
- a sulfide-based inorganic solid electrolyte material obtained by using the above phosphorus sulfide composition as a raw material is provided.
- a solid electrolyte containing the sulfide-based inorganic solid electrolyte material is provided.
- a solid electrolyte membrane containing the above solid electrolyte as a main component is provided.
- a lithium ion battery including a positive electrode including a positive electrode active material layer, an electrolyte layer, and a negative electrode including a negative electrode active material layer.
- a lithium ion battery in which at least one of the positive electrode active material layer, the electrolyte layer, and the negative electrode active material layer contains the sulfide-based inorganic solid electrolyte material is provided.
- a phosphorus sulfide composition capable of improving the lithium ion conductivity of the obtained sulfide-based inorganic solid electrolyte material.
- the phosphorus sulfide composition according to the present embodiment is a phosphorus sulfide composition for a sulfide-based inorganic solid electrolyte material (hereinafter, also referred to as a phosphorus sulfide composition), and includes P 4 S 10 and P 4 S 9 . , Calculated from the solid 31 P-NMR spectrum when the total content of P 4 S 10 , P 4 S 9 , P 4 S 7 and P 4 S 3 in the phosphorus sulfide composition is 100% by mass.
- the content of P 4 S 10 is 70% by mass or more and 99% by mass or less, preferably 72% by mass or more, more preferably 75% by mass or more, further preferably 77% by mass or more, and particularly preferably 80% by mass or more.
- the upper limit of the content of P 4 S 10 calculated from the solid 31 P-NMR spectrum is not particularly limited, but may be 98% by mass or less, or 95% by mass or less.
- the phosphorus sulfide composition according to the present embodiment can improve the lithium ion conductivity of the obtained sulfide-based inorganic solid electrolyte material when the content of P 4 S 10 is at least the above lower limit value. Is not necessarily clear about this reason, phosphorus sulfide compositions according to the present embodiment, since a relatively high content of P 4 S 10, phosphorus sulfide compounds having a boiling point below comparable P 4 S 10 (P It is considered that this is because the content of 4 S 9 , P 4 S 7 , P 4 S 3 etc.) or phosphorus sulfide polymer (insoluble sulfur) is reduced.
- the phosphorus sulfide composition according to the present embodiment has a relatively small amount of the phosphorus sulfide compound or the phosphorus sulfide polymer having a relatively low boiling point, it can be obtained by using the phosphorus sulfide composition according to the present embodiment. It is considered that the lithium ion conductivity of the sulfide-based inorganic solid electrolyte material can be improved.
- the phosphorus sulfide composition in which the content of P 4 S 10 is within the above range is, for example, P 4 in the phosphorus sulfide composition by subjecting the raw material composition of phosphorus sulfide to vacuum heating.
- the content of P 4 S 9 calculated from the solid 31 P-NMR spectrum is preferably 1% by mass or more and 30% by mass or less.
- the upper limit of the content of P 4 S 9 calculated from the solid 31 P-NMR spectrum is preferably 28% by mass or less, more preferably 25% by mass or less, still more preferably 23% by mass or less, and in particular. It is preferably 20% by mass or less.
- the lower limit of the content of P 4 S 9 calculated from the solid 31 P-NMR spectrum is not particularly limited, but may be 2% by mass or more, or 5% by mass or more.
- the solid 31 P-NMR spectrum can be measured by, for example, the following method. First, filling the test sample into the sample tube for measurement of 3.2mm diameter in a glove box purged with N 2 gas, the magic angle to the external magnetic field (54.7 °) rotation in an inclined state (Magic Angle spining : MAS) and measure under the following conditions.
- the integral value of the peaks derived from each component is proportional to the number of moles of phosphorus contained. Therefore, the content ratio can be calculated from the obtained integrated value and the molecular weight of each component.
- the chemical shift of P 4 S 10 is 40 to 52 ppm
- the chemical shift of P 4 S 9 is 52 to 70 ppm
- the chemical shift of P 4 S 7 is 80 to 90 ppm, 90 to 100 ppm, 110 to 115 ppm, chemistry of P 4 S 3.
- the shift is 80 to 90 ppm and 90 to 100 ppm.
- the solid 31 P-NMR spectrum when the solid 31 P-NMR spectrum is measured, it is preferable that no peak is observed in the range of 80 ppm or more and 90 ppm or less. That is, it is preferable that the peaks of P 4 S 7 and P 4 S 3 are not observed.
- it is possible to increase the ratio of P 4 S 10 in phosphorus sulfide composition it is possible to further improve the lithium ion conductive sulfide-based inorganic solid electrolyte material obtained.
- the phosphorus sulfide composition according to this embodiment contains P 4 S 10 and P 4 S 9.
- the total content of P 4 S 10 and P 4 S 9 in the phosphorus sulfide composition according to the present embodiment is 95 mass from the viewpoint that the lithium ion conductivity of the obtained sulfide-based inorganic solid electrolyte material can be further improved. % Or more is preferable, 97% by mass or more is more preferable, 98% by mass or more is further preferable, and 99% by mass or more is even more preferable.
- the upper limit of the total content of P 4 S 10 and P 4 S 9 in the phosphorus sulfide composition according to the present embodiment is not particularly limited, but is, for example, 100% by mass or less.
- examples of the components that may be contained in addition to P 4 S 10 and P 4 S 9 include P 4 S 7 and P 4 S 3.
- Examples of the properties of the phosphorus sulfide composition according to the present embodiment include powder. Since the sulfide-based inorganic solid electrolyte material described later is generally produced by a dry method, if the phosphorus sulfide composition according to the present embodiment is in the form of powder, the sulfide-based inorganic solid electrolyte material can be produced. It will be easier.
- the method for producing a phosphorus sulfide composition according to the present embodiment is different from the conventional method for producing a phosphorus sulfide composition. That is, the phosphorus sulfide composition in which the content of P 4 S 10 is within the above range is equivalent to P 4 S 10 in the phosphorus sulfide composition by, for example, vacuum heating the raw material composition of phosphorus sulfide.
- the method for producing a phosphorus sulfide composition includes, for example, the following steps (X) and (Y).
- a raw material composition of phosphorus sulfide is prepared. Is not particularly restricted but includes raw material composition of phosphorus sulfide used as the raw material, it may be used as it is diphosphorus pentasulfide, which is commercially available (P 4 S 10), the manufacturing method commonly known diphosphorus pentasulfide You may use the raw material composition of phosphorus sulfide obtained by using.
- the raw material composition of phosphorus sulfide for example, in vacuum, a phosphorus sulfide compound having a boiling point equal to or lower than that of P 4 S 10 in the phosphorus sulfide composition (P 4 S 9 , P 4 S 7 , P 4 S) 3 etc.) and reduce the amount of phosphorus sulfide polymer.
- vacuum heating is performed until the content of P 4 S 10 is within the above range.
- the phosphorus sulfide composition according to the present embodiment can be obtained.
- the raw material composition of phosphorus sulfide is, for example, vacuum-heated
- the component that accumulates at the bottom of the container without evaporating is usually the phosphorus sulfide composition according to the present embodiment.
- Conditions such as pressure, heating temperature, and treatment time when the raw material composition of phosphorus sulfide is vacuum-heated can be appropriately determined depending on the amount of the raw material composition of phosphorus sulfide to be treated.
- the pressure in the vacuum heating device when the raw material composition of phosphorus sulfide is vacuum-heated is, for example, ⁇ 0.01 MPa or less, preferably ⁇ 0.07 MPa or less.
- the heating temperature when the raw material composition of phosphorus sulfide is vacuum-heated is, for example, 220 ° C. or higher and 500 ° C. or lower, and preferably 250 ° C. or higher and 350 ° C. or lower.
- the time for vacuum-heating the phosphorus sulfide raw material composition is, for example, 0.5 hours or more and 24 hours or less, preferably 1 hour or more and 5 hours or less.
- the sulfide-based inorganic solid electrolyte material according to the present embodiment can be obtained by using the phosphorus sulfide composition according to the present embodiment as a raw material.
- the sulfide-based inorganic solid electrolyte material according to the present embodiment contains Li, P, and S as constituent elements from the viewpoint of further improving the electrochemical stability, the stability in moisture and air, and the handleability. Is preferable. Further, the sulfide-based inorganic solid electrolyte material according to the present embodiment is the sulfide from the viewpoint of further improving lithium ion conductivity, electrochemical stability, stability in water and air, handleability, and the like.
- the molar ratio of the Li content to the P content in the based inorganic solid electrolyte material is preferably 1.0 or more and 5.0 or less, more preferably 2.0 or more and 4.0 or less.
- the contents of Li, P and S in the sulfide-based inorganic solid electrolyte material according to the present embodiment can be determined by, for example, ICP emission spectroscopic analysis or X-ray analysis.
- the degree is preferably 0.5 ⁇ 10 -3 S ⁇ cm -1 or more, more preferably 0.6 ⁇ 10 -3 S ⁇ cm -1 or more, still more preferably 0.8 ⁇ 10 -3 S ⁇ cm ⁇ . 1 or more, particularly preferably 1.0 ⁇ 10 -3 S ⁇ cm -1 or more.
- the lithium ion conductivity of the sulfide-based inorganic solid electrolyte material according to the present embodiment is at least the above lower limit value, a lithium ion battery having more excellent battery characteristics can be obtained. Further, when such a sulfide-based inorganic solid electrolyte material is used, a lithium ion battery having more excellent input / output characteristics can be obtained.
- Examples of the shape of the sulfide-based inorganic solid electrolyte material according to the present embodiment include particulate matter.
- the particulate sulfide-based inorganic solid electrolyte material according to the present embodiment is not particularly limited, but the average particle size d 50 in the weight-based particle size distribution measured by the laser diffraction / scattering particle size distribution measurement method is preferably 1 ⁇ m or more and 100 ⁇ m or less. , More preferably 3 ⁇ m or more and 80 ⁇ m or less, and further preferably 5 ⁇ m or more and 60 ⁇ m or less.
- the sulfide-based inorganic solid electrolyte material according to the present embodiment preferably has excellent electrochemical stability.
- the electrochemical stability means, for example, a property that is difficult to be redoxed in a wide voltage range. More specifically, in the sulfide-based inorganic solid electrolyte material according to the present embodiment, the sulfide-based inorganic solid electrolyte material measured under the conditions of a temperature of 25 ° C., a sweep voltage range of 0 to 5 V, and a voltage sweep rate of 5 mV / sec.
- the maximum value of the oxidative decomposition current of the above is preferably 0.50 ⁇ A or less, more preferably 0.20 ⁇ A or less, further preferably 0.10 ⁇ A or less, and even more preferably 0.05 ⁇ A or less. It is preferably 0.03 ⁇ A or less, and particularly preferably 0.03 ⁇ A or less. It is preferable that the maximum value of the oxidative decomposition current of the sulfide-based inorganic solid electrolyte material is not more than the above upper limit value because the oxidative decomposition of the sulfide-based inorganic solid electrolyte material can be suppressed in the lithium ion battery.
- the lower limit of the maximum value of the oxidative decomposition current of the sulfide-based inorganic solid electrolyte material is not particularly limited, but is, for example, 0.0001 ⁇ A or more.
- the sulfide-based inorganic solid electrolyte material according to the present embodiment can be used in any application that requires lithium ion conductivity. Above all, the sulfide-based inorganic solid electrolyte material according to the present embodiment is preferably used for a lithium ion battery. More specifically, it is used for a positive electrode active material layer, a negative electrode active material layer, an electrolyte layer and the like in a lithium ion battery.
- the sulfide-based inorganic solid electrolyte material according to the present embodiment is suitably used for the positive electrode active material layer, the negative electrode active material layer, the solid electrolyte layer and the like constituting the all-solid-state lithium ion battery, and the all-solid-state lithium ion. It is particularly preferably used for the solid electrolyte layer constituting the battery.
- An example of an all-solid-state lithium-ion battery to which the sulfide-based inorganic solid electrolyte material according to the present embodiment is applied includes a positive electrode, a solid electrolyte layer, and a negative electrode laminated in this order.
- the method for producing the sulfide-based inorganic solid electrolyte material according to the present embodiment is, for example, mechanically using the raw material composition of the sulfide-based inorganic solid electrolyte material containing the phosphorus sulfide composition according to the present embodiment and lithium sulfide. Includes processing steps. More specifically, the sulfide-based inorganic solid electrolyte material according to the present embodiment can be obtained, for example, by a production method including the following steps (A) and (B).
- the method for producing a sulfide-based inorganic solid electrolyte material according to the present embodiment may further include the following steps (C) and (D), if necessary.
- Step (C) Obtained by mechanically treating the raw material composition to vitrify the raw material phosphorus sulfide composition and lithium sulfide while chemically reacting to obtain a glassy sulfide-based inorganic solid electrolyte material. Step of heating at least a part of the sulfide-based inorganic solid electrolyte material in a glass state Step (D): Step of crushing, classifying, or granulating the obtained sulfide-based inorganic solid electrolyte material.
- Step (A) of preparing a raw material composition of a sulfide-based inorganic solid electrolyte material First, a raw material composition of a sulfide-based inorganic solid electrolyte material containing the phosphorus sulfide composition according to the present embodiment, which is a raw material, and lithium nitride, and further containing lithium nitride, if necessary, is prepared. Here, the mixing ratio of each raw material in the raw material composition is adjusted so that the obtained sulfide-based inorganic solid electrolyte material has a desired composition ratio.
- the method of mixing each raw material is not particularly limited as long as it is a mixing method capable of uniformly mixing each raw material, but for example, a ball mill, a bead mill, a vibration mill, a striking crusher, a mixer (pug mixer, ribbon mixer, tumbler mixer, drum). Mixing can be performed using a mixer, a V-type mixer, etc.), a kneader, a twin-screw kneader, an air flow crusher, a crusher, a rotary blade type crusher, or the like. Mixing conditions such as stirring speed, processing time, temperature, reaction pressure, and gravitational acceleration applied to the mixture when mixing each raw material can be appropriately determined depending on the processing amount of the mixture.
- the lithium sulfide used as a raw material is not particularly limited, and commercially available lithium sulfide may be used, or for example, lithium sulfide obtained by reacting lithium hydroxide with hydrogen sulfide may be used. From the viewpoint of obtaining a high-purity sulfide-based inorganic solid electrolyte material and suppressing side reactions, it is preferable to use lithium sulfide having few impurities.
- lithium sulfide also includes lithium polysulfide.
- Lithium nitride may be used as a raw material.
- nitrogen in lithium nitride is discharged into the system as N 2 , by using lithium nitride as the raw material inorganic compound, a sulfide-based inorganic solid containing Li, P, and S as constituent elements. It is possible to increase only the Li composition with respect to the electrolyte material.
- the lithium nitride are commercially available (for example, Li 3 N, etc.) may be used, for example, metallic lithium (eg, Li foil) and a nitrogen gas Lithium nitride obtained by the above reaction may be used. From the viewpoint of obtaining a high-purity solid electrolyte material and suppressing side reactions, it is preferable to use lithium nitride having a small amount of impurities.
- Step (B) for obtaining a glassy sulfide-based inorganic solid electrolyte material Subsequently, by mechanically treating the raw material composition of the sulfide-based inorganic solid electrolyte material, the raw materials, the phosphorus sulfide composition and lithium sulfide, are vitrified while being chemically reacted, and the sulfide-based inorganic solid electrolyte in a glass state is vitrified. Get the material.
- the mechanical treatment can be vitrified while chemically reacting by mechanically colliding two or more kinds of inorganic compounds, and examples thereof include mechanochemical treatment.
- the mechanochemical treatment is a method of vitrifying the target composition while applying mechanical energy such as a shearing force or a collision force.
- the mechanochemical treatment is preferably a dry mechanochemical treatment from the viewpoint of easily realizing an environment in which water and oxygen are removed at a high level.
- each raw material can be mixed while being crushed into fine particles, so that the contact area of each raw material can be increased. As a result, the reaction of each raw material can be promoted, so that the sulfide-based inorganic solid electrolyte material according to the present embodiment can be obtained even more efficiently.
- the mechanochemical treatment is a method of vitrifying while applying mechanical energy such as shearing force, collision force or centrifugal force to the mixing target.
- Devices that perform vitrification by mechanochemical treatment include crushers and dispersers such as ball mills, bead mills, vibration mills, turbo mills, mechanofusions, disc mills, and roll mills; rock drills and vibrations.
- Rotation / impact crushing device consisting of a mechanism that combines rotation (shear stress) and impact (compressive stress) represented by drills, impact drivers, etc .; high-pressure gliding rolls; roller-type vertical mills, ball-type vertical mills, etc. Vertical mills and the like can be mentioned.
- ball mills and bead mills are preferable, and ball mills are particularly preferable, from the viewpoint of being able to efficiently generate extremely high impact energy.
- a roll mill a rotary / impact crusher consisting of a mechanism that combines rotation (shear stress) and impact (compressive stress) represented by a rock drill, a vibration drill, an impact driver, etc.
- High-pressure gliding roll Vertical mills such as roller-type vertical mills and ball-type vertical mills are preferable.
- the mixing conditions such as rotation speed, processing time, temperature, reaction pressure, and gravitational acceleration applied to the raw material inorganic composition when mechanically processing the raw material composition of the sulfide-based inorganic solid electrolyte material are the types of the raw material inorganic composition. It can be appropriately determined depending on the amount of processing and the amount of processing. In general, the faster the rotation speed, the faster the glass formation rate, and the longer the processing time, the higher the conversion rate to glass. Normally, when X-ray diffraction analysis using CuK ⁇ beam as a radiation source is performed, if the diffraction peak derived from the raw material disappears or decreases, the raw material composition of the sulfide-based inorganic solid electrolyte material is vitrified, which is desired. It can be determined that a sulfide-based inorganic solid electrolyte material has been obtained.
- the lithium ion conductivity of the sulfide-based inorganic solid electrolyte material by the AC impedance method under the measurement conditions of 27.0 ° C., an applied voltage of 10 mV, and a measurement frequency range of 0.1 Hz to 7 MHz is preferable.
- a glass-ceramic state also referred to as crystallized glass.
- the sulfide-based inorganic solid electrolyte material according to the present embodiment is preferably in a glass-ceramic state (crystallized glass state) from the viewpoint of excellent lithium ion conductivity.
- the temperature at which the glassy sulfide-based inorganic solid electrolyte material is heated is preferably in the range of 220 ° C. or higher and 500 ° C. or lower, and more preferably in the range of 250 ° C. or higher and 350 ° C. or lower.
- the time for heating the sulfide-based inorganic solid electrolyte material in the glass state is not particularly limited as long as the desired sulfide-based inorganic solid electrolyte material in the glass ceramic state can be obtained, but is not particularly limited, for example, 0.5. It is in the range of time or more and 24 hours or less, preferably 1 hour or more and 3 hours or less.
- the heating method is not particularly limited, and examples thereof include a method using a firing furnace. The conditions such as temperature and time for heating can be appropriately adjusted in order to optimize the characteristics of the sulfide-based inorganic solid electrolyte material according to the present embodiment.
- the heating of the sulfide-based inorganic solid electrolyte material in the glass state is preferably performed in an inert gas atmosphere, for example.
- an inert gas atmosphere for example.
- the inert gas when heating the glassy sulfide-based inorganic solid electrolyte material include argon gas, helium gas, nitrogen gas and the like. The higher the purity of these inert gases is, the more preferable it is to prevent impurities from being mixed into the product, and the dew point is preferably ⁇ 30 ° C. or lower, preferably ⁇ 70 ° C., in order to avoid contact with moisture.
- the temperature is more preferably ° C. or lower, and particularly preferably ⁇ 80 ° C. or lower.
- the method of introducing the inert gas into the mixed system is not particularly limited as long as the inside of the mixed system is filled with the inert gas atmosphere, but the method of purging the inert gas and the method of continuously introducing a certain amount of the inert gas are continued. The method and the like can be mentioned.
- Step of crushing, classifying, or granulating (D) In the method for producing a sulfide-based inorganic solid electrolyte material according to the present embodiment, a step of pulverizing, classifying, or granulating the obtained sulfide-based inorganic solid electrolyte material may be further performed, if necessary.
- a sulfide-based inorganic solid electrolyte material having a desired particle size can be obtained by making the particles finer by pulverization and then adjusting the particle size by a classification operation or a granulation operation.
- the crushing method is not particularly limited, and known crushing methods such as a mixer, airflow crushing, mortar, rotary mill, and coffee mill can be used.
- the classification method is not particularly limited, and a known method such as a sieve can be used. These pulverizations or classifications are preferably carried out in an inert gas atmosphere or a vacuum atmosphere from the viewpoint of preventing contact with moisture in the air.
- the method for producing the sulfide-based inorganic solid electrolyte material according to the present embodiment is not limited to the above method, and by appropriately adjusting various conditions, the sulfide-based inorganic solid electrolyte material according to the present embodiment is used. A solid electrolyte material can be obtained.
- the solid electrolyte according to the present embodiment includes the sulfide-based inorganic solid electrolyte material according to the present embodiment.
- the solid electrolyte according to the present embodiment is not particularly limited, but as a component other than the sulfide-based inorganic solid electrolyte material according to the present embodiment, for example, as long as the object of the present invention is not impaired, the above-described embodiment It may contain a different kind of solid electrolyte material from the sulfide-based inorganic solid electrolyte material according to the above.
- the solid electrolyte according to the present embodiment may contain a different type of solid electrolyte material from the sulfide-based inorganic solid electrolyte material according to the above-described embodiment.
- the type of solid electrolyte material different from the sulfide-based inorganic solid electrolyte material according to the present embodiment is not particularly limited as long as it has ionic conductivity and insulating properties, but is generally used for lithium ion batteries. Can be used.
- an inorganic solid electrolyte material such as a sulfide-based inorganic solid electrolyte material different from the sulfide-based inorganic solid electrolyte material according to the present embodiment, an oxide-based inorganic solid electrolyte material, and other lithium-based inorganic solid electrolyte materials;
- organic solid electrolyte materials such as polymer electrolytes.
- Examples of the sulfide-based inorganic solid electrolyte material different from the sulfide-based inorganic solid electrolyte material according to the present embodiment described above include Li 2 SP 4 S 10 material, Li 2 S-Si S 2 material, and Li 2 S.
- the Li 2 SP 4 S 10 material is preferable because it has excellent lithium ion conductivity and stability that does not cause decomposition in a wide voltage range.
- the Li 2 SP 4 S 10 material is a solid obtained by chemically reacting an inorganic composition containing at least Li 2 S (lithium sulfide) and P 4 S 10 with each other by mechanical treatment. Means electrolyte material.
- lithium sulfide also includes lithium polysulfide.
- oxide-based inorganic solid electrolyte material examples include NASICON type materials such as LiTi 2 (PO 4 ) 3 , LiZr 2 (PO 4 ) 3 , LiGe 2 (PO 4 ) 3 , and (La 0.5 + x Li 0.5).
- NASICON type materials such as LiTi 2 (PO 4 ) 3 , LiZr 2 (PO 4 ) 3 , LiGe 2 (PO 4 ) 3 , and (La 0.5 + x Li 0.5).
- Perovskite type such as TiO 3 , Li 2 O-P 2 O 5 material, Li 2 O-P 2 O 5 -Li 3 N material and the like can be mentioned.
- examples of other lithium-based inorganic solid electrolyte materials include LiPON, LiNbO 3 , LiTaO 3 , Li 3 PO 4 , LiPO 4-x N x (x is 0 ⁇ x ⁇ 1), LiN, LiI, and LISION. Be done. Further, glass ceramic
- organic solid electrolyte material for example, a polymer electrolyte such as a dry polymer electrolyte or a gel electrolyte can be used.
- polymer electrolyte those generally used for lithium ion batteries can be used.
- the solid electrolyte membrane according to the present embodiment contains a solid electrolyte containing the sulfide-based inorganic solid electrolyte material according to the above-described embodiment as a main component.
- the solid electrolyte membrane according to the present embodiment is used, for example, in the solid electrolyte layer constituting the all-solid-state lithium ion battery.
- An example of an all-solid-state lithium-ion battery to which the solid electrolyte membrane according to the present embodiment is applied includes a battery in which a positive electrode, a solid electrolyte layer, and a negative electrode are laminated in this order.
- the solid electrolyte layer is composed of the solid electrolyte membrane.
- the average thickness of the solid electrolyte membrane according to the present embodiment is preferably 5 ⁇ m or more and 500 ⁇ m or less, more preferably 10 ⁇ m or more and 200 ⁇ m or less, and further preferably 20 ⁇ m or more and 100 ⁇ m or less.
- the average thickness of the solid electrolyte membrane is at least the above lower limit value, the lack of the solid electrolyte and the occurrence of cracks on the surface of the solid electrolyte membrane can be further suppressed.
- the average thickness of the solid electrolyte membrane is not more than the upper limit value, the impedance of the solid electrolyte membrane can be further lowered. As a result, the battery characteristics of the obtained all-solid-state lithium-ion battery can be further improved.
- the solid electrolyte membrane according to the present embodiment is preferably a pressure-molded particulate solid electrolyte containing the sulfide-based inorganic solid electrolyte material according to the above-described embodiment. That is, it is preferable to pressurize the particulate solid electrolyte to form a solid electrolyte membrane having a certain strength due to the anchor effect between the solid electrolyte materials.
- the pressure molded product By forming the pressure molded product, the solid electrolytes are bonded to each other, and the strength of the obtained solid electrolyte membrane is further increased. As a result, the lack of the solid electrolyte and the occurrence of cracks on the surface of the solid electrolyte membrane can be further suppressed.
- the content of the sulfide-based inorganic solid electrolyte material according to the present embodiment described above in the solid electrolyte membrane according to the present embodiment is preferably 50% by mass or more, more preferably, when the entire solid electrolyte membrane is 100% by mass. It is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
- the contact property between the solid electrolytes is improved, and the interfacial contact resistance of the solid electrolyte membrane can be reduced.
- the lithium ion conductivity of the solid electrolyte membrane can be further improved.
- the upper limit of the content of the sulfide-based inorganic solid electrolyte material according to the above-described embodiment in the solid electrolyte membrane according to the present embodiment is not particularly limited, but is, for example, 100% by mass or less.
- the planar shape of the solid electrolyte membrane is not particularly limited and can be appropriately selected according to the shape of the electrode or the current collector, but can be, for example, a rectangle.
- the solid electrolyte film according to the present embodiment may contain a binder resin, but the content of the binder resin is preferably less than 0.5% by mass when the whole solid electrolyte film is 100% by mass. , More preferably 0.1% by mass or less, still more preferably 0.05% by mass or less, still more preferably 0.01% by mass or less. Further, it is even more preferable that the solid electrolyte membrane according to the present embodiment is substantially free of the binder resin, and most preferably no binder resin is contained. As a result, the contact property between the solid electrolytes is improved, and the interfacial contact resistance of the solid electrolyte membrane can be reduced. As a result, the lithium ion conductivity of the solid electrolyte membrane can be further improved.
- substantially free of binder resin means that the binder resin may be contained to the extent that the effect of the present embodiment is not impaired.
- the binder resin refers to a binder generally used in lithium ion batteries for binding inorganic solid electrolyte materials, for example, polyvinyl alcohol, polyacrylic acid, carboxymethyl cellulose, and polytetrafluoro. Examples thereof include ethylene, polyvinylidene fluoride, styrene-butadiene rubber, and polyimide.
- the solid electrolyte membrane according to the present embodiment is obtained by, for example, depositing a particulate solid electrolyte on the surface of the cavity of the mold or on the surface of the base material in a film shape, and then pressurizing the solid electrolyte deposited in the film shape.
- the method of pressurizing the solid electrolyte is not particularly limited. For example, when the particulate solid electrolyte is deposited on the surface of the cavity of the die, it is pressed by the die and the stamp, and the particulate solid electrolyte is applied to the surface of the base material. When deposited on top, a press with a die and a stamp, a roll press, a flat plate press, or the like can be used.
- the pressure for pressurizing the solid electrolyte is, for example, 10 MPa or more and 500 MPa or less.
- the inorganic solid electrolyte deposited in the form of a film may be pressurized and heated.
- the solid electrolytes are fused and bonded to each other, and the strength of the obtained solid electrolyte membrane is further increased.
- the temperature at which the solid electrolyte is heated is, for example, 40 ° C. or higher and 500 ° C. or lower.
- FIG. 1 is a cross-sectional view showing an example of the structure of the lithium ion battery 100 according to the embodiment of the present invention.
- the lithium ion battery 100 according to the present embodiment includes, for example, a positive electrode 110 including a positive electrode active material layer 101, an electrolyte layer 120, and a negative electrode 130 including a negative electrode active material layer 103. Then, at least one of the positive electrode active material layer 101, the negative electrode active material layer 103, and the electrolyte layer 120 contains the sulfide-based inorganic solid electrolyte material according to the present embodiment.
- the positive electrode active material layer 101, the negative electrode active material layer 103, and the electrolyte layer 120 contain the sulfide-based inorganic solid electrolyte material according to the present embodiment.
- the layer containing the positive electrode active material is referred to as the positive electrode active material layer 101.
- the positive electrode 110 may or may not include the current collector 105 in addition to the positive electrode active material layer 101, if necessary.
- the layer containing the negative electrode active material is referred to as the negative electrode active material layer 103.
- the negative electrode 130 may or may not include the current collector 105 in addition to the negative electrode active material layer 103, if necessary.
- the shape of the lithium ion battery 100 according to the present embodiment is not particularly limited, and examples thereof include a cylindrical type, a coin type, a square type, a film type, and any other shape.
- the lithium ion battery 100 is manufactured according to a generally known method.
- a positive electrode 110, an electrolyte layer 120, and a negative electrode 130 are stacked to form a cylindrical shape, a coin shape, a square shape, a film shape, or any other shape, and if necessary, a non-aqueous electrolyte solution is sealed therein. It is made.
- the positive electrode 110 is not particularly limited, and those generally used for lithium ion batteries can be used.
- the positive electrode 110 is not particularly limited, but can be manufactured according to a generally known method. For example, it can be obtained by forming a positive electrode active material layer 101 containing a positive electrode active material on the surface of a current collector 105 such as an aluminum foil.
- the thickness and density of the positive electrode active material layer 101 are appropriately determined according to the intended use of the battery and the like, and are not particularly limited, and can be set according to generally known information.
- the positive electrode active material layer 101 contains a positive electrode active material.
- Lithium-manganese-nickel oxide LiNi 1/3 Mn 1/3 Co 1/3 O 2
- olivine-type lithium phosphorus oxide LiFePO 4
- other compound oxides molecule; Li 2 S, CuS, Li -CuS compounds, TiS 2, FeS, MoS 2 , Li-MoS compounds, Li-TiS compounds, Li-V-S compounds, Li-FeS compound Sulfide-based positive electrode active materials such as, acetylene black impregnated with sulfur, porous carbon impregnated with sulfur, materials using sulfur as an active material such as a mixed powder of sulfur and carbon; and the like can be used. These positive electrode active materials may be used alone or in combination of two or more.
- a sulfide-based positive electrode active material is preferable from the viewpoint of having a higher discharge capacity density and being superior in cycle characteristics, and Li-Mo-S compound, Li-Ti-S compound, and Li-VS. More preferably, one or more selected from the compounds.
- the Li-Mo-S compound contains Li, Mo, and S as constituent elements, and the inorganic compositions containing molybdenum sulfide and lithium sulfide, which are usually raw materials, are chemically treated with each other by mechanical treatment. It can be obtained by reacting.
- the Li—Ti—S compound contains Li, Ti, and S as constituent elements, and an inorganic composition containing titanium sulfide and lithium sulfide, which are usually raw materials, is chemically reacted with each other by mechanical treatment. It can be obtained by letting it.
- the Li-VS compound contains Li, V, and S as constituent elements, and an inorganic composition containing vanadium sulfide and lithium sulfide, which are usually raw materials, is chemically reacted with each other by mechanical treatment. Can be obtained by
- the positive electrode active material layer 101 is not particularly limited, but may contain one or more materials selected from, for example, a binder resin, a thickener, a conductive auxiliary agent, a solid electrolyte material, and the like as components other than the positive electrode active material. .. Hereinafter, each material will be described.
- the positive electrode active material layer 101 may contain a binder resin having a role of binding the positive electrode active materials to each other and the positive electrode active material to the current collector 105.
- the binder resin according to the present embodiment is not particularly limited as long as it is a normal binder resin that can be used in a lithium ion battery, and for example, polyvinyl alcohol, polyacrylic acid, carboxymethyl cellulose, polytetrafluoroethylene, polyvinylidene fluoride, styrene, and the like. Examples thereof include butadiene rubber and polyimide. These binders may be used alone or in combination of two or more.
- the positive electrode active material layer 101 may contain a thickener from the viewpoint of ensuring the fluidity of the slurry suitable for coating.
- the thickener is not particularly limited as long as it is a normal thickener that can be used in a lithium ion battery, and for example, cellulosic polymers such as carboxymethyl cellulose, methyl cellulose, and hydroxypropyl cellulose, and ammonium salts and alkali metal salts thereof. Examples thereof include water-soluble polymers such as polycarboxylic acid, polyethylene oxide, polyvinylpyrrolidone, polyacrylate, and polyvinyl alcohol. These thickeners may be used alone or in combination of two or more.
- the positive electrode active material layer 101 may contain a conductive auxiliary agent from the viewpoint of improving the conductivity of the positive electrode 110.
- the conductive auxiliary agent is not particularly limited as long as it is an ordinary conductive auxiliary agent that can be used in a lithium ion battery, and examples thereof include carbon black such as acetylene black and kechen black, and carbon materials such as vapor phase carbon fiber. ..
- the positive electrode according to the present embodiment may contain a solid electrolyte containing the sulfide-based inorganic solid electrolyte material according to the present embodiment described above, and may be of a different type from the sulfide-based inorganic solid electrolyte material according to the present embodiment. It may contain a solid electrolyte containing a solid electrolyte material.
- the type of solid electrolyte material different from the sulfide-based inorganic solid electrolyte material according to the present embodiment is not particularly limited as long as it has ionic conductivity and insulating properties, but is generally used for lithium ion batteries. Can be used.
- inorganic solid electrolyte materials such as sulfide-based inorganic solid electrolyte materials, oxide-based inorganic solid electrolyte materials, and other lithium-based inorganic solid electrolyte materials; and organic solid electrolyte materials such as polymer electrolytes can be mentioned. More specifically, the inorganic solid electrolyte material mentioned in the description of the solid electrolyte according to the present embodiment can be used.
- the blending ratio of various materials in the positive electrode active material layer 101 is appropriately determined according to the intended use of the battery and the like, and is not particularly limited, and can be set according to generally known information.
- the negative electrode 130 is not particularly limited, and those generally used for lithium ion batteries can be used.
- the negative electrode 130 is not particularly limited, but can be manufactured according to a generally known method. For example, it can be obtained by forming a negative electrode active material layer 103 containing a negative electrode active material on the surface of a current collector 105 such as copper.
- the thickness and density of the negative electrode active material layer 103 are appropriately determined according to the intended use of the battery and the like, and are not particularly limited, and can be set according to generally known information.
- the negative electrode active material layer 103 contains a negative electrode active material.
- the negative electrode active material is not particularly limited as long as it is a normal negative electrode active material that can be used for the negative electrode of a lithium ion battery, and for example, natural graphite, artificial graphite, resin charcoal, carbon fiber, activated charcoal, hard carbon, and soft carbon.
- Carbon materials such as lithium, lithium alloy, tin, tin alloy, silicon, silicon alloy, gallium, gallium alloy, indium, indium alloy, aluminum, aluminum alloy, etc.
- Conductive polymer Lithium-titanium composite oxide (for example, Li 4 Ti 5 O 12 ) and the like. These negative electrode active materials may be used alone or in combination of two or more.
- the negative electrode active material layer 103 is not particularly limited, but may contain one or more materials selected from, for example, a binder resin, a thickener, a conductive auxiliary agent, a solid electrolyte material, and the like as components other than the negative electrode active material. .. These materials are not particularly limited, and examples thereof include the same materials as those used for the positive electrode 110 described above.
- the blending ratio of various materials in the negative electrode active material layer 103 is appropriately determined according to the intended use of the battery and the like, and is not particularly limited, and can be set according to generally known information.
- the electrolyte layer 120 is a layer formed between the positive electrode active material layer 101 and the negative electrode active material layer 103.
- Examples of the electrolyte layer 120 include a separator impregnated with a non-aqueous electrolyte solution and a solid electrolyte layer containing a solid electrolyte.
- the separator according to the present embodiment is not particularly limited as long as it has a function of electrically insulating the positive electrode 110 and the negative electrode 130 and transmitting lithium ions, but for example, a porous membrane can be used.
- a microporous polymer film is preferably used as the porous film, and examples of the material include polyolefin, polyimide, polyvinylidene fluoride, polyester and the like.
- a porous polyolefin film is preferable, and specific examples thereof include a porous polyethylene film and a porous polypropylene film.
- the non-aqueous electrolyte solution is a solution in which an electrolyte is dissolved in a solvent.
- Any known lithium salt can be used as the electrolyte, and it may be selected according to the type of active material.
- the solvent for dissolving the electrolyte is not particularly limited as long as it is usually used as a liquid for dissolving the electrolyte, and ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate (DMC).
- EC ethylene carbonate
- PC propylene carbonate
- BC butylene carbonate
- DMC dimethyl carbonate
- Sulfolans such as 3-methyl-2-oxazolidinone
- sultons such as 1,3-propanesulton, 1,4-butanesulton, naphthalusulton; and the like. These may be used individually by 1 type, or may be used in combination of 2 or more type.
- the solid electrolyte layer according to the present embodiment is a layer formed between the positive electrode active material layer 101 and the negative electrode active material layer 103, and is a layer formed of a solid electrolyte containing a solid electrolyte material.
- the solid electrolyte contained in the solid electrolyte layer is not particularly limited as long as it has lithium ion conductivity, but in the present embodiment, the solid containing the sulfide-based inorganic solid electrolyte material according to the present embodiment. It is preferably an electrolyte.
- the content of the solid electrolyte in the solid electrolyte layer according to the present embodiment is not particularly limited as long as the desired insulating property can be obtained, but is, for example, in the range of 10% by volume or more and 100% by volume or less. Above all, it is preferably in the range of 50% by volume or more and 100% by volume or less. In particular, in the present embodiment, it is preferable that the solid electrolyte layer is composed only of the solid electrolyte containing the sulfide-based inorganic solid electrolyte material according to the present embodiment.
- the solid electrolyte layer according to the present embodiment may contain a binder resin.
- a binder resin By containing the binder resin, a flexible solid electrolyte layer can be obtained.
- the binder resin include fluorine-containing binders such as polytetrafluoroethylene and polyvinylidene fluoride.
- the thickness of the solid electrolyte layer is, for example, preferably in the range of 0.1 ⁇ m or more and 1000 ⁇ m or less, and more preferably in the range of 0.1 ⁇ m or more and 300 ⁇ m or less.
- the content ratio was calculated from the obtained integral value and the molecular weight of each component.
- P 4 S 10 chemical shifts are 40 ⁇ 52ppm
- P 4 chemical shifts of S 9 is 52 ⁇ 70 ppm
- the chemical shifts are 80 ⁇ 90 ppm of P 4 S 7, 90 ⁇ 100ppm , 110 ⁇ 115ppm
- chemical P 4 S 3 The shift is 80 to 90 ppm and 90 to 100 ppm.
- the lithium ion conductivity of the sulfide-based inorganic solid electrolyte materials obtained in Examples and Comparative Examples was measured by the AC impedance method.
- the lithium ion conductivity was measured using a potentiostat / galvanostat SP-300 manufactured by Biologic.
- the size of the sample was 9.5 mm in diameter and 1.2 to 2.0 mm in thickness, and the measurement conditions were an applied voltage of 10 mV, a measurement temperature of 27.0 ° C., a measurement frequency range of 0.1 Hz to 7 MHz, and an electrode of Li foil. ..
- a sulfide-based inorganic solid electrolyte material was produced by the following procedure.
- the raw material Li 2 S (Furukawa Co., purity 99.9%) was used and Li 3 N (Furukawa Co., Ltd.), phosphorus sulfide obtained in Examples and Comparative Examples are as phosphosulfurized Each composition was used.
- a rotary blade type crusher and an alumina pot are placed in the glove box, and then high-purity dry argon gas (H) obtained through a gas purifier is placed in the glove box. Injection of 2 O ⁇ 1 ppm, O 2 ⁇ 1 ppm) and vacuum degassing were performed three times.
- Li 2 S powder Li 2 S powder
- phosphorus sulfide composition Li 3 N powder
- the raw material inorganic composition and 500 g of ZrO 2 balls having a diameter of 10 mm were put into an alumina pot (internal volume 400 mL) in the glove box, and the pot was sealed.
- the alumina pot was taken out from the glove box, the alumina pot was attached to a ball mill machine installed in an atmosphere of dry dry air introduced through a membrane air dryer, and the mechanochemical treatment was performed at 120 rpm for 500 hours to prepare the raw material.
- the inorganic composition was vitrified. After every 48 hours of mixing, the powder on the inner wall of the pot was scraped off in the glove box, sealed, and milling was continued in a dry air atmosphere.
- Example 2 As the raw material composition 2 for phosphorus sulfide, diphosphorus pentasulfide (product name: Normal S) manufactured by Perimeter Solutions was used. Next, the raw material composition 2 of phosphorus sulfide was placed in a quartz container and set in a vacuum heating device (manufactured by Furukawa Co., Ltd.). Then, it was vacuum-heated at 300 ° C. for 2 hours under a reduced pressure of ⁇ 0.094 MPa. Next, the components accumulated at the bottom of the quartz container were collected to obtain phosphorus sulfide composition 2. Each evaluation was performed on the obtained phosphorus sulfide composition 2. The results obtained are shown in Table 1.
- Example 3 As the raw material composition 3 of phosphorus sulfide, diphosphorus pentasulfide (product name: Special S) manufactured by Perimeter Solutions Co., Ltd. was used. Next, the raw material composition of phosphorus sulfide was placed in a quartz container and set in a vacuum heating device (manufactured by Furukawa Co., Ltd.). Then, it was vacuum-heated at 300 ° C. for 2 hours under a reduced pressure of ⁇ 0.094 MPa. Next, the components accumulated at the bottom of the quartz container were collected to obtain a phosphorus sulfide composition 3. Each evaluation was performed on the obtained phosphorus sulfide composition 3. The results obtained are shown in Table 1.
- the sulfide-based inorganic solid electrolyte material obtained by using the phosphorus sulfide composition of Examples as a raw material has more lithium ions than the sulfide-based inorganic solid electrolyte material obtained by using the phosphorus sulfide composition of Comparative Example as a raw material. It had excellent conductivity.
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Abstract
Description
100×A/B≧37…(1)
(式中、Aは31PNMRスペクトル解析において、ピーク位置が57.2ppm以上58.3ppm以下、及び、63.0ppm以上64.5ppm以下の範囲に現れるピークのピーク面積を示し、Bは測定されるすべてのピークのピーク面積の合計を示す。)
以上から、リチウムイオン電池に利用される硫化物系無機固体電解質材料は電気化学安定性を有しつつ、リチウムイオン伝導性のさらなる向上が求められている。
硫化物系無機固体電解質材料用の硫化リン組成物であって、
P4S10よびP4S9を含み、
当該硫化リン組成物中のP4S10、P4S9、P4S7およびP4S3の含有量の合計を100質量%としたとき、
固体31P-NMRスペクトルから算出される上記P4S10の含有量が70質量%以上99質量%以下である硫化リン組成物が提供される。
上記硫化リン組成物と、硫化リチウムと、を含む、硫化物系無機固体電解質材料の原料組成物が提供される。
上記硫化物系無機固体電解質材料の原料組成物を機械的処理する工程を含む硫化物系無機固体電解質材料の製造方法が提供される。
上記硫化リン組成物を原料として用いて得られる硫化物系無機固体電解質材料が提供される。
上記硫化物系無機固体電解質材料を含む固体電解質が提供される。
上記固体電解質を主成分として含む固体電解質膜が提供される。
正極活物質層を含む正極と、電解質層と、負極活物質層を含む負極とを備えたリチウムイオン電池であって、
上記正極活物質層、上記電解質層および上記負極活物質層のうち少なくとも一つが、上記硫化物系無機固体電解質材料を含むリチウムイオン電池が提供される。
はじめに、本実施形態に係る硫化リン組成物について説明する。
本実施形態に係る硫化リン組成物は、硫化物系無機固体電解質材料用の硫化リン組成物(以下、硫化リン組成物とも呼ぶ。)であって、P4S10およびP4S9を含み、当該硫化リン組成物中のP4S10、P4S9、P4S7およびP4S3の含有量の合計を100質量%としたとき、固体31P-NMRスペクトルから算出されるP4S10の含有量が70質量%以上99質量%以下であり、72質量%以上が好ましく、75質量%以上がより好ましく、77質量%以上がさらに好ましく、80質量%以上が特に好ましい。
固体31P-NMRスペクトルから算出されるP4S10の含有量の上限は特に限定されないが、98質量%以下であってもよいし、95質量%以下であってもよい。
この理由については必ずしも明らかではないが、本実施形態に係る硫化リン組成物はP4S10の含有量が相対的に多いため、P4S10と同等以下の沸点を有する硫化リン化合物(P4S9、P4S7、P4S3等)あるいは硫化リン重合体(不溶解性硫黄)の含有量が少なくなるからだと考えられる。
以上の理由から、本実施形態に係る硫化リン組成物は相対的に低沸点の硫化リン化合物あるいは硫化リン重合体の量が少ないため、本実施形態に係る硫化リン組成物を用いると、得られる硫化物系無機固体電解質材料のリチウムイオン伝導性を向上させることができると考えられる。
本実施形態において、P4S10の含有量が上記範囲内である硫化リン組成物は、例えば、硫化リンの原料組成物に対し、真空加熱をおこなうことにより、硫化リン組成物中のP4S10と同等以下の沸点を有する硫化リン化合物(P4S9、P4S7、P4S3等)や硫化リン重合体の量を低下させる処理等をおこなうことで得ることが可能である。
固体31P-NMRスペクトルから算出されるP4S9の含有量の下限は特に限定されないが、2質量%以上であってもよいし、5質量%以上であってもよい。
はじめに、N2ガスでパージしたグローボックス内で3.2mm径の測定用試料管に試験試料を充填し、外部磁場に対してマジック角(54.7度)傾斜した状態で回転(Magic Angle Spining:MAS)させ、以下の条件で測定をおこなう。
装置:(株)JEOL RESONANCE製JNM-ECA-600
観測周波数:242.95MHz
パルス幅:90°パルス
パルス待ち時間:2800秒
積算回数:64回
測定モード:シングルパルス法
MAS速度:12kHz
標準物質:(NH4)2HPO4・1.33ppm
試験試料の31P-NMRスペクトルにおいて検出されたピークについて、参考文献1「Hellmut Eckert, Cheryl S. Liang and Galen D. Stucky : 31P magic angle spinning NMR of crystalline phosphorous sulfides. Correlation of 31P chemical shielding tensors with local environments, J. Phys. Chem, 1989, 93, 452-457」を参照し、下記のピーク帰属に基づいてガウス関数を用いた波形分離を実施し、各ピークの積分値を算出する。各成分に由来するピークの積分値は、含有するリンのモル数に比例する。そのため、得られた積分値と各成分の分子量より含有比率を算出することができる。
P4S10の化学シフトは40~52ppm、P4S9の化学シフトは52~70ppm、P4S7の化学シフトは80~90ppm、90~100ppm、110~115ppm、P4S3の化学シフトは80~90ppm、90~100ppmである。
次に、本実施形態に係る硫化リン組成物の製造方法について説明する。
本実施形態に係る硫化リン組成物の製造方法は、従来の硫化リン組成物の製造方法とは異なるものである。すなわち、P4S10の含有量が上記範囲内である硫化リン組成物は、硫化リンの原料組成物に対し、例えば真空加熱をおこなうことにより、硫化リン組成物中のP4S10と同等以下の沸点を有する硫化リン化合物(P4S9、P4S7、P4S3等)や硫化リン重合体(不溶解性硫黄)の量を低下させる処理等の製法上の工夫点を採用することによって初めて得ることができる。
ただし、本実施形態に係る硫化リン組成物の製造方法は、上記製法上の工夫点を採用することを前提に、例えば、具体的な製造条件は種々のものを採用することができる。
以下、本実施形態に係る硫化リン組成物の製造方法をより具体的に説明する。
工程(X):硫化リンの原料組成物を準備する工程
工程(Y):硫化リンの原料組成物を例えば真空加熱することにより、硫化リン組成物中のP4S10と同等以下の沸点を有する硫化リン化合物(P4S9、P4S7、P4S3等)や硫化リン重合体(不溶解性硫黄)の量を低下させる工程
原料として用いる硫化リンの原料組成物としては特に限定されず、市販されている五硫化二リン(P4S10)をそのまま用いてもよいし、一般的に公知の五硫化二リンの製造方法を用いて得られる硫化リンの原料組成物を用いてもよい。
上記硫化リンの原料組成物を真空加熱する際の真空加熱装置内の圧力は、例えば-0.01MPa以下であり、-0.07MPa以下であることが好ましい。
上記硫化リンの原料組成物を真空加熱する際の加熱温度は、例えば220℃以上500℃以下であり、250℃以上350℃以下であることが好ましい。
上記硫化リンの原料組成物を真空加熱する時間は、例えば0.5時間以上24時間以下であり、好ましくは1時間以上5時間以下である。
以下、本実施形態に係る硫化物系無機固体電解質材料について説明する。
本実施形態に係る硫化物系無機固体電解質材料は、本実施形態に係る硫化リン組成物を原料として用いて得ることができる。
また、本実施形態に係る硫化物系無機固体電解質材料は、リチウムイオン伝導性、電気化学的安定性、水分や空気中での安定性および取り扱い性等をより一層向上させる観点から、当該硫化物系無機固体電解質材料中の上記Pの含有量に対する上記Liの含有量のモル比Li/Pが好ましくは1.0以上5.0以下であり、より好ましくは2.0以上4.0以下であり、さらに好ましくは2.5以上3.8以下であり、さらにより好ましくは2.8以上3.6以下であり、さらにより好ましくは3.0以上3.5以下であり、さらにより好ましくは3.1以上3.4以下、特に好ましくは3.1以上3.3以下であり、そして上記Pの含有量に対する上記Sの含有量のモル比S/Pが、好ましくは2.0以上6.0以下であり、より好ましくは3.0以上5.0以下であり、さらに好ましくは3.5以上4.5以下であり、さらにより好ましくは3.8以上4.2以下、さらにより好ましくは3.9以上4.1以下、特に好ましくは4.0である。
ここで、本実施形態に係る硫化物系無機固体電解質材料中のLi、PおよびSの含有量は、例えば、ICP発光分光分析やX線分析により求めることができる。
本実施形態に係る硫化物系無機固体電解質材料のリチウムイオン伝導度が上記下限値以上であると、電池特性により一層優れたリチウムイオン電池を得ることができる。さらに、このような硫化物系無機固体電解質材料を用いると、入出力特性により一層優れたリチウムイオン電池を得ることができる。
本実施形態に係る粒子状の硫化物系無機固体電解質材料は特に限定されないが、レーザー回折散乱式粒度分布測定法による重量基準粒度分布における平均粒子径d50が、好ましくは1μm以上100μm以下であり、より好ましくは3μm以上80μm以下、さらに好ましくは5μm以上60μm以下である。
硫化物系無機固体電解質材料の平均粒子径d50を上記範囲内とすることにより、良好なハンドリング性を維持すると共にリチウムイオン伝導性をより一層向上させることができる。
硫化物系無機固体電解質材料の酸化分解電流の最大値が上記上限値以下であると、リチウムイオン電池内での硫化物系無機固体電解質材料の酸化分解を抑制することができるため好ましい。
硫化物系無機固体電解質材料の酸化分解電流の最大値の下限値は特に限定されないが、例えば、0.0001μA以上である。
本実施形態に係る硫化物系無機固体電解質材料を適用した全固体型リチウムイオン電池の例としては、正極と、固体電解質層と、負極とがこの順番に積層されたものが挙げられる。
次に、本実施形態に係る硫化物系無機固体電解質材料の製造方法について説明する。
本実施形態に係る硫化物系無機固体電解質材料の製造方法は、例えば、本実施形態に係る硫化リン組成物と、硫化リチウムと、を含む硫化物系無機固体電解質材料の原料組成物を機械的処理する工程を含む。
より具体的には、本実施形態に係る硫化物系無機固体電解質材料は、例えば、以下の工程(A)および(B)を含む製造方法により得ることができる。また、本実施形態に係る硫化物系無機固体電解質材料の製造方法は、必要に応じて、以下の工程(C)および工程(D)をさらに含んでもよい。
工程(A):本実施形態に係る硫化リン組成物と、硫化リチウムと、を含む硫化物系無機固体電解質材料の原料組成物を準備する工程
工程(B):硫化物系無機固体電解質材料の原料組成物を機械的処理することにより、原料である硫化リン組成物および硫化リチウムを化学反応させながらガラス化して、ガラス状態の硫化物系無機固体電解質材料を得る工程
工程(C)得られたガラス状態の硫化物系無機固体電解質材料を加熱し、少なくとも一部を結晶化する工程
工程(D):得られた硫化物系無機固体電解質材料を粉砕、分級、または造粒する工程
はじめに、原料である本実施形態に係る硫化リン組成物と、硫化リチウムと、を含み、必要に応じて窒化リチウムをさらに含む硫化物系無機固体電解質材料の原料組成物を準備する。ここで、原料組成物中の各原料の混合比は、得られる硫化物系無機固体電解質材料が所望の組成比になるように調整する。
各原料を混合する方法としては各原料を均一に混合できる混合方法であれば特に限定されないが、例えば、ボールミル、ビーズミル、振動ミル、打撃粉砕装置、ミキサー(パグミキサー、リボンミキサー、タンブラーミキサー、ドラムミキサー、V型混合器等)、ニーダー、2軸ニーダー、気流粉砕機、クラッシャー、回転刃式の粉砕機等を用いて混合することができる。
各原料を混合するときの攪拌速度や処理時間、温度、反応圧力、混合物に加えられる重力加速度等の混合条件は、混合物の処理量によって適宜決定することができる。
ここで、本実施形態において、硫化リチウムには多硫化リチウムも含まれる。
本実施形態に係る窒化リチウムとしては特に限定されず、市販されている窒化リチウム(例えば、Li3N等)を使用してもよいし、例えば、金属リチウム(例えば、Li箔)と窒素ガスとの反応により得られる窒化リチウムを使用してもよい。高純度な固体電解質材料を得る観点および副反応を抑制する観点から、不純物の少ない窒化リチウムを使用することが好ましい。
つづいて、硫化物系無機固体電解質材料の原料組成物を機械的処理することにより、原料である硫化リン組成物および硫化リチウムを化学反応させながらガラス化して、ガラス状態の硫化物系無機固体電解質材料を得る。
また、工程(B)において、メカノケミカル処理は、水分や酸素を高いレベルで除去した環境下を実現しやすい観点から、乾式メカノケミカル処理であることが好ましい。
メカノケミカル処理を用いると、各原料を微粒子状に粉砕しながら混合することができるため、各原料の接触面積を大きくすることができる。それにより、各原料の反応を促進することができるため、本実施形態に係る硫化物系無機固体電解質材料をより一層効率良く得ることができる。
通常は、線源としてCuKα線を用いたX線回折分析をしたとき、原料由来の回折ピークが消失または低下していたら、硫化物系無機固体電解質材料の原料組成物はガラス化され、所望の硫化物系無機固体電解質材料が得られていると判断することができる。
つづいて、得られたガラス状態の硫化物系無機固体電解質材料を加熱することにより、硫化物系無機固体電解質材料の少なくとも一部を結晶化して、ガラスセラミックス状態(結晶化ガラスとも呼ばれる。)の硫化物系無機固体電解質材料を生成する。こうすることにより、より一層リチウムイオン伝導性に優れた硫化物系無機固体電解質材料を得ることができる。
すなわち、本実施形態に係る硫化物系無機固体電解質材料は、リチウムイオン伝導性に優れる点から、ガラスセラミックス状態(結晶化ガラス状態)が好ましい。
ガラス状態の硫化物系無機固体電解質材料を加熱する時間は、所望のガラスセラミックス状態の硫化物系無機固体電解質材料が得られる時間であれば特に限定されるものではないが、例えば、0.5時間以上24時間以下の範囲内であり、好ましくは1時間以上3時間以下である。加熱の方法は特に限定されるものではないが、例えば、焼成炉を用いる方法を挙げることができる。なお、このような加熱する際の温度、時間等の条件は、本実施形態に係る硫化物系無機固体電解質材料の特性を最適なものにするため適宜調整することができる。
ガラス状態の硫化物系無機固体電解質材料を加熱するときの不活性ガスとしては、例えば、アルゴンガス、ヘリウムガス、窒素ガス等が挙げられる。これらの不活性ガスは、製品への不純物の混入を防止するために、高純度である程好ましく、また、水分の接触を避けるために、露点が-30℃以下であることが好ましく、-70℃以下であることがより好ましく、-80℃以下であることが特に好ましい。混合系への不活性ガスの導入方法としては、混合系内が不活性ガス雰囲気で満たされる方法であれば特に限定されないが、不活性ガスをパージする方法、不活性ガスを一定量導入し続ける方法等が挙げられる。
本実施形態に係る硫化物系無機固体電解質材料の製造方法では、必要に応じて、得られた硫化物系無機固体電解質材料を粉砕、分級、または造粒する工程をさらにおこなってもよい。例えば、粉砕により微粒子化し、その後、分級操作や造粒操作によって粒子径を調整することにより、所望の粒子径を有する硫化物系無機固体電解質材料を得ることができる。上記粉砕方法としては特に限定されず、ミキサー、気流粉砕、乳鉢、回転ミル、コーヒーミル等公知の粉砕方法を用いることができる。また、上記分級方法としては特に限定されず、篩等公知の方法を用いることができる。
これらの粉砕または分級は、空気中の水分との接触を防ぐことができる点から、不活性ガス雰囲気下または真空雰囲気下で行うことが好ましい。
つぎに、本実施形態に係る固体電解質について説明する。本実施形態に係る固体電解質は、本実施形態に係る硫化物系無機固体電解質材料を含む。
そして、本実施形態に係る固体電解質は特に限定されないが、本実施形態に係る硫化物系無機固体電解質材料以外の成分として、例えば、本発明の目的を損なわない範囲内で、上述した本実施形態に係る硫化物系無機固体電解質材料とは異なる種類の固体電解質材料を含んでもよい。
これらの中でも、リチウムイオン伝導性に優れ、かつ広い電圧範囲で分解等を起こさない安定性を有する点から、Li2S-P4S10材料が好ましい。ここで、例えば、Li2S-P4S10材料とは、少なくともLi2S(硫化リチウム)とP4S10とを含む無機組成物を機械的処理により互いに化学反応させることにより得られる固体電解質材料を意味する。
ここで、本実施形態において、硫化リチウムには多硫化リチウムも含まれる。
その他のリチウム系無機固体電解質材料としては、例えば、LiPON、LiNbO3、LiTaO3、Li3PO4、LiPO4-xNx(xは0<x≦1)、LiN、LiI、LISICON等が挙げられる。
さらに、これらの無機固体電解質の結晶を析出させて得られるガラスセラミックスも無機固体電解質材料として用いることができる。
ポリマー電解質としては、一般的にリチウムイオン電池に用いられるものを用いることができる。
次に、本実施形態に係る固体電解質膜について説明する。
本実施形態に係る固体電解質膜は、前述した本実施形態に係る硫化物系無機固体電解質材料を含む固体電解質を主成分として含む。
本実施形態に係る固体電解質膜を適用した全固体型リチウムイオン電池の例としては、正極と、固体電解質層と、負極とがこの順番に積層されたものが挙げられる。この場合、固体電解質層が固体電解質膜により構成されたものである。
加圧成形体とすることにより、固体電解質同士の結合が起こり、得られる固体電解質膜の強度はより一層高くなる。その結果、固体電解質の欠落や、固体電解質膜表面のクラックの発生をより一層抑制できる。
本実施形態に係る固体電解質膜中の上記した本実施形態に係る硫化物系無機固体電解質材料の含有量の上限は特に限定されないが、例えば、100質量%以下である。
これにより、固体電解質間の接触性が改善され、固体電解質膜の界面接触抵抗を低下させることができる。その結果、固体電解質膜のリチウムイオン伝導性をより一層向上させることができる。そして、このようなリチウムイオン伝導性に優れた固体電解質膜を用いることにより、得られる全固体型リチウムイオン電池の電池特性を向上できる。
なお、「バインダー樹脂を実質的に含まない」とは、本実施形態の効果が損なわれない程度には含有してもよいことを意味する。また、固体電解質層と正極または負極との間に粘着性樹脂層を設ける場合、固体電解質層と粘着性樹脂層との界面近傍に存在する粘着性樹脂層由来の粘着性樹脂は、「固体電解質膜中のバインダー樹脂」から除かれる。
上記固体電解質を加圧する方法は特に限定されず、例えば、金型のキャビティ表面上に粒子状の固体電解質を堆積させた場合は金型と押し型によるプレス、粒子状の固体電解質を基材表面上に堆積させた場合は金型と押し型によるプレスやロールプレス、平板プレス等を用いることができる。
固体電解質を加圧する圧力は、例えば、10MPa以上500MPa以下である。
固体電解質を加熱する温度は、例えば、40℃以上500℃以下である。
図1は、本発明に係る実施形態のリチウムイオン電池100の構造の一例を示す断面図である。
本実施形態に係るリチウムイオン電池100は、例えば、正極活物質層101を含む正極110と、電解質層120と、負極活物質層103を含む負極130とを備えている。そして、正極活物質層101、負極活物質層103および電解質層120の少なくとも一つが、本実施形態に係る硫化物系無機固体電解質材料を含有する。また、正極活物質層101、負極活物質層103および電解質層120のすべてが、本実施形態に係る硫化物系無機固体電解質材料を含有していることが好ましい。なお、本実施形態では特に断りがなければ、正極活物質を含む層を正極活物質層101と呼ぶ。正極110は、必要に応じて、正極活物質層101に加えて集電体105をさらに含んでもよいし、集電体105を含まなくてもよい。また、本実施形態では特に断りがなければ、負極活物質を含む層を負極活物質層103と呼ぶ。負極130は、必要に応じて、負極活物質層103に加えて集電体105をさらに含んでもよいし、集電体105を含まなくてもよい。
本実施形態に係るリチウムイオン電池100の形状は特に限定されず、円筒型、コイン型、角型、フィルム型その他任意の形状が挙げられる。
正極110は特に限定されず、リチウムイオン電池に一般的に用いられているものを使用することができる。正極110は特に限定されないが、一般的に公知の方法に準じて製造することができる。例えば、正極活物質を含む正極活物質層101をアルミ箔等の集電体105の表面に形成することにより得ることができる。
正極活物質層101の厚みや密度は、電池の使用用途等に応じて適宜決定されるため特に限定されず、一般的に公知の情報に準じて設定することができる。
正極活物質としては特に限定されず一般的に公知のものを使用することができる。例えば、リチウムコバルト酸化物(LiCoO2)、リチウムニッケル酸化物(LiNiO2)、リチウムマンガン酸化物(LiMn2O4)、固溶体酸化物(Li2MnO3-LiMO2(M=Co、Ni等))、リチウム-マンガン-ニッケル酸化物(LiNi1/3Mn1/3Co1/3O2)、オリビン型リチウムリン酸化物(LiFePO4)等の複合酸化物;ポリアニリン、ポリピロール等の導電性高分子;Li2S、CuS、Li-Cu-S化合物、TiS2、FeS、MoS2、Li-Mo-S化合物、Li-Ti-S化合物、Li-V-S化合物、Li-Fe-S化合物等の硫化物系正極活物質;硫黄を含浸したアセチレンブラック、硫黄を含浸した多孔質炭素、硫黄と炭素の混合粉等の硫黄を活物質とした材料;等を用いることができる。これらの正極活物質は1種単独で使用してもよいし、2種以上を組み合わせて使用してもよい。
これらの中でも、より高い放電容量密度を有し、かつ、サイクル特性により優れる観点から、硫化物系正極活物質が好ましく、Li-Mo-S化合物、Li-Ti-S化合物、Li-V-S化合物から選択される一種または二種以上がより好ましい。
また、Li-Ti-S化合物は構成元素としてLi、Ti、およびSを含んでいるものであり、通常は原料であるチタン硫化物および硫化リチウムを含む無機組成物を機械的処理により互いに化学反応させることにより得ることができる。
Li-V-S化合物は構成元素としてLi、V、およびSを含んでいるものであり、通常は原料であるバナジウム硫化物および硫化リチウムを含む無機組成物を機械的処理により互いに化学反応させることにより得ることができる。
本実施形態に係るバインダー樹脂はリチウムイオン電池に使用可能な通常のバインダー樹脂であれば特に限定されないが、例えば、ポリビニルアルコール、ポリアクリル酸、カルボキシメチルセルロース、ポリテトラフルオロエチレン、ポリフッ化ビニリデン、スチレン・ブタジエン系ゴム、ポリイミド等が挙げられる。これらのバインダーは一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。
負極130は特に限定されず、リチウムイオン電池に一般的に用いられているものを使用することができる。負極130は特に限定されないが、一般的に公知の方法に準じて製造することができる。例えば、負極活物質を含む負極活物質層103を銅等の集電体105の表面に形成することにより得ることができる。
負極活物質層103の厚みや密度は、電池の使用用途等に応じて適宜決定されるため特に限定されず、一般的に公知の情報に準じて設定することができる。
上記負極活物質としては、リチウムイオン電池の負極に使用可能な通常の負極活物質であれば特に限定されないが、例えば、天然黒鉛、人造黒鉛、樹脂炭、炭素繊維、活性炭、ハードカーボン、ソフトカーボン等の炭素質材料;リチウム、リチウム合金、スズ、スズ合金、シリコン、シリコン合金、ガリウム、ガリウム合金、インジウム、インジウム合金、アルミニウム、アルミニウム合金等を主体とした金属系材料;ポリアセン、ポリアセチレン、ポリピロール等の導電性ポリマー;リチウムチタン複合酸化物(例えばLi4Ti5O12)等が挙げられる。これらの負極活物質は、1種単独で使用してもよいし、2種以上を組み合わせて使用してもよい。
負極活物質層103中の各種材料の配合割合は、電池の使用用途等に応じて、適宜決定されるため特に限定されず、一般的に公知の情報に準じて設定することができる。
次に、電解質層120について説明する。電解質層120は、正極活物質層101および負極活物質層103の間に形成される層である。
電解質層120とは、セパレーターに非水電解液を含浸させたものや、固体電解質を含む固体電解質層が挙げられる。
上記電解質としては、公知のリチウム塩がいずれも使用でき、活物質の種類に応じて選択すればよい。例えば、LiClO4、LiBF6、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiB10Cl10、LiAlCl4、LiCl、LiBr、LiB(C2H5)4、CF3SO3Li、CH3SO3Li、LiCF3SO3、LiC4F9SO3、Li(CF3SO2)2N、低級脂肪酸カルボン酸リチウム等が挙げられる。
本実施形態に係る固体電解質層における固体電解質の含有量は、所望の絶縁性が得られる割合であれば特に限定されるものではないが、例えば、10体積%以上100体積%以下の範囲内、中でも、50体積%以上100体積%以下の範囲内であることが好ましい。特に、本実施形態においては、固体電解質層が本実施形態に係る硫化物系無機固体電解質材料を含む固体電解質のみから構成されていることが好ましい。
なお、本発明は前述の実施形態に限定されるものではなく、本発明の目的を達成できる範囲での変形、改良等は本発明に含まれるものである。
はじめに、以下の実施例および比較例における測定方法を説明する。
レーザー回折散乱式粒度分布測定装置(マルバーン社製、マスターサイザー3000)を用いて、レーザー回折法により、実施例および比較例で得られた硫化物系無機固体電解質材料の粒度分布を測定した。測定結果から、硫化物系無機固体電解質材料について、重量基準の累積分布における50%累積時の粒径(d50、平均粒子径)を求めた。
実施例および比較例で得られた硫化リン組成物に対して、次のようにして固体31P-NMR測定をそれぞれ行った。
はじめに、N2ガスでパージしたグローボックス内で3.2mm径の測定用試料管に試験試料を充填し、外部磁場に対してマジック角(54.7度)傾斜した状態で回転(Magic Angle Spining:MAS)させ、以下の条件で測定をおこなった。
装置:(株)JEOL RESONANCE製JNM-ECA-600
観測周波数:242.95MHz
パルス幅:90°パルス
パルス待ち時間:2800秒
積算回数:64回
測定モード:シングルパルス法
MAS速度:12kHz
標準物質:(NH4)2HPO4・1.33ppm
試験試料の31P-NMRスペクトルにおいて検出されたピークについて、参考文献1「Hellmut Eckert, Cheryl S. Liang and Galen D. Stucky : 31P magic angle spinning NMR of crystalline phosphorous sulfides. Correlation of 31P chemical shielding tensors with local environments, J. Phys. Chem, 1989, 93, 452-457」を参照し、下記のピーク帰属に基づいてガウス関数を用いた波形分離を実施し、各ピークの積分値を算出した。得られた積分値と各成分の分子量より含有比率を算出した。
P4S10の化学シフトは40~52ppm、P4S9の化学シフトは52~70ppm、P4S7の化学シフトは80~90ppm、90~100ppm、110~115ppm、P4S3の化学シフトは80~90ppm、90~100ppmである。
ICP発光分光分析装置(セイコーインスツルメント社製、SPS3000)を用いて、ICP発光分光分析法により測定し、実施例および比較例で得られた硫化物系無機固体電解質材料中のLi、PおよびSの質量%をそれぞれ求め、それに基づいて、各元素のモル比をそれぞれ計算した。
実施例および比較例で得られた硫化物系無機固体電解質材料に対して、交流インピーダンス法によるリチウムイオン伝導度の測定をおこなった。
リチウムイオン伝導度の測定はバイオロジック社製、ポテンショスタット/ガルバノスタットSP-300を用いた。試料の大きさは直径9.5mm、厚さ1.2~2.0mm、測定条件は、印加電圧10mV、測定温度27.0℃、測定周波数域0.1Hz~7MHz、電極はLi箔とした。
ここで、リチウムイオン伝導度測定用の試料としては、プレス装置を用いて、実施例および比較例で得られた粉末状の硫化物系無機固体電解質材料150mgを270MPa、10分間プレスして得られる直径9.5mm、厚さ1.2~2.0mmの板状の硫化物系無機固体電解質材料を用いた。
硫化物系無機固体電解質材料を以下の手順で作製した。
原料には、Li2S(古河機械金属社製、純度99.9%)およびLi3N(古河機械金属社製)を使用し、硫化リンとしては実施例および比較例で得られた硫化リン組成物をそれぞれ使用した。
はじめに、グローブボックス内に回転刃式の粉砕機およびアルミナ製のポット(内容積400mL)を配置し、次いで、グローブボックス内に対して、ガス精製装置を通じて得られた高純度のドライアルゴンガス(H2O<1ppm、O2<1ppm)の注入および真空脱気を3回おこなった。
次いで、グローブボックス内で、回転刃式の粉砕機(回転数18000rpm)を用いて、Li2S粉末と硫化リン組成物とLi3N粉末(Li2S:硫化リン組成物:Li3N=71.1:23.7:5.3(モル%))の合計5gの混合(混合10秒および静置10秒の操作を10回(累計混合時間:100秒))をおこなうことにより、原料無機組成物を調製した。
次いで、グローブボックス内から、アルミナ製のポットを取り出し、メンブレンエアドライヤーを通して導入した乾燥したドライエアーの雰囲気下に設置したボールミル機にアルミナ製のポットを取り付け、120rpmで500時間メカノケミカル処理し、原料無機組成物のガラス化をおこなった。48時間混合する毎にグローブボックス内でポットの内壁についた粉末を掻き落とし、密封後、乾燥した大気雰囲気下でミリングを継続した。
次いで、グローブボックス内にアルミナ製のポットを入れ、得られた粉末をアルミナ製のポットからカーボンるつぼに移し、グローブボックス内に設置した加熱炉で290℃、2時間のアニール処理をおこなった。
得られた硫化物系無機固体電解質材料について各評価をおこなった。得られた結果を表1に示す。
<実施例1>
硫化リンの原料組成物1として、LIAONING RUIXING CHEMICAL GROUP社製の五硫化二リン(製品名:SUPERIOR GRADE Powder)を用いた。
次いで、硫化リンの原料組成物1を石英容器に入れて真空加熱装置(古河機械金属社製)にセットした。次いで、-0.094MPaの減圧下で、300℃、2時間真空加熱した。次いで、石英容器の底部に溜まった成分を採取し、硫化リン組成物1を得た。得られた硫化リン組成物1に対して各評価をおこなった。得られた結果を表1に示す。
硫化リンの原料組成物2として、Perimeter Solutions社製の五硫化二リン(製品名:Normal S)を用いた。
次いで、硫化リンの原料組成物2を石英容器に入れて真空加熱装置(古河機械金属社製)にセットした。次いで、-0.094MPaの減圧下で、300℃、2時間真空加熱した。次いで、石英容器の底部に溜まった成分を採取し、硫化リン組成物2を得た。得られた硫化リン組成物2に対して各評価をおこなった。得られた結果を表1に示す。
硫化リンの原料組成物3として、Perimeter Solutions社製の五硫化二リン(製品名:Special S)を用いた。
次いで、硫化リンの原料組成物を石英容器に入れて真空加熱装置(古河機械金属社製)にセットした。次いで、-0.094MPaの減圧下で、300℃、2時間真空加熱した。次いで、石英容器の底部に溜まった成分を採取し、硫化リン組成物3を得た。得られた硫化リン組成物3に対して各評価をおこなった。得られた結果を表1に示す。
硫化リン組成物4として、LIAONING RUIXING CHEMICAL GROUP社製の五硫化二リン(製品名:SUPERIOR GRADE Powder)をそのまま用いた。硫化リン組成物4に対して各評価をおこなった。得られた結果を表1に示す。
硫化リン組成物5として、Perimeter Solutions社製の五硫化二リン(製品名:Special S)をそのまま用いた。硫化リン組成物5に対して各評価をおこなった。得られた結果を表1に示す。
101 正極活物質層
103 負極活物質層
105 集電体
110 正極
120 電解質層
130 負極
Claims (11)
- 硫化物系無機固体電解質材料用の硫化リン組成物であって、
P4S10およびP4S9を含み、
当該硫化リン組成物中のP4S10、P4S9、P4S7およびP4S3の含有量の合計を100質量%としたとき、
固体31P-NMRスペクトルから算出される前記P4S10の含有量が70質量%以上99質量%以下である硫化リン組成物。 - 請求項1に記載の硫化リン組成物において、
固体31P-NMRスペクトルから算出される前記P4S9の含有量が1質量%以上30質量%以下である硫化リン組成物。 - 請求項1に記載の硫化リン組成物において、
固体31P-NMRスペクトルを測定したとき、80ppm以上90ppm以下の範囲にピークが観察されない硫化リン組成物。 - 請求項1乃至3のいずれか一項に記載の硫化リン組成物において、
P4S10およびP4S9の合計含有量が95質量%以上である硫化リン組成物。 - 請求項1乃至4のいずれか一項に記載の硫化リン組成物において、
粉末状である硫化リン組成物。 - 請求項1乃至5のいずれか一項に記載の硫化リン組成物と、硫化リチウムと、を含む、硫化物系無機固体電解質材料の原料組成物。
- 請求項6に記載の硫化物系無機固体電解質材料の原料組成物を機械的処理する工程を含む硫化物系無機固体電解質材料の製造方法。
- 請求項1乃至5のいずれか一項に記載の硫化リン組成物を原料として用いて得られる硫化物系無機固体電解質材料。
- 請求項8に記載の硫化物系無機固体電解質材料を含む固体電解質。
- 請求項9に記載の固体電解質を主成分として含む固体電解質膜。
- 正極活物質層を含む正極と、電解質層と、負極活物質層を含む負極とを備えたリチウムイオン電池であって、
前記正極活物質層、前記電解質層および前記負極活物質層のうち少なくとも一つが、請求項8に記載の硫化物系無機固体電解質材料を含むリチウムイオン電池。
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WO2024101239A1 (ja) * | 2022-11-11 | 2024-05-16 | 古河機械金属株式会社 | 硫化物系無機固体電解質材料の製造方法、硫化リン組成物の製造方法、硫化リン組成物の評価方法および硫化リン組成物 |
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KR20220059514A (ko) | 2022-05-10 |
CN114467148A (zh) | 2022-05-10 |
EP4039642A1 (en) | 2022-08-10 |
JP2023126791A (ja) | 2023-09-12 |
EP4039642A4 (en) | 2022-12-14 |
JP7297911B2 (ja) | 2023-06-26 |
CN114467148B (zh) | 2024-04-12 |
JPWO2021065228A1 (ja) | 2021-04-08 |
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