JP2020164366A - Diphosphorus pentasulfide composition for sulfide-based inorganic solid electrolyte material - Google Patents

Abstract

To provide a diphosphorus pentasulfide composition that can improve the lithium ion conductivity of the obtained sulfide-based inorganic solid electrolyte material.SOLUTION: A diphosphorus pentasulfide composition, which is a diphosphorus pentasulfide composition for sulfide-based inorganic solid electrolyte material, and in which the mole ratio (S/P) of the sulfur (S) content to the phosphorus (P) content is 2.40 or more and 2.49 or less.SELECTED DRAWING: None

Description

The present invention relates to a diphosphorus pentasulfide 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.

Currently commercially available lithium ion batteries use an electrolytic solution containing a flammable organic solvent. On the other hand, a lithium-ion battery (hereinafter, also referred to as an all-solid-state lithium-ion battery) in which the electrolytic solution is replaced with a solid electrolyte and the battery is completely solidified 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.

As a 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) has a peak at the position of 2θ = 29.86 ° ± 1.00 ° in X-ray diffraction measurement using CuKα ray, and Li _{2y + 3} PS ₄ (0). A sulfide-based solid electrolyte material having a composition of .1 ≦ y ≦ 0.175) is described.

Japanese Unexamined Patent Publication No. 2016-27545

The sulfide-based inorganic solid electrolyte material was excellent in electrochemical stability and lithium ion conductivity, but 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 diphosphorus pentasulfide 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. As a result, as a raw material for producing a sulfide-based inorganic solid electrolyte material, the molar ratio (S / P) of the sulfur (S) content to the phosphorus (P) content is in a specific range. We have found that the use of a phosphorus composition can improve the lithium ion conductivity of the obtained sulfide-based inorganic solid electrolyte material, leading to the present invention.

That is, according to the present invention.
A diphosphorus pentasulfide composition for sulfide-based inorganic solid electrolyte materials.
Provided is a diphosphorus pentasulfide composition in which the molar ratio (S / P) of the sulfur (S) content to the phosphorus (P) content is 2.40 or more and 2.49 or less.

Further, according to the present invention,
A raw material composition for a sulfide-based inorganic solid electrolyte material containing the above diphosphorus pentasulfide composition and lithium sulfide is provided.

Further, according to the present invention
Provided is 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.

Further, according to the present invention
A sulfide-based inorganic solid electrolyte material obtained by using the above diphosphorus pentasulfide composition as a raw material is provided.

Further, according to the present invention
A solid electrolyte containing the sulfide-based inorganic solid electrolyte material is provided.

Further, according to the present invention
A solid electrolyte membrane containing the above solid electrolyte as a main component is provided.

Further, according to the present invention
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.

According to the present invention, it is possible to provide a diphosphorus pentasulfide composition capable of improving the lithium ion conductivity of the obtained sulfide-based inorganic solid electrolyte material.

It is sectional drawing which shows an example of the structure of the lithium ion battery of embodiment which concerns on this invention. It is a figure for demonstrating the baseline used when calculating the calorific value of the endothermic peak. It is a figure for demonstrating the baseline used when calculating the half width of an endothermic peak. It is a figure which shows the DSC curve of the diphosphorus pentasulfide composition obtained in an Example. It is a figure which shows the DSC curve of the diphosphorus pentasulfide composition obtained in the comparative example.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all drawings, similar components are designated by a common reference numeral, and description thereof will be omitted as appropriate. Further, the figure is a schematic view and does not match the actual dimensional ratio. Unless otherwise specified, "A to B" in the numerical range represent A or more and B or less.

[Phosphorus pentasulfide composition]
First, the diphosphorus pentasulfide composition according to the present embodiment will be described.
The diphosphorus pentasulfide composition according to the present embodiment is a diphosphorus pentasulfide composition for a sulfide-based inorganic solid electrolyte material (hereinafter, also referred to as a diphosphorus pentasulfide composition), and is of phosphorus (P). The molar ratio (S / P) of the sulfur (S) content to the content is 2.40 or more and 2.49 or less.
The lower limit of S / P is preferably 2.41 or more, more preferably 2.42 or more, still more preferably 2.41 or more, from the viewpoint of further improving the stability of the obtained sulfide-based inorganic solid electrolyte material over time. It is 43 or more.

When the S / P of the diphosphorus pentasulfide composition according to the present embodiment is within the above range, the lithium ion conductivity of the obtained sulfide-based inorganic solid electrolyte material can be improved.
In the present embodiment, the diphosphorus pentasulfide composition having an S / P within the above range is contained in the diphosphorus pentasulfide composition by, for example, vacuum-heating the raw material composition of diphosphorus pentasulfide. It can be obtained by reducing the amount of sulfur component.

The present embodiment is obtained by measuring using a differential scanning calorimeter under the conditions of a starting temperature of 25 ° C., a measurement temperature range of 30 to 350 ° C., a heating rate of 5 ° C./min, and argon at 100 ml / min. In the DSC curve of the diphosphorus pentoxide composition, the DSC curve preferably has an endothermic peak in a temperature region of 280 ° C. or higher and 300 ° C. or lower, and the lower limit of the half-value width of the endothermic peak is 4.1 ° C. or higher. It is more preferably 4.3 ° C. or higher, further preferably 4.5 ° C. or higher, and particularly preferably 4.7 ° C. or higher. Thereby, the lithium ion conductivity and the stability over time of the obtained sulfide-based inorganic solid electrolyte material can be further improved.
The upper limit of the half width of the endothermic peak is not particularly limited, but is, for example, 7.0 ° C. or lower, preferably 6.8 ° C. or lower.
Here, the endothermic peak observed in the temperature range of 280 ° C. or higher and 300 ° C. or lower is the melting point of diphosphorus pentasulfide (P ₂ S ₅ ).
In the present embodiment, in the DSC curve, the diphosphorus pentasulfide composition in which the half-value width of the heat absorption peak is within the above range is obtained by, for example, vacuum-heating the raw material composition of diphosphorus pentasulfide. It can be obtained by performing a treatment for reducing the amount of a low-boiling phosphorus sulfide compound (P ₄ S ₃ , P ₆ S ₅ O _10, etc.) or a phosphorus sulfide polymer in the diphosphorus composition.

The heat of fusion of the endothermic peak is preferably 70 J / g or more, preferably 80 J / g or more, more preferably 85 J / g or more, still more preferably 90 J / g or more, and particularly preferably 95 J / g or more. is there. The upper limit of the amount of heat of fusion of the endothermic peak is not particularly limited, but for example, it may be 150 J / g or less, 130 J / g or less, 120 J / g or less, or 110 J / g or less. May be good.
In the present embodiment, in the DSC curve, the diphosphorus pentasulfide composition in which the heat of fusion of the heat absorption peak is within the above range is, for example, phosphorus pentasulfide by subjecting the raw material composition of diphosphorus pentasulfide to vacuum heating. It can be obtained by performing a treatment for reducing the amount of a low-boiling phosphorus sulfide compound (P ₄ S ₃ , P ₆ S ₅ O _10, etc.) or a phosphorus sulfide polymer in the diphosphorus composition.

The lower limit of the melting point of the diphosphorus pentasulfide composition according to the present embodiment, which is measured by a differential scanning calorimeter, is preferably 291 ° C. or higher. Thereby, the lithium ion conductivity and the stability over time of the obtained sulfide-based inorganic solid electrolyte material can be further improved.
The upper limit of the melting point of the diphosphorus pentasulfide composition according to the present embodiment is not particularly limited, but is, for example, 300 ° C. or lower, preferably 298 ° C. or lower, and more preferably 295 ° C. or lower.
In the present embodiment, the diphosphorus pentasulfide composition having a melting point within the above range in the DSC curve is, for example, a diphosphorus pentasulfide composition obtained by subjecting a raw material composition of diphosphorus pentasulfide to vacuum heating. It can be obtained by performing a treatment for reducing the amount of a phosphorus sulfide compound having a low boiling point (P ₄ S ₃ , P ₆ S ₅ O _10, etc.) or a phosphorus sulfide polymer.

The DSC curve can be measured by, for example, the following method.
First, 20 to 25 mg of the diphosphorus pentasulfide composition is weighed in an aluminum pan in an argon atmosphere, and then covered with an aluminum lid and sealed with a sample sealer. The reference aluminum container is empty. The differential scanning calorimetry is performed using a differential scanning calorimeter under the conditions of a starting temperature of 25 ° C., a measurement temperature range of 30 to 350 ° C., a heating rate of 5 ° C./min, and an atmosphere of 100 ml of argon per minute. The differential scanning calorimeter is not particularly limited, but for example, DSC6300 (manufactured by Seiko Instruments Inc.) can be used.
When the diphosphorus pentasulfide composition contains a solvent, it is preferable to dry-remove the solvent from the diphosphorus pentasulfide composition before measurement.
From the DSC curve obtained thereby, the presence or absence of an endothermic peak can be observed in the temperature range of 280 ° C. or higher and 300 ° C. or lower.
Here, the amount of heat of fusion of the endothermic peak is calculated by obtaining the area surrounded by the endothermic curve of fusion including the endothermic peak and the baseline. Since the heat capacity peculiar to a substance is different before and after the thermal change, the baseline before and after the endothermic peak is not straight.
Therefore, in the present embodiment, the baseline at the endothermic peak is a line connecting the points R and S shown in FIG. The point R is an intersection of a line parallel to the Y-axis and an endothermic curve that passes through the intersection P of the baseline before the endothermic peak and the tangent of the endothermic peak. The point S is an intersection of a line parallel to the Y-axis and an endothermic curve that passes through the intersection Q of the baseline after the endothermic peak and the tangent of the endothermic peak.
Further, in the diphosphorus pentasulfide composition according to the present embodiment, the endothermic peak observed in the temperature range of 280 ° C. or higher and 300 ° C. or lower is usually one.

Phosphorus pentasulfide compositions according to the present embodiment includes as a main component diphosphorus pentasulfide (P 2 _{S 5).} The content of diphosphorus pentasulfide contained in the diphosphorus pentasulfide composition according to the present embodiment is 95% by mass or more from the viewpoint that the lithium ion conductivity of the obtained sulfide-based inorganic solid electrolyte material can be further improved. Preferably, 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 content of diphosphorus pentasulfide contained in the diphosphorus pentasulfide composition according to the present embodiment is not particularly limited, but is, for example, 100% by mass or less. In the diphosphorus pentasulfide composition according to the present embodiment, examples of the components contained in addition to diphosphorus pentasulfide (P ₂ S ₅ ) include P ₄ S ₃ and P ₆ S ₅ O ₁₀ .

Examples of the properties of the diphosphorus pentasulfide composition according to the present embodiment include powder. Since the production of the sulfide-based inorganic solid electrolyte material described later is generally performed by a dry method, if the properties of the diphosphorus pentasulfide composition according to the present embodiment are powdery, the sulfide-based inorganic solid electrolyte material It will be easier to manufacture.

[Method for producing diphosphorus pentasulfide composition]
Next, a method for producing the diphosphorus pentasulfide composition according to the present embodiment will be described.
The method for producing a diphosphorus pentasulfide composition according to the present embodiment is different from the conventional method for producing a diphosphorus pentasulfide composition. That is, the diphosphorus pentasulfide composition in which the molar ratio (S / P) of the content of sulfur (S) to the content of phosphorus (P) is within the above range is based on the raw material composition of diphosphorus pentasulfide. For example, it can be obtained for the first time by adopting a manufacturing method device such as a treatment for reducing the amount of low-boiling sulfur component in the diphosphorus pentasulfide composition by performing vacuum heating.
However, as the method for producing the diphosphorus pentasulfide composition according to the present embodiment, for example, various specific production conditions can be adopted on the premise that the above-mentioned ingenuity in the production method is adopted.
Hereinafter, the method for producing the diphosphorus pentasulfide composition according to the present embodiment will be described more specifically.

The method for producing a diphosphorus pentasulfide composition according to the present embodiment includes, for example, the following steps (X) and (Y).
Step (X): Step of preparing the raw material composition of diphosphorus pentasulfide Step (Y): Five of the low boiling point in the diphosphorus pentasulfide composition by, for example, vacuum heating the raw material composition of diphosphorus pentasulfide. A step of reducing the amount of low-boiling sulfur components in a diphosphorus sulfide composition and reducing the molar ratio (S / P) of the sulfur (S) content to the phosphorus (P) content.

First, a raw material composition of diphosphorus pentasulfide is prepared.
It is not particularly limited as phosphorus pentasulfide in the raw material composition used as the raw material, to phosphorus pentasulfide, which is commercially available (P 2 _{S 5)} may be used as it is, generally known diphosphorus pentasulfide A raw material composition of diphosphorus pentasulfide obtained by using the production method may be used.

The raw material composition of diphosphorus pentasulfide is then vacuum heated, for example, to reduce the amount of low boiling point sulfur components in the diphosphorus pentasulfide composition. Here, vacuum heating is performed until the S / P becomes 2.40 or more and 2.49 or less. As a result, the diphosphorus pentasulfide composition according to the present embodiment can be obtained. Here, when the raw material composition of diphosphorus pentasulfide is, for example, vacuum-heated, the component that accumulates at the bottom of the container without evaporating is usually the diphosphorus pentasulfide composition according to the present embodiment.

Conditions such as pressure, heating temperature, and treatment time when the raw material composition of diphosphorus pentasulfide is vacuum-heated can be appropriately determined depending on the treatment amount of the raw material composition of diphosphorus pentasulfide.
The pressure in the vacuum heating apparatus when vacuum-heating the raw material composition of diphosphorus pentasulfide is, for example, −0.01 MPa or less, preferably −0.07 MPa or less.
The heating temperature when vacuum-heating the raw material composition of diphosphorus pentasulfide 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 raw material composition of diphosphorus pentasulfide is, for example, 0.5 hours or more and 24 hours or less, preferably 1 hour or more and 5 hours or less.

[Sulfide-based inorganic solid electrolyte material]
Hereinafter, the sulfide-based inorganic solid electrolyte material according to the present embodiment will be described.
The sulfide-based inorganic solid electrolyte material according to the present embodiment can be obtained by using the diphosphorus pentasulfide 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 Li / P 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. Yes, more preferably 2.5 or more and 3.8 or less, even more preferably 2.8 or more and 3.6 or less, even more preferably 3.0 or more and 3.5 or less, still more preferably. It is 3.1 or more and 3.4 or less, particularly preferably 3.1 or more and 3.3 or less, and the molar ratio S / P of the content of S to the content of P is preferably 2.0 or more and 6 or more. It is 0.0 or less, more preferably 3.0 or more and 5.0 or less, still more preferably 3.5 or more and 4.5 or less, still more preferably 3.8 or more and 4.2 or less, even more preferably. Is 3.9 or more and 4.1 or less, particularly preferably 4.0.
Here, 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.

In the sulfide-based inorganic solid electrolyte material according to the present embodiment, lithium ion conduction of the sulfide-based inorganic solid electrolyte material by the AC impedance method under the measurement conditions of 27.0 ° C., applied voltage of 10 mV, and measurement frequency range of 0.1 Hz to 7 MHz. 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 ^{−. It is 1} or more, particularly preferably 1.0 × 10 ^-3 S · cm ^-1 or more.
When 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 μm or more and 100 μm or less. , More preferably 3 μm or more and 80 μm or less, and further preferably 5 μm or more and 60 μm or less.
By setting the average particle size d ₅₀ of the sulfide-based inorganic solid electrolyte material within the above range, good handleability can be maintained and lithium ion conductivity can be further improved.

The sulfide-based inorganic solid electrolyte material according to the present embodiment preferably has excellent electrochemical stability. Here, 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 μA or less, more preferably 0.20 μA or less, further preferably 0.10 μA or less, and even more preferably 0.05 μA or less. It is preferably 0.03 μA or less, and particularly preferably 0.03 μA 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 μA 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. Further, 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.

[Manufacturing method of sulfide-based inorganic solid electrolyte material]
Next, a method for producing the sulfide-based inorganic solid electrolyte material according to the present embodiment will be described.
The method for producing a sulfide-based inorganic solid electrolyte material according to the present embodiment is, for example, a raw material composition for a sulfide-based inorganic solid electrolyte material containing the diphosphorus pentasulfide composition according to the present embodiment and lithium sulfide. Includes the process of mechanical processing.
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). In addition, the method for producing the sulfide-based inorganic solid electrolyte material according to the present embodiment may further include the following steps (C) and (D), if necessary.
Step (A): Step of preparing a raw material composition of a sulfide-based inorganic solid electrolyte material containing the diphosphorus pentasulfide composition according to the present embodiment and lithium sulfide Step (B): Sulfide-based inorganic solid electrolyte A process of mechanically treating the raw material composition of the material to vitrify the raw materials diphosphoride pentasulfide composition and lithium sulfide while chemically reacting to obtain a glassy sulfide-based inorganic solid electrolyte material (C). ) Step of heating the obtained sulfide-based inorganic solid electrolyte material in a glass state and crystallizing at least a part of it Step (D): Grinding, classifying, or granulating the obtained sulfide-based inorganic solid electrolyte material. Process

(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 diphosphorus pentasulfide 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.
Here, in the present embodiment, lithium sulfide also includes lithium polysulfide.

Lithium nitride may be used as a raw material. Here, since 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.
Is not particularly restricted but includes lithium nitride according to the present embodiment, 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 diphosphorus pentasulfide composition and lithium sulfide, are vitrified while chemically reacting, and the sulfide-based inorganic in a glass state is obtained. Obtain a solid electrolyte material.

Here, 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. Here, the mechanochemical treatment is a method of vitrifying the target composition while applying mechanical energy such as a shearing force or a collision force.
Further, in the step (B), 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.
When the mechanochemical treatment is used, 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 more efficiently.

Here, the mechanochemical treatment is a method of vitrifying a mixture object while applying mechanical energy such as shear force, collision force or centrifugal force. Devices that perform vitrification by mechanochemical treatment (hereinafter referred to as vitrification devices) 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. Among these, 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. In addition, from the viewpoint of excellent continuous productivity, a roll mill; a rotary / impact crusher consisting of a mechanism that combines rotation (shear stress) and impact (compressive stress) represented by rock drills, vibration drills, impact drivers, etc. High-pressure gliding roll; Vertical mills such as roller-type vertical mills and ball-type vertical mills are preferable.

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 CuKα 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 and desired. It can be determined that a sulfide-based inorganic solid electrolyte material has been obtained.

Here, in the step (B), 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. 1.0 × 10 ^-4 S · cm ^-1 or more, more preferably 2.0 × 10 ^-4 S · cm ^-1 or more, still more preferably 3.0 × 10 ^-4 S · cm ^-1 or more, particularly preferably It is preferable to carry out the vitrification treatment until the ^value becomes 4.0 × 10 ^-4 S · cm ^-1 or more. As a result, a sulfide-based inorganic solid electrolyte material having more excellent lithium ion conductivity can be obtained.

(Step of crystallizing at least a part of the sulfide-based inorganic solid electrolyte material (C))
Subsequently, by heating the obtained sulfide-based inorganic solid electrolyte material in a glass state, at least a part of the sulfide-based inorganic solid electrolyte material is crystallized to be in a glass-ceramic state (also referred to as crystallized glass). Produces a sulfide-based inorganic solid electrolyte material. By doing so, it is possible to obtain a sulfide-based inorganic solid electrolyte material having further excellent lithium ion conductivity.
That is, 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.

Further, the heating of the sulfide-based inorganic solid electrolyte material in the glass state is preferably performed in an inert gas atmosphere, for example. Thereby, deterioration (for example, oxidation) of the sulfide-based inorganic solid electrolyte material can be prevented.
Examples of 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 −70 ° C. or lower, preferably −80 ° C., in order to avoid contact with moisture. It is particularly preferable that the temperature is below ° C. 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. For example, 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. Further, 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.

In order to obtain the sulfide-based inorganic solid electrolyte material according to the present embodiment, it is important to appropriately adjust each of the above steps. However, 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.

[Solid electrolyte]
Next, the solid electrolyte according to the present embodiment will be described. 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. For example, 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 different from the sulfide-based inorganic solid electrolyte materials according to the present embodiment; Examples thereof include 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 ₂ S ₅ material, Li ₂ S-Si S ₂ material, and Li ₂ S. -GeS ₂ material, Li ₂ S-Al ₂ S ₃ material, Li ₂ S-SiS ₂ -Li ₃ PO ₄ material, Li ₂ S-P ₂ S _5- GeS ₂ material, Li ₂ S-Li ₂ OP ₂ S _5- SiS ₂ material, Li ₂ S-GeS _2- P ₂ S _5- SiS ₂ material, Li ₂ S-SnS _2- P ₂ S _5- SiS ₂ material, Li ₂ S-P ₂ S ₅ -Li Examples thereof include ₃ N material, Li ₂ S _{2 +} XP ₄ S ₃ material, Li ₂ SP ₂ S ₅ −P ₄ S ₃ material and the like. These may be used individually by 1 type, or may be used in combination of 2 or more type.
Among these, the Li ₂ SP ₂ S ₅ material is preferable because it has excellent lithium ion conductivity and stability that does not cause decomposition in a wide voltage range. Here, for example, the Li ₂ SP ₂ S ₅ material is a solid obtained by chemically reacting an inorganic composition containing at least Li ₂ S (lithium sulfide) and P ₂ S ₅ with each other by mechanical treatment. Means electrolyte material.
Here, in the present embodiment, lithium sulfide also includes lithium polysulfide.

Examples of the oxide-based inorganic solid electrolyte material 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). -3x} ) 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.
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 ceramics obtained by precipitating crystals of these inorganic solid electrolytes can also be used as the inorganic solid electrolyte material.

As the organic solid electrolyte material, for example, a polymer electrolyte such as a dry polymer electrolyte or a gel electrolyte can be used.
As the polymer electrolyte, those generally used for lithium ion batteries can be used.

[Solid electrolyte membrane]
Next, the solid electrolyte membrane according to this embodiment will be described.
The solid electrolyte membrane according to the present embodiment contains, as a main component, a solid electrolyte containing the sulfide-based inorganic solid electrolyte material according to the above-mentioned embodiment.

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. In this case, 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 μm or more and 500 μm or less, more preferably 10 μm or more and 200 μm or less, and further preferably 20 μm or more and 100 μm or less. When 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. Further, when 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.
By forming the pressure-molded body, 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, further preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more. 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. Then, by using such a solid electrolyte membrane having excellent lithium ion conductivity, the battery characteristics of the obtained all-solid-state lithium ion battery 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.

Further, 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. Then, by using such a solid electrolyte membrane having excellent lithium ion conductivity, the battery characteristics of the obtained all-solid-state lithium ion battery can be improved.
In addition, "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. When an adhesive resin layer is provided between the solid electrolyte layer and the positive electrode or the negative electrode, the adhesive resin derived from the adhesive resin layer existing near the interface between the solid electrolyte layer and the adhesive resin layer is "solid electrolyte. It is removed from the "binder resin in the film".

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, for example, by 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. Obtainable.
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 substrate. 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.

Further, if necessary, the inorganic solid electrolyte deposited in the form of a film may be pressurized and heated. When heating and pressurizing are performed, the solid electrolytes are fused and 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 temperature at which the solid electrolyte is heated is, for example, 40 ° C. or higher and 500 ° C. or lower.

[Lithium-ion battery]
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. Further, it is preferable that all of 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. In the present embodiment, unless otherwise specified, the layer containing the positive electrode active material is referred to as the positive electrode active material layer 101. If necessary, the positive electrode 110 may further include a current collector 105 in addition to the positive electrode active material layer 101, or may not include the current collector 105. Further, in the present embodiment, unless otherwise specified, 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 according to the present embodiment is manufactured according to a generally known method. For example, 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.

(Positive electrode)
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.
The positive electrode active material is not particularly limited, and generally known materials can be used. For example, lithium cobalt oxide (LiCoO ₂ ), lithium nickel oxide (LiNiO ₂ ), lithium manganese oxide (LiMn ₂ O ₄ ), solid solution oxide (Li ₂ MnO _3- LiMO ₂ (M = Co, Ni, etc.)) ), Lithium-manganese-nickel oxide (LiNi _1/3 Mn _1/3 Co _1/3 O ₂ ), olivine type lithium phosphorus oxide (LiFePO ₄ ) and other composite oxides; polyaniline, polypyrrole and other highly conductive _{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 Lithium-based positive electrode active materials such as, lithium-impregnated acetylene black, lithium-impregnated porous carbon, lithium-based materials 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.
Among these, 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.

Here, 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.
Further, 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 this 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, ammonium salts thereof, and alkali metal salts. 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. For example, 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.

(Negative electrode)
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 coal, carbon fiber, activated charcoal, hard carbon, and soft carbon. Carbon materials such as lithium, lithium alloys, tin, tin alloys, silicon, silicon alloys, gallium, gallium alloys, indium, indium alloys, aluminum, aluminum alloys, etc. Metal-based materials; polyacene, polyacetylene, polypyrrole, 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.

(Electrolyte layer)
Next, the electrolyte layer 120 will be described. 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, and 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. In particular, 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. For _{example, LiClO 4, LiBF 6, LiPF} 6, LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiB 10 Cl 10, LiAlCl 4, LiCl, LiBr, LiB (C 2 H 5) 4, CF 3 Examples thereof include SO ₃ Li, CH ₃ SO ₃ Li, LiCF ₃ SO ₃ , LiC ₄ F ₉ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, and lower fatty acid lithium carboxylate.

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). , Diethyl carbonate (DEC), methyl ethyl carbonate (MEC), vinylene carbonate (VC) and other solvents; γ-butyrolactone, γ-valerolactone and other lactones; trimethoxymethane, 1,2-dimethoxyethane, diethyl ether , 2-ethoxyethane, tetrahydrofuran, 2-methyl tetrahydrofuran and other ethers; dimethyl sulfoxide and other sulfoxides; 1,3-dioxolane, 4-methyl-1,3-dioxolane and other oxolanes; acetonitrile, nitromethane, formamide, Nitrogen-containing substances such as dimethylformamide; organic acid esters such as methyl formate, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate; phosphate triesters and jiglimes; triglimes; sulfolanes, methyl sulfolanes, etc. Sulfolans; oxazolidinones such as 3-methyl-2-oxazolidinone; sulton species such as 1,3-propane sulton, 1,4-butane sulton, nafta sulton; 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.

Further, the solid electrolyte layer according to the present embodiment may contain a binder resin. By containing the binder resin, a flexible solid electrolyte layer can be obtained. Examples of 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 μm or more and 1000 μm or less, and more preferably in the range of 0.1 μm or more and 300 μm or less.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted.
The present invention is not limited to the above-described embodiment, and modifications, improvements, and the like within the range in which the object of the present invention can be achieved are included in the present invention.

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[1] Measurement method First, the measurement methods in the following Examples and Comparative Examples will be described.

(1) Particle size distribution The particle size distribution of the sulfide-based inorganic solid electrolyte material obtained in Examples and Comparative Examples by the laser diffraction method using a laser diffraction scattering type particle size distribution measuring device (Mastersizer 3000 manufactured by Malvern). Was measured. From the measurement results, the particle size (d ₅₀ , average particle size) at 50% cumulative in the weight-based cumulative distribution of the sulfide-based inorganic solid electrolyte material was determined.

(2) Quantitative analysis of phosphorus (P) and sulfur (S) in the diphosphorus pentasulfide composition Energy-dispersed X-ray analysis (EDX) was performed on the diphosphorus pentasulfide compositions obtained in Examples and Comparative Examples. Quantitative analysis of phosphorus and sulfur was performed.
First, in an argon atmosphere, particles of 0.5 mm or more were selected from the diphosphorus pentasulfide composition and crushed by lightly pressing with a pestle. Next, the crushed product of the diphosphorus pentasulfide composition was fixed to the sample pedestal of a scanning electron microscope (S-4700 manufactured by Hitachi, Ltd.) using a carbon conductive tape so that the flat surface formed by crushing was facing up. Furthermore, gold was attached by sputtering to secure a pedestal and a conduction path. By the above operation, the image is stabilized by suppressing the charge-up and the detection of characteristic X-rays is promoted. After observing the flat surface of the crushed product of the diphosphorus sulfide composition at an electron beam accelerating voltage of 15 kV, an emission current of 10 ± 1 μA, a work distance of 12 mm, and a magnification of 500 times, it is confirmed that the flat surface is smooth, and then energy is used. Semi-quantitative analysis of phosphorus (P) and sulfur (S) was performed with a distributed analyzer (EMAX-7000 manufactured by Horiba Seisakusho).
In the semi-quantitative analysis, the characteristic X-ray is measured for 300 seconds with an electron beam accelerating voltage of 15 kV, an electron beam incident angle of 90 °, an X-ray extraction angle of 35 °, a pulse processing time of P3, and a dead time of 10 to 30%. As the quantitative conditions, the background points are set to 0.67, 1.14, 1.70, 2.86, 4.04 keV, and the quantitative correction method: standardless φ (ρz), peak separation method: overlap factor method, No mass concentration normalization, no atomic number normalization, and no low energy GB correction. The phosphorus (P) and sulfur (S) concentrations from the observation field of view of 0.25 mm × 0.17 mm were measured at any five locations on the flat surface of the crushed product of the diphosphorus sulfide composition, and the average values thereof were adopted.

(3) DSC measurement The DSC measurement was performed on the diphosphorus pentasulfide compositions obtained in Examples and Comparative Examples as follows. First, 20 to 25 mg of the diphosphorus pentasulfide composition was weighed into an aluminum pan in an argon atmosphere to prepare a sample. The aluminum pan was sealed with an aluminum cover. Next, the differential scanning calorimeter (DSC6300, Seiko Instruments Inc.) was applied to the sample under the conditions of a starting temperature of 25 ° C., a measurement temperature range of 30 to 350 ° C., a heating rate of 5 ° C./min, and an atmosphere of argon at 100 ml / min. The differential scanning calorimetry was performed using (manufactured by the company). From the DSC curve obtained as a result, the presence or absence of an endothermic peak in the temperature range of 280 ° C. or higher and 300 ° C. or lower, the amount of heat of fusion (J / g) of the endothermic peak, the half-value width (° C.) of the endothermic peak, and the endothermic peak. The peak temperature, that is, the melting point (° C.) was calculated respectively.
The amount of heat of fusion of the heat absorption peak was calculated by obtaining the area surrounded by the fusion heat absorption curve including the heat absorption peak and the baseline. The baseline at the endothermic peak was a line connecting the points R and S shown in FIG.
Further, the half width of the endothermic peak was calculated by obtaining the temperature width W at the midpoint X of the endothermic peak. The baseline at the endothermic peak was a line connecting the points R and S shown in FIG.

(4) Measurement of composition ratio of sulfide-based inorganic solid electrolyte material Measured by ICP emission spectroscopy using an ICP emission spectroscopic analyzer (manufactured by Seiko Instruments, SPS3000), and obtained in Examples and Comparative Examples. The mass% of Li, P, and S in the obtained sulfide-based inorganic solid electrolyte material were determined, and the molar ratio of each element was calculated based on the mass%.

(5) Measurement of Lithium Ion Conductivity 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.
For the measurement of lithium ion conductivity, a potentiostat / galvanostat SP-300 manufactured by Biologic was used. 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. ..
Here, as a sample for measuring the lithium ion conductivity, 150 mg of the powdered sulfide-based inorganic solid electrolyte material obtained in Examples and Comparative Examples is pressed at 270 MPa for 10 minutes using a press device. A plate-shaped sulfide-based inorganic solid electrolyte material having a diameter of 9.5 mm and a thickness of 1.2 to 2.0 mm was used.
Further, the sulfide-based inorganic solid electrolyte materials obtained in Examples and Comparative Examples were placed in a closed glass bottle and stored in an argon glove box having H ₂ O <1 ppm and O ₂ <1 ppm, and first lithium ion conduction. 150 days after the degree was measured, the lithium ion conductivity of the sulfide-based inorganic solid electrolyte material was measured by the same method as described above, and the reduction rate (%) of the ion conductivity was determined.

[2] Production of Solid Electrolyte Material A sulfide-based inorganic solid electrolyte material was produced by the following procedure.
As raw materials, Li ₂ S (manufactured by Furukawa Co., Ltd., purity 99.9%) and Li ₃ N (manufactured by Furukawa Co., Ltd.) were used, and P ₂ S ₅ was obtained in Examples and Comparative Examples. P ₂ S ₅ were used respectively.
First, a rotary blade type crusher and an alumina pot (internal volume 400 mL) 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.
Next, in the glove box, using a rotary blade type crusher (rotation speed 18000 rpm), Li ₂ S powder, P ₂ S ₅ powder and Li ₃ N powder (Li ₂ S: P ₂ S ₅ : Li ₃ N). = 71.1: 23.7: 5.3 (mol%)) by mixing a total of 5 g (mixing for 10 seconds and standing for 10 seconds 10 times (cumulative mixing time: 100 seconds)). A raw material inorganic composition was prepared.

Subsequently, 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.
Next, 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 then milling was continued in a dry air atmosphere.
Next, an alumina pot was placed in the glove box, the obtained powder was transferred from the alumina pot to a carbon crucible, and annealing treatment was performed at 290 ° C. for 2 hours in a heating furnace installed in the glove box.
Each evaluation was performed on the obtained sulfide-based inorganic solid electrolyte material. The results obtained are shown in Table 1.

[3] Production of P ₂ S ₅ <Example 1>
As a raw material composition of diphosphorus pentasulfide, diphosphorus pentasulfide (product name: SUPERIOR GRADE Powerer) manufactured by LIAONING RUIXING CHEMICAL GROUP was used.
Next, the raw material composition of diphosphorus pentasulfide 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 diphosphorus pentasulfide composition 1. Each evaluation was performed on the obtained diphosphorus pentasulfide composition 1. The results obtained are shown in Table 1.

<Example 2>
As the raw material composition of diphosphorus pentasulfide, diphosphorus pentasulfide (product name: SUPERIOR GRADE Flake) manufactured by LIAONING RUIXING CHEMICAL GROUP was used.
Next, the raw material composition of diphosphorus pentasulfide 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 diphosphorus pentasulfide composition 2. Each evaluation was performed on the obtained diphosphorus pentasulfide composition 2. The results obtained are shown in Table 1.

<Example 3>
As a raw material composition of diphosphorus pentasulfide, diphosphorus pentasulfide (product name: SUPERIOR GRADE Powder and Flake 1) manufactured by LIAONING RUIXING CHEMICAL GROUP was used.
Next, the raw material composition of diphosphorus pentasulfide 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 diphosphorus pentasulfide composition 3. Each evaluation was performed on the obtained diphosphorus pentasulfide composition 3. The results obtained are shown in Table 1.

<Example 4>
As a raw material composition of diphosphorus pentasulfide, diphosphorus pentasulfide (product name: SUPERIOR GRADE Powerer and Flake 2) manufactured by LIAONING RUIXING CHEMICAL GROUP was used.
Next, the raw material composition of diphosphorus pentasulfide 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 diphosphorus pentasulfide composition 4. Each evaluation was performed on the obtained diphosphorus pentasulfide composition 4. The results obtained are shown in Table 1.

<Example 5>
As the raw material composition of diphosphorus pentasulfide, diphosphorus pentasulfide (product name: deer first grade) manufactured by Kanto Chemical Co., Inc. was used.
Next, the raw material composition of diphosphorus pentasulfide 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 diphosphorus pentasulfide composition 5. Each evaluation was performed on the obtained diphosphorus pentasulfide composition 5. The results obtained are shown in Table 1.

<Example 6>
As a raw material composition for diphosphorus pentasulfide, diphosphorus pentasulfide manufactured by Aldrich was used.
Next, the raw material composition of diphosphorus pentasulfide 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 diphosphorus pentasulfide composition 6. Each evaluation was performed on the obtained diphosphorus pentasulfide composition 6. The results obtained are shown in Table 1.

<Comparative example 1>
As the diphosphorus pentasulfide composition 7, diphosphorus pentasulfide (product name: SUPERIOR GRADE Powerer) manufactured by LIAONING RUIXING CHEMICAL GROUP was used as it was. Each evaluation was performed on the diphosphorus pentasulfide composition 7. The results obtained are shown in Table 1.

<Comparative example 2>
As the diphosphorus pentasulfide composition 8, diphosphorus pentasulfide (product name: SUPERIOR GRADE Flake) manufactured by LIAONING RUIXING CHEMICAL GROUP was used as it was. Each evaluation was performed on the diphosphorus pentasulfide composition 8. The results obtained are shown in Table 1.

<Comparative example 3>
As the diphosphorus pentasulfide composition 9, diphosphorus pentasulfide (product name: SUPERIOR GRADE Powerer and Flake 1) manufactured by LIAONING RUIXING CHEMICAL GROUP was used as it was. Each evaluation was performed on the diphosphorus pentasulfide composition 9. The results obtained are shown in Table 1.

<Comparative example 4>
As the diphosphorus pentasulfide composition 10, diphosphorus pentasulfide (product name: SUPERIOR GRADE Powerer and Flake 2) manufactured by LIAONING RUIXING CHEMICAL GROUP was used as it was. Each evaluation was performed on the diphosphorus pentasulfide composition 10. The results obtained are shown in Table 1.

<Comparative example 5>
As the raw material composition 11 for diphosphorus pentasulfide, diphosphorus pentasulfide (product name: S Special) manufactured by Perimeter Solutions was used as it was. Each evaluation was performed on the diphosphorus pentasulfide composition 11. The results obtained are shown in Table 1.

<Comparative Example 6>
As the raw material composition 12 for diphosphorus pentasulfide, diphosphorus pentasulfide (product name: 99%) manufactured by Aldrich was used. Each evaluation was performed on the diphosphorus pentasulfide composition 12. The results obtained are shown in Table 1.

Here, the raw material composition of diphosphorus pentasulfide manufactured by LIAONING RUIXING CHEMICAL GROUP, the raw material composition of diphosphorus pentasulfide manufactured by Perimeter Solutions, and the raw material composition of diphosphorus pentasulfide manufactured by Kanto Chemical Co., Inc. used in Examples and Comparative Examples. The phosphorus raw material composition and the raw material composition of diphosphorus pentasulfide manufactured by Aldrich Co., Ltd. are sold as high-purity grades, respectively.

The sulfide-based inorganic solid electrolyte material obtained by using the diphosphorus pentasulfide composition of the example as a raw material is a sulfide-based inorganic solid electrolyte material obtained by using the diphosphorus pentasulfide composition of Comparative Example as a raw material. It was superior in lithium ion conductivity and stability over time.
Here, the DSC curves of the diphosphorus pentasulfide composition in Examples and Comparative Examples are shown in FIGS. 4 and 5, respectively.

100 Lithium-ion battery 101 Positive electrode active material layer 103 Negative electrode active material layer 105 Current collector 110 Positive electrode 120 Electrolyte layer 130 Negative electrode

Claims (11)

A diphosphorus pentasulfide composition for sulfide-based inorganic solid electrolyte materials.
A diphosphorus pentasulfide composition in which the molar ratio (S / P) of the sulfur (S) content to the phosphorus (P) content is 2.40 or more and 2.49 or less. In the diphosphorus pentasulfide composition according to claim 1,
The diphosphorus pentasulfide obtained by measuring with a differential scanning calorimeter under the conditions of a starting temperature of 25 ° C., a measurement temperature range of 30 to 350 ° C., a heating rate of 5 ° C./min, and argon at 100 ml / min. In the DSC curve of the composition, the DSC curve has an endothermic peak in a temperature region of 280 ° C. or higher and 300 ° C. or lower, and the half-value width of the heat absorption peak is 4.1 ° C. or higher. In the diphosphorus pentasulfide composition according to claim 1 or 2.
A diphosphorus pentasulfide composition having a melting point of 291 ° C. or higher as measured by a differential scanning calorimeter. In the diphosphorus pentasulfide composition according to any one of claims 1 to 3,
A diphosphorus pentasulfide composition in which the content of diphosphorus pentasulfide in the diphosphorus pentasulfide composition is 95% by mass or more. In the diphosphorus pentasulfide composition according to any one of claims 1 to 4.
A powdery diphosphorus pentasulfide composition. A raw material composition for a sulfide-based inorganic solid electrolyte material, which comprises the diphosphorus pentasulfide composition according to any one of claims 1 to 5 and lithium sulfide. 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 according to claim 6. A sulfide-based inorganic solid electrolyte material obtained by using the diphosphorus pentasulfide composition according to any one of claims 1 to 5 as a raw material. A solid electrolyte containing the sulfide-based inorganic solid electrolyte material according to claim 8. A solid electrolyte membrane containing the solid electrolyte according to claim 9 as a main component. 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 according to claim 8.

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