JP2020061305A - Phosphorus pentasulfide composition for sulfide-based inorganic solid electrolytic material - Google Patents

Abstract

To provide a phosphorus pentasulfide composition which enables the enhancement of the lithium ion-conducting property of a sulfide-based inorganic solid electrolytic material obtained therefrom.SOLUTION: The phosphorus pentasulfide composition is arranged for a sulfide-based inorganic solid electrolytic material. With the phosphorus pentasulfide composition, the ratio (P2/P1) of a quantitative value of each P2p state calculated from a peak showing the binding state of oxygen and phosphorus to a quantitative value P1 of each P2p state calculated from a peak showing the binding state of sulfur and phosphorus in P2p spectra measured by X-ray photoelectron spectroscopy (XPS) is 0.25 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 mobile devices such as mobile phones and notebook computers. In addition to lithium-ion batteries, lithium-ion batteries have recently begun to be used as a power source for electric vehicles and electric power storage.

  An electrolyte solution containing a flammable organic solvent is used in a lithium ion battery currently on the market. On the other hand, a lithium-ion battery (hereinafter, also referred to as an all-solid-state lithium-ion battery) in which the battery is made into an all-solid-state battery by replacing the electrolytic solution with a solid electrolyte does not use a flammable organic solvent in the battery. It is believed that the manufacturing cost and productivity can be improved by simplifying the manufacturing process.

  As a solid electrolyte material used for such a solid electrolyte, for example, a sulfide-based inorganic solid electrolyte material is known.

In Patent Document 1 (JP-A-2016-27545), there is a peak at a position of 2θ = 29.86 ° ± 1.00 ° in X-ray diffraction measurement using CuKα ray, and Li _{2y + 3} PS ₄ (0 .1 ≦ y ≦ 0.175), and a sulfide-based solid electrolyte material is described.

JP, 2016-27545, A

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, it is required that the sulfide-based inorganic solid electrolyte material used for the lithium-ion battery has electrochemical stability and further improve the lithium-ion conductivity.

  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 earnestly studied to provide a sulfide-based inorganic solid electrolyte material with improved lithium ion conductivity. As a result, as a raw material for producing the sulfide-based inorganic solid electrolyte material, calculated from the peak representing the bonding state of oxygen and phosphorus with respect to the P2p state-based quantitative value P1 calculated from the peak representing the bonding state of sulfur and phosphorus It is possible to improve the lithium ion conductivity of the obtained sulfide-based inorganic solid electrolyte material by using a diphosphorus pentasulfide composition having a ratio (P2 / P1) of the determined P2p state-based quantitative value P2 of 0.25 or less. Heading out, the present invention was reached.

That is, according to the present invention,
A phosphorus pentasulfide composition for a sulfide-based inorganic solid electrolyte material,
Calculated from the peak showing the binding state of oxygen and phosphorus with respect to the quantitative value P1 for each P2p state calculated from the peak showing the binding state of sulfur and phosphorus in the P2p spectrum measured by X-ray photoelectron spectroscopy (XPS) A phosphorus pentasulfide composition having a ratio (P2 / P1) of P2p quantitative values P2 by state is 0.25 or less.

Further, according to the present invention,
There is provided a raw material composition of a sulfide-based inorganic solid electrolyte material, which comprises the above-mentioned diphosphorus pentasulfide composition and lithium sulfide.

Further according to the invention,
There is provided a method for producing a sulfide-based inorganic solid electrolyte material, which includes a step of mechanically treating the raw material composition of the sulfide-based inorganic solid electrolyte material.

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

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

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

Further according to the invention,
A lithium-ion battery comprising a positive electrode including a positive electrode active material layer, an electrolyte layer, and a negative electrode including a negative electrode active material layer,
There is provided 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 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 which shows the XPS spectrum of the phosphorus pentasulfide composition obtained in the Example. It is a figure which shows the XPS spectrum of the phosphorus pentasulfide composition obtained in the comparative example.

  Embodiments of the present invention will be described below with reference to the drawings. In all the drawings, the same constituents will be referred to with the same numerals, and the description thereof will not be repeated. Moreover, the figure is a schematic view and does not match the actual dimensional ratio. Unless otherwise specified, “A to B” in the numerical range represents A or more and B or less.

[Diphosphorus pentasulfide composition]
First, the diphosphorus pentasulfide composition according to the present embodiment will be described.
The phosphorus pentasulfide composition according to the present embodiment is a phosphorus pentasulfide composition for a sulfide-based inorganic solid electrolyte material (hereinafter, also referred to as phosphorus pentasulfide composition), and is an X-ray photoelectron spectroscopy method. Quantitative value for each P2p state calculated from the peak representing the bound state of oxygen and phosphorus with respect to the P2p state-specific quantified value P1 calculated from the peak representing the bound state of sulfur and phosphorus in the P2p spectrum measured by (XPS) The ratio of P2 (P2 / P1) is 0.25 or less, preferably 0.20 or less. Since the lower P2 / P1 is more preferable, the lower limit of P2 / P1 is not particularly limited, but is, for example, 0.01 or more, 0.03 or more, or 0.05 or more, It may be 0.08 or more.

Here, the P2 / P1 can be obtained by the following procedure.
First, monochromatic Al (1486.6 eV) was used as an X-ray source, and a detection region of 100 μmφ and a detection depth of about 4 to 5 nm (extraction angle of 45 °) were measured by X-ray photoelectron spectroscopy (XPS). For example, the P2p, S2p, O1s, C1s, N1s, and F1s spectra of the phosphorus pentasulfide composition are measured. Of these, waveform analysis is performed on the P2p spectrum. A peak showing a bond of SP (S-P-S, SP = S, etc.) having a binding energy of 132.90 eV, that is, a peak showing a binding state of sulfur and phosphorus is P1, and P ₂ having a binding energy of 134.55 eV. The peak indicating the bond of O ₅ or the like, that is, the peak indicating the bond state of oxygen and phosphorus is designated as P2, and the combined spectrum of these is fitted to the measured spectrum to determine the bond state existence ratio (waveform area ratio). Calculated as the waveform analysis result (%).
The quantitative value (atomic%) for each state of P1 and P2 can be obtained by multiplying the quantitative value (atomic%) of phosphorus (P) by the waveform analysis result (%).
Moreover, when the phosphorus pentasulfide composition contains a solvent, it is preferable to measure after drying and removing the solvent from the phosphorus pentasulfide composition.

In the phosphorus disulfide composition according to the present embodiment, when P2 / P1 is equal to or less than the above upper limit value, the lithium ion conductivity of the obtained sulfide-based inorganic solid electrolyte material can be improved.
Although the reason for this is not necessarily clear, the diphosphorus pentasulfide composition according to the present embodiment is an oxide of phosphorus sulfide (P ₆ S ₅ O ₁₀ or the like) or phosphorus oxide (P ₂ O ₅ or the like). It is thought that this is because the content of is small.
Therefore, P2 / P1 represents an index of the amount of oxides such as phosphorus sulfide oxides (P ₆ S ₅ O _10, etc.) and phosphorus oxides (P ₂ O ₅ etc.) in the phosphorus pentasulfide composition. It is thought that That is, as the P2 / P1 is small, is considered as the amount of oxide _{(P 6} S _{5 O 10,} etc.) or phosphorus oxide _(P 2 _{O 5,} etc.) oxide such as phosphorus sulfide is small.
For the above reasons, the phosphorus disulfide pentasulfide composition according to the present embodiment is considered to reduce the lithium ion conductivity of the obtained sulfide-based inorganic solid electrolyte material, and is considered to be an oxide of phosphorus sulfide (P ₆ S ₅ O). ₁₀ ) and phosphorus oxide (P ₂ O ₅ etc.) and the like, the amount of oxides is small. Therefore, when the phosphorus pentasulfide composition according to the present embodiment is used, the lithium ion of the obtained sulfide-based inorganic solid electrolyte material is increased. It is thought that the conductivity can be improved.
In the present embodiment, the phosphorus pentasulfide composition having P2 / P1 of not more than the above upper limit value is obtained by subjecting the phosphorus pentasulfide raw material composition to vacuum heating to produce a phosphorus pentasulfide composition. It can be obtained by carrying out a treatment for reducing the amount of the oxide of phosphorus sulfide (P ₆ S ₅ O ₁₀ etc.) or phosphorus oxide (P ₂ O ₅ etc.).

  In the phosphorus disulfide composition according to the present embodiment, the P2p state-based quantitative value P2 is preferably 5.0 atomic% or less from the viewpoint of further improving the lithium ion conductivity of the obtained sulfide-based inorganic solid electrolyte material. And more preferably 4.0 atomic% or less, further preferably 3.5 atomic% or less, and even more preferably 3.2 atomic% or less. The lower the P2p state-based quantitative value P2 is, the better. Therefore, the lower limit of P2 is not particularly limited, but may be, for example, 0.1 atomic% or more, and may be 0.5 atomic% or more.

  In the phosphorus disulfide composition according to the present embodiment, the P2p state-based quantitative value P1 is preferably 15.0 atomic% or more from the viewpoint of further improving the lithium ion conductivity of the obtained sulfide-based inorganic solid electrolyte material. Is more preferable, 16.0 atomic% or more is more preferable, and 17.0 atomic% or more is still more preferable. The higher the P2p state-based quantitative value P1 is, the better. Therefore, the upper limit of P1 is not particularly limited, but may be, for example, 25.0 atomic% or less, or 23.0 atomic% or less.

The phosphorus pentasulfide composition according to the present embodiment contains phosphorus pentasulfide (P ₂ S ₅ ) as a main component. 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. It is preferably 97 mass% or more, more preferably 98 mass% or more, still more preferably 99 mass% or more. 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 phosphorus pentasulfide composition according to the present embodiment, examples of components other than phosphorus disulfide (P ₂ S ₅ ) include P ₄ S ₃ , P ₆ S ₅ O ₁₀ , P ₂ O _{5 and the} like. To be

  The properties of the phosphorus pentasulfide composition according to the present embodiment include, for example, powder. Since the production of the sulfide-based inorganic solid electrolyte material described below is generally carried out in a dry system, when the property of the phosphorus pentasulfide composition according to the present embodiment is powdery, the sulfide-based inorganic solid electrolyte material is Manufacturing is easier.

[Method for producing phosphorus pentasulfide composition]
Next, a method for producing the phosphorus pentasulfide composition according to this embodiment will be described.
The manufacturing method of the phosphorus pentasulfide composition according to the present embodiment is different from the conventional manufacturing method of the phosphorus pentasulfide composition. That is, the phosphorus / diphosphorus pentasulfide composition in which P2 / P1 is equal to or less than the above upper limit value is obtained by subjecting the phosphorus / phosphorus pentasulfide raw material composition to, for example, vacuum heating to remove phosphorus sulfide in the phosphorus / phosphorus pentasulfide composition. It can be obtained for the first time by adopting manufacturing process devises such as treatment for reducing the amount of oxides such as oxides (P ₆ S ₅ O ₁₀ etc.) and phosphorus oxides (P ₂ O ₅ etc.).
However, in the method for producing the diphosphorus pentasulfide composition according to the present embodiment, for example, various specific production conditions can be employed on the assumption that the ingenuity in the production method is adopted.
Hereinafter, the method for producing the phosphorus disulfide composition according to the present embodiment will be described more specifically.

The method for producing a phosphorus pentasulfide composition according to this embodiment includes, for example, the following steps (X) and (Y).
Step (X): Step of preparing a raw material composition of phosphorus pentasulfide Step (Y): Oxidation of phosphorus sulfide in the phosphorus pentasulfide composition by heating the raw material composition of phosphorus pentasulfide, for example, in vacuum Of reducing the amount of oxides such as oxides (P ₆ S ₅ O _10, etc.) and phosphorus oxides (P ₂ O _5, etc.)

First, a raw material composition of diphosphorus pentasulfide is prepared.
The raw material composition of diphosphorus pentasulfide used as a raw material is not particularly limited, and commercially available diphosphorus pentasulfide (P ₂ S ₅ ) may be used as it is. A raw material composition of diphosphorus pentasulfide obtained by using the production method may be used.

Next, by heating the raw material composition of diphosphorus pentasulfide, for example, in vacuum, the oxides of phosphorus sulfide (P ₆ S ₅ O _10, etc.) and phosphorus oxides (P ₂ O _5, etc.) in the phosphorus pentasulfide composition are heated. Reduce the amount of oxides such as. Here, vacuum heating is performed until P2 / P1 becomes equal to or less than the above upper limit value. Thereby, the diphosphorus pentasulfide composition according to the present embodiment can be obtained. Here, when the raw material composition of diphosphorus pentasulfide is heated, for example, in vacuum, the component which is not evaporated and is collected at the bottom of the container is usually the diphosphorus pentasulfide composition according to the present embodiment.

The conditions such as the pressure, the heating temperature, and the treatment time when the above-described phosphorus pentasulfide raw material composition is vacuum-heated can be appropriately determined depending on the treatment amount of the phosphorus pentasulfide raw material composition.
The pressure in the vacuum heating device when vacuum-heating the raw material composition of diphosphorus pentasulfide is, for example, −0.01 MPa or less, and preferably −0.07 MPa or less.
The heating temperature at which the above-mentioned raw material composition of diphosphorus pentasulfide is heated in vacuum is, for example, 220 ° C or more and 500 ° C or less, and preferably 250 ° C or more and 350 ° C or less.
The time period for heating the phosphorus disulfide pentasulfide raw material composition under vacuum is, for example, 0.5 hours or more and 24 hours or less, preferably 1 hour or more and 5 hours or less.

[Sulfide inorganic solid electrolyte material]
Hereinafter, the sulfide-based inorganic solid electrolyte material according to this embodiment will be described.
The sulfide-based inorganic solid electrolyte material according to this embodiment can be obtained by using the diphosphorus pentasulfide composition according to this 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 electrochemical stability, stability in water and air, handling property, and the like. It is preferable.
Further, the sulfide-based inorganic solid electrolyte material according to the present embodiment, lithium ion conductivity, electrochemical stability, from the viewpoint of further improving the stability and handleability in water and air, the sulfide The molar ratio Li / P of the content of Li to the content of P in the inorganic 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, still more preferably 3.0 or more and 3.5 or less, and even 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 less. 0.0 or less, more preferably It is 3.0 or more and 5.0 or less, more preferably 3.5 or more and 4.5 or less, even more preferably 3.8 or more and 4.2 or less, still more preferably 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 obtained by, for example, ICP emission spectroscopy 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 10 mV, and measurement frequency range 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, further preferably 0.8 × 10 ⁻³ S · cm ^{−. 1} or more, and 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. Furthermore, 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 a particulate shape.
The particulate sulfide-based inorganic solid electrolyte material according to the present embodiment is not particularly limited, but the average particle diameter 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, still more preferably 5 μm or more and 60 μm or less.
By setting the average particle diameter d ₅₀ of the sulfide-based inorganic solid electrolyte material within the above range, it is possible to maintain good handling properties and further improve lithium ion conductivity.

The sulfide-based inorganic solid electrolyte material according to this embodiment is preferably excellent in electrochemical stability. Here, the electrochemical stability refers to, for example, the property of being hardly oxidized and reduced 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 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 is preferably 0.50 μA or less, more preferably 0.20 μA or less, still more preferably 0.10 μA or less, still 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 in the lithium ion battery can be suppressed.
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 this embodiment can be used for any application requiring 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. Furthermore, the sulfide-based inorganic solid electrolyte material according to the present embodiment is preferably used for a positive electrode active material layer, a negative electrode active material layer, a solid electrolyte layer, and the like that form an all-solid-state lithium ion battery, and all-solid-state lithium ion It is particularly preferably used for a solid electrolyte layer that constitutes a battery.
An example of the all-solid-state lithium-ion battery to which the sulfide-based inorganic solid electrolyte material according to the present embodiment is applied is a positive electrode, a solid electrolyte layer, and a negative electrode stacked in this order.

[Method for producing sulfide-based inorganic solid electrolyte material]
Next, a method for manufacturing the sulfide-based inorganic solid electrolyte material according to this embodiment will be described.
The method for producing a sulfide-based inorganic solid electrolyte material according to the present embodiment, for example, a phosphorus pentasulfide composition according to the present embodiment, and a raw material composition of a sulfide-based inorganic solid electrolyte material containing lithium sulfide, It includes a step of mechanical treatment.
More specifically, the sulfide-based inorganic solid electrolyte material according to the present embodiment can be obtained, for example, by a manufacturing method including the following steps (A) and (B). Further, the method for producing a sulfide-based inorganic solid electrolyte material according to this embodiment may further include the following step (C) and step (D), if necessary.
Step (A): Step of preparing a raw material composition of a sulfide-based inorganic solid electrolyte material containing the phosphorus pentasulfide composition according to the present embodiment and lithium sulfide Step (B): Sulfide-based inorganic solid electrolyte A step of mechanically treating the raw material composition of the material to vitrify the raw material diphosphorus pentasulfide composition and lithium sulfide while chemically reacting to obtain a sulfide-based inorganic solid electrolyte material in a glass state. ) A step of heating the obtained sulfide-based inorganic solid electrolyte material in a glass state to crystallize at least a part thereof Step (D): crushing, 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 a diphosphorus pentasulfide composition according to the present embodiment which is a raw material and lithium sulfide, and further containing lithium nitride as 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 the respective raw materials is not particularly limited as long as it is a mixing method capable of uniformly mixing the respective raw materials, and for example, a ball mill, a bead mill, a vibration mill, an impact crushing device, a mixer (pug mixer, ribbon mixer, tumbler mixer, drum). A mixer, a V-type mixer, etc.), a kneader, a twin-screw kneader, an air flow crusher, a crusher, a rotary blade crusher, and the like can be used for mixing.
The mixing conditions such as stirring speed, processing time, temperature, reaction pressure, and gravitational acceleration applied to the mixture when mixing the respective raw materials can be appropriately determined depending on the amount of the mixture to be processed.

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 the reaction of lithium hydroxide and 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 containing few impurities.
Here, in the present embodiment, lithium polysulfide 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 an inorganic compound as a raw material, 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 according to the present embodiment is not particularly limited, and commercially available lithium nitride (for example, Li ₃ N or the like) may be used. For example, metallic lithium (for example, Li foil) and nitrogen gas may be used. You may use the lithium nitride obtained by the reaction of. From the viewpoint of obtaining a high-purity solid electrolyte material and suppressing side reactions, it is preferable to use lithium nitride containing few impurities.

(Step (B) of obtaining a sulfide-based inorganic solid electrolyte material in a glass state)
Next, by mechanically treating the raw material composition of the sulfide-based inorganic solid electrolyte material, the raw material diphosphorus pentasulfide composition and lithium sulfide are vitrified while chemically reacting, and the sulfide-based inorganic material in the glass state is vitrified. Obtain a solid electrolyte material.

Here, the mechanical treatment is a treatment capable of vitrifying 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 while applying mechanical energy such as shearing force or collision force to the target composition.
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 pulverized into fine particles, so that the contact area of each raw material can be increased. Thereby, 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 vitrification while applying mechanical energy such as shearing force, collision force or centrifugal force to the mixture. As a device for vitrification by mechanochemical treatment (hereinafter referred to as a vitrification device), a ball mill, a bead mill, a vibration mill, a turbo mill, a mechanofusion, a disc mill, a mill such as a roll mill; A rotary / striking crusher consisting of a mechanism that combines rotation (shear stress) and striking (compressive stress) typified by a drill and impact driver; a high-pressure type gliding roll; a roller-type vertical mill, a ball-type vertical mill, etc. A vertical mill and the like can be mentioned. Among these, a ball mill and a bead mill are preferable, and a ball mill is particularly preferable, from the viewpoint that very high impact energy can be efficiently generated. In addition, from the viewpoint of excellent continuous productivity, a roll mill; a rotary / percussion crushing device including a mechanism that combines rotation (shear stress) and impact (compressive stress) represented by rock drills, vibration drills, impact drivers, etc. High pressure type gliding rolls; vertical type mills such as roller type vertical type mills and ball type vertical type mills are preferred.

Mixing conditions such as rotation speed and processing time when mechanically treating the raw material composition of the sulfide-based inorganic solid electrolyte material, temperature, reaction pressure, and gravitational acceleration applied to the raw material inorganic composition are the types of the raw material inorganic composition. It can be determined as appropriate depending on the amount and the processing amount. In general, the faster the rotation speed, the faster the glass production rate, and the longer the treatment time, the higher the conversion rate to glass.
Usually, when the X-ray diffraction analysis using CuKα ray as a radiation source shows that 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 the desired composition is obtained. It can be judged 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 is preferably 27.0 ° C., the applied voltage is 10 mV, and the measurement frequency range is 0.1 Hz to 7 MHz. 1.0 × 10 ⁻⁴ S · cm ⁻¹ or more, more preferably 2.0 × 10 ⁻⁴ S · cm ⁻¹ or more, further preferably 3.0 × 10 ⁻⁴ S · cm ⁻¹ or more, particularly preferably Is preferably vitrified until it becomes 4.0 × 10 ⁻⁴ S · cm ⁻¹ or more. This makes it possible to obtain a sulfide-based inorganic solid electrolyte material that is more excellent in lithium ion conductivity.

(Step (C) of crystallizing at least a part of the sulfide-based inorganic solid electrolyte material)
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 obtain a glass-ceramic state (also referred to as crystallized glass). A sulfide-based inorganic solid electrolyte material is produced. By doing so, it is possible to obtain a sulfide-based inorganic solid electrolyte material having even more excellent lithium ion conductivity.
That is, the sulfide-based inorganic solid electrolyte material according to this embodiment is preferably in a glass ceramics state (crystallized glass state) from the viewpoint of excellent lithium ion conductivity.

The temperature at which the sulfide-based inorganic solid electrolyte material in the glass state is heated is preferably in the range of 220 ° C. or higher and 500 ° C. or lower, and more preferably 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 it is the time for obtaining the desired sulfide-based inorganic solid electrolyte material in the glass-ceramic state. It is within a range of from time to 24 hours, preferably from 1 hour to 3 hours. The heating method is not particularly limited, but for example, a method using a firing furnace can be mentioned. The conditions such as temperature and time during heating can be adjusted as appropriate in order to optimize the characteristics of the sulfide-based inorganic solid electrolyte material according to this embodiment.

Moreover, it is preferable that the sulfide-based inorganic solid electrolyte material in the glass state is heated, for example, in an inert gas atmosphere. Thereby, deterioration (for example, oxidation) of the sulfide-based inorganic solid electrolyte material can be prevented.
Examples of the inert gas used when heating the sulfide-based inorganic solid electrolyte material in the glass state include argon gas, helium gas, and nitrogen gas. These inert gases preferably have a high purity in order to prevent impurities from being mixed into the product, and preferably have a dew point of −70 ° C. or lower in order to avoid contact with water. It is particularly preferable that the temperature is not higher than ° C. The method of introducing the inert gas into the mixed system is not particularly limited as long as it is a method in which the mixed system is filled with an inert gas atmosphere, but a method of purging the inert gas, a constant amount of the inert gas is continuously introduced. Methods and the like.

(Step (D) of crushing, classifying, or granulating)
In the method for producing a sulfide-based inorganic solid electrolyte material according to this 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 diameter can be obtained by pulverizing to fine particles and then adjusting the particle diameter by a classification operation or a granulation operation. The crushing method is not particularly limited, and a known crushing method such as a mixer, an air flow crushing, a mortar, a rotary mill and a coffee mill can be used. The classification method is not particularly limited, and a known method such as sieving can be used.
The pulverization or classification is preferably performed 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 this embodiment, it is important to properly adjust the above steps. However, the method for producing a sulfide-based inorganic solid electrolyte material according to the present embodiment is not limited to the above method, by appropriately adjusting various conditions, the sulfide-based inorganic solid electrolyte material according to the present embodiment. 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 this embodiment includes the sulfide-based inorganic solid electrolyte material according to this 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, within the range not impairing the object of the present invention, the present embodiment described above. A solid electrolyte material of a type different from the sulfide-based inorganic solid electrolyte material according to the present invention may be included.

  The solid electrolyte according to the present embodiment may include a different type of solid electrolyte material from the sulfide-based inorganic solid electrolyte material according to the present embodiment described above. 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 ion conductivity and insulating properties, but generally used for lithium ion batteries Can be used. For example, 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, or another lithium-based inorganic solid electrolyte material; An organic solid electrolyte material such as a polymer electrolyte can be mentioned.

Examples of the sulfide-based inorganic solid electrolyte material different from the above-described sulfide-based inorganic solid electrolyte material according to the present embodiment include Li ₂ S-P ₂ S ₅ material, Li ₂ S-SiS 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 O} -P 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 ₃ N _{materials, Li 2 S 2 + X -P} 4 S 3 _{material, Li 2 S-P 2 S} 5 -P 4 S 3 material, and the like. These may be used alone or in combination of two or more.
Among these, the Li ₂ S—P ₂ S ₅ material is preferable because it has excellent lithium ion conductivity and stability that does not cause decomposition or the like in a wide voltage range. Here, for _example, a Li 2 _S-P 2 _{S 5} material, obtained by chemical reaction with one another by a mechanical treatment of the inorganic composition comprising at least _Li 2 S and (lithium sulfide) and _P 2 _{S 5} solid It means an electrolyte material.
Here, in the present embodiment, lithium polysulfide also includes lithium polysulfide.

Examples of the oxide-based inorganic solid electrolyte material include NASICON types such as LiTi ₂ (PO ₄ ) ₃ , LiZr ₂ (PO ₄ ) ₃ and LiGe ₂ (PO ₄ ) ₃ , and (La _{0.5 + x} Li _{0.5 -3X)} TiO ₃ or the like _{perovskite, 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−xN x} (x is 0 <x ≦ 1), LiN, LiI, and LISON. To be
Furthermore, glass ceramics obtained by depositing 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 in 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, the solid electrolyte containing the sulfide-based inorganic solid electrolyte material according to the present embodiment described above.

The solid electrolyte membrane according to this embodiment is used, for example, in a solid electrolyte layer forming an all-solid-state lithium ion battery.
An example of the all-solid-state lithium-ion battery to which the solid electrolyte membrane according to the present embodiment is applied is one 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 a 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 equal to or more than the lower limit value, the lack of 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 reduced. 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 this embodiment is preferably a pressure-molded body of a particulate solid electrolyte containing the sulfide-based inorganic solid electrolyte material according to this embodiment described above. That is, it is preferable to pressurize the particulate solid electrolyte to form a solid electrolyte membrane having a certain strength due to the anchoring 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, it is possible to further suppress the lack of the solid electrolyte and the occurrence of cracks on the surface of the solid electrolyte membrane.

The content of the above-mentioned sulfide-based inorganic solid electrolyte material according to the present embodiment in the solid electrolyte membrane according to the present embodiment is preferably 50% by mass or more, 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, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Thereby, 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 present 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 shapes of the electrode and the current collector, but can be, for example, rectangular.

Further, the solid electrolyte membrane according to the present embodiment may contain a binder resin, but the content of the binder resin is preferably less than 0.5 mass% when the entire solid electrolyte membrane is 100 mass%. , More preferably 0.1% by mass or less, further 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 does not substantially contain a binder resin, and it is most preferable that the solid electrolyte membrane does not contain a binder resin.
Thereby, 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.
The phrase "substantially free of binder resin" means that the binder resin may be contained to the extent that the effects of the present embodiment are not impaired. Further, when the 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 in the vicinity of the interface between the solid electrolyte layer and the adhesive resin layer is “solid electrolyte "Binder resin in the film".

  The binder resin, in order to bind between the inorganic solid electrolyte material, refers to a binder generally used in lithium ion batteries, for example, polyvinyl alcohol, polyacrylic acid, carboxymethyl cellulose, polytetrafluoro Examples thereof include ethylene, polyvinylidene fluoride, styrene / butadiene rubber, and polyimide.

The solid electrolyte membrane according to the present embodiment, for example, by depositing a particulate solid electrolyte on the cavity surface of the mold or on the surface of the substrate in a film shape, and then pressurizing the solid electrolyte deposited in a film shape. Obtainable.
The method for pressurizing the solid electrolyte is not particularly limited. For example, when a particulate solid electrolyte is deposited on the cavity surface of the mold, pressing with a mold and a pressing mold, the particulate solid electrolyte on the substrate surface When it is deposited on the upper surface, a press using a mold and a pressing die, 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 pressing are performed, fusion and bonding of the solid electrolytes occur, and the strength of the obtained solid electrolyte membrane is further increased. As a result, it is possible to further suppress the lack of the solid electrolyte and the occurrence of cracks on the surface of the solid electrolyte membrane.
The temperature for heating the solid electrolyte is, for example, 40 ° C. or higher and 500 ° C. or lower.

[Lithium-ion battery]
FIG. 1 is a sectional view showing an example of the structure of a lithium ion battery 100 according to an 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 this embodiment, a layer containing a positive electrode active material is referred to as a positive electrode active material layer 101 unless otherwise specified. 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, as necessary. In addition, in this embodiment, a layer containing a negative electrode active material is referred to as a negative electrode active material layer 103 unless otherwise specified. The negative electrode 130 may further include the current collector 105 in addition to the negative electrode active material layer 103, or may not include the current collector 105, as necessary.
The shape of the lithium ion battery 100 according to the present embodiment is not particularly limited, and may be a cylindrical shape, a coin shape, a square shape, a film shape, or any other shape.

  The lithium-ion battery 100 according to the present embodiment is manufactured according to a generally known method. For example, by stacking the positive electrode 110, the electrolyte layer 120, and the negative electrode 130 in a cylindrical shape, a coin shape, a square shape, a film shape, or any other shape, and enclosing a nonaqueous electrolyte solution as necessary. 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 the positive electrode active material layer 101 containing the positive electrode active material on the surface of the current collector 105 such as an aluminum foil.
The thickness and density of the positive electrode active material layer 101 are appropriately determined depending on 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 complex oxides; polyaniline, polypyrrole, and other highly conductive 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 material such as sulfur; acetylene black impregnated with sulfur, porous carbon impregnated with sulfur, sulfur-containing active material such as mixed powder of sulfur and carbon And materials; 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 more excellent in cycle characteristics, and a Li-Mo-S compound, a Li-Ti-S compound, a Li-V-S. One or more selected from the compounds are more preferable.

Here, the Li-Mo-S compound contains Li, Mo, and S as constituent elements, and usually an inorganic composition containing molybdenum sulfide and lithium sulfide as raw materials is chemically treated with each other by mechanical treatment. It can be obtained by reacting.
In addition, the Li-Ti-S compound contains Li, Ti, and S as constituent elements, and usually an inorganic composition containing titanium sulfide and lithium sulfide, which are raw materials, chemically react with each other by mechanical treatment. Can be obtained.
The Li-V-S compound contains Li, V, and S as constituent elements, and is usually obtained by chemically reacting an inorganic composition containing vanadium sulfide and lithium sulfide, which are raw materials, with each other by mechanical treatment. Can be obtained by

  The positive electrode active material layer 101 is not particularly limited, but may include, as a component other than the positive electrode active material, one or more kinds of materials selected from, for example, a binder resin, a thickener, a conductive aid, a solid electrolyte material, and the like. . Hereinafter, each material will be described.

The positive electrode active material layer 101 may include a binder resin having a role of binding the positive electrode active materials to each other and the positive electrode active material and 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, for example, polyvinyl alcohol, polyacrylic acid, carboxymethyl cellulose, polytetrafluoroethylene, polyvinylidene fluoride, styrene. Butadiene-based rubber, polyimide, etc. may be mentioned. These binders may be used alone or in combination of two or more.

  The positive electrode active material layer 101 may include a thickener in order to ensure 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 lithium ion batteries, for example, carboxymethyl cellulose, methyl cellulose, cellulose polymers such as hydroxypropyl cellulose and their ammonium salts and alkali metal salts, Examples thereof include water-soluble polymers such as polycarboxylic acid, polyethylene oxide, polyvinylpyrrolidone, polyacrylic acid salt and polyvinyl alcohol. These thickeners may be used alone or in combination of two or more.

  The positive electrode active material layer 101 may include a conductive additive from the viewpoint of improving the conductivity of the positive electrode 110. The conductive additive is not particularly limited as long as it is a normal conductive additive that can be used in lithium ion batteries, and examples thereof include carbon black such as acetylene black and ketjen black, and carbon materials such as vapor grown carbon fiber. .

  The positive electrode according to the present embodiment may include a solid electrolyte containing the sulfide-based inorganic solid electrolyte material according to the present embodiment described above, and a different type from the sulfide-based inorganic solid electrolyte material according to the present embodiment. It may include a solid electrolyte including 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 ion conductivity and insulating properties, but generally used for lithium ion batteries Can be used. Examples thereof include 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; organic solid electrolyte materials such as polymer electrolytes. More specifically, the inorganic solid electrolyte material mentioned in the description of the solid electrolyte according to this embodiment can be used.

  The blending ratio of various materials in the positive electrode active material layer 101 is appropriately determined depending on 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 in 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 the negative electrode active material layer 103 containing the negative electrode active material on the surface of the current collector 105 such as copper.
The thickness and density of the negative electrode active material layer 103 are appropriately determined depending on 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 a negative electrode of a lithium ion battery, and examples thereof include natural graphite, artificial graphite, resin carbon, carbon fiber, activated carbon, hard carbon, soft carbon. Carbonaceous materials such as: Lithium, lithium alloys, tin, tin alloys, silicon, silicon alloys, gallium, gallium alloys, indium, indium alloys, aluminum, aluminum alloys and other metal-based materials; polyacene, polyacetylene, polypyrrole, etc. A 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 include, as a component other than the negative electrode active material, one or more kinds of materials selected from, for example, a binder resin, a thickener, a conductive additive, a solid electrolyte material, and the like. . Although these materials are not particularly limited, for example, the same materials as those used for the positive electrode 110 described above can be mentioned.
The blending ratio of various materials in the negative electrode active material layer 103 is appropriately determined depending on 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 nonaqueous electrolytic 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 film 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 of an electrolyte in a solvent.
Any known lithium salt can be used as the electrolyte, and it may be selected depending on the type of the 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 _{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, lithium and the like lower fatty acid.

  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 carbonates; γ-butyrolactone, γ-valerolactone and other lactones; trimethoxymethane, 1,2-dimethoxyethane, diethyl ether , Ethers such as 2-ethoxyethane, tetrahydrofuran and 2-methyltetrahydrofuran; sulfoxides such as dimethylsulfoxide; oxolanes such as 1,3-dioxolane and 4-methyl-1,3-dioxolane; acetonite Nitrogen-containing compounds such as ril, nitromethane, formamide and dimethylformamide; organic acid esters such as methyl formate, methyl acetate, ethyl acetate, butyl acetate, methyl propionate and ethyl propionate; phosphoric acid triesters and diglymes; triglymes And sulfolanes such as sulfolane and methylsulfolane; oxazolidinones such as 3-methyl-2-oxazolidinone; sultones such as 1,3-propanesultone, 1,4-butanesultone, and naphthalsultone; and the like. These may be used alone or in combination of two or more.

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, a 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 a desired insulating property can be obtained, 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. Particularly, 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.

  Moreover, 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.
It should be noted that the present invention is not limited to the above-described embodiment, and modifications, improvements, etc. within the scope of achieving the object of the present invention 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] Measuring Method First, the measuring method in the following Examples and Comparative Examples will be described.

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

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

(3) Measurement of X-ray Photoelectron Spectroscopy (XPS) Spectrum The phosphorous disulfide pentasulfide compositions obtained in Examples and Comparative Examples were each subjected to XPS measurement as follows.
Using a pressing device in an argon atmosphere having a water concentration of 1 ppm or less, the powder of the diphosphorus pentasulfide composition (200 mg) obtained in Examples and Comparative Examples was disc-shaped with a diameter of 9.5 mm at 25 ° C. and 270 MPa. Was press-molded for 10 minutes to obtain a test piece having a thickness of 1260 μm. Then, the XPS spectrum of the test piece was measured under the following conditions using an X-ray photoelectron spectrometer.
(XPS analysis conditions)
Measuring device: "Quantera II" manufactured by ULVAC-PHI, Inc.
X-ray source: Monochromatic Al (1486.6 eV)
Detection area: 100 μmφ
Detection location: Center of test piece Detection depth: Approximately 4 to 5 nm (extraction angle 45 °)
Measurement spectrum: P2p, S2p, O1s, C1s, N1s, F1s
Element quantification method: The background was obtained by the Shirley method, and the peak area was quantified by the relative sensitivity coefficient method. For data processing, MultiPak manufactured by ULVAC-PHI, Inc. was used.
Here, waveform analysis was performed on the P2p spectrum, and P1, P2, and P2 / P1 were calculated. A peak representing the binding state of sulfur and phosphorus such as SP (SPPS, SP = S) having a binding energy of 132.90 eV is P1, and oxygen such as P ₂ O ₅ having a binding energy of 134.55 eV is P1. The peak representing the binding state of phosphorus and phosphorus is set to P2, and the combined spectrum of these is fitted to the measured spectrum to obtain the binding state existence ratio (waveform area ratio) of P1 and P2, and set it as the waveform analysis result (%). .
The quantitative value (atomic%) for each state of P1 and P2 was obtained by multiplying the quantitative value (atomic%) of phosphorus (P) by the waveform analysis result (%).

(4) Measurement of lithium ion conductivity With respect to the sulfide-based inorganic solid electrolyte materials obtained in Examples and Comparative Examples, lithium ion conductivity was measured by an 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, 1.2 to 2.0 mm in thickness, 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 electrodes were Li foil. .
Here, as the sample for measuring lithium ion conductivity, 150 mg of the powdery sulfide-based inorganic solid electrolyte material obtained in Examples and Comparative Examples was pressed at 270 MPa for 10 minutes using a pressing 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.

(5) Measurement of maximum value of oxidative decomposition current Using a pressing device, 120 to 150 mg of the powdery sulfide-based inorganic solid electrolyte material obtained in Examples and Comparative Examples was pressed at 270 MPa for 10 minutes to have a diameter of 9. A plate-shaped sulfide-based inorganic solid electrolyte material (pellets) having a thickness of 5 mm and a thickness of 1.3 mm was obtained. Then, Li foil as a reference electrode / counter electrode was press-bonded to one surface of the obtained pellets under the conditions of 18 MPa and 10 minutes, and SUS314 foil was adhered to the other surface as a working electrode.
Then, oxidative decomposition of the sulfide-based inorganic solid electrolyte material 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, using a potentiostat / galvanostat SP-300 manufactured by Biologics. The maximum value of the current was obtained and evaluated according to the following criteria.
⊚: 0.03 μA or less ◯: Exceeds 0.03 μA 0.50 μA or less ×: Exceeds 0.50 μA

[2] Production of solid electrolyte material A sulfide-based inorganic solid electrolyte material was produced by the following procedure.
Li ₂ S (Furukawa Kikai Metal Co., Ltd., purity 99.9%) and Li ₃ N (Furukawa Kikai Metal Co., Ltd.) were used as raw materials, and P ₂ S ₅ was obtained in Examples and Comparative Examples. P ₂ S ₅ was used respectively.
First, a rotary blade type pulverizer and an alumina pot (internal volume: 400 mL) were placed in the glove box, and then the high-purity dry argon gas (H Injection of ₂ O <1 ppm, O ₂ <1 ppm) and vacuum deaeration were performed 3 times.
Then, in a glove box, a Li ₂ S powder, a P ₂ S ₅ powder, and a Li ₃ N powder (Li ₂ S: P ₂ S ₅ : Li ₃ N) were used by using a rotary blade type pulverizer (rotation speed 18000 rpm). = 71.1: 23.7: 5.3 (mol%)) by a total of 5 g (10 times of mixing and 10 seconds of standing 10 times (cumulative mixing time: 100 seconds)). A raw inorganic composition was prepared.

Subsequently, the raw material inorganic composition and 500 g of ZrO ₂ balls having a diameter of 10 mm were placed inside an alumina pot (internal volume 400 mL) in the glove box, and the pot was sealed.
Then, take out the alumina pot from the glove box, attach the alumina pot to the ball mill machine installed under the atmosphere of dry dry air introduced through the membrane air dryer, and perform mechanochemical treatment 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 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 annealed 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 Powder) manufactured by LIAONING RUIXING CHEMICAL GROUP was used.
Then, the raw material composition of diphosphorus pentasulfide was placed in a quartz container and set in a vacuum heating device (manufactured by Furukawa Machinery Co., Ltd.). Then, it was heated under vacuum at -0.094 MPa for 2 hours at 300 ° C. Then, the components accumulated at the bottom of the quartz container were collected to obtain phosphorus pentasulfide composition 1. Each evaluation was performed on the obtained phosphorus 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 Flakes) manufactured by LIAONING RUIXING CHEMICAL GROUP was used.
Then, the raw material composition of diphosphorus pentasulfide was placed in a quartz container and set in a vacuum heating device (manufactured by Furukawa Machinery Co., Ltd.). Then, it was heated under vacuum at -0.094 MPa for 2 hours at 300 ° C. Then, the components accumulated at the bottom of the quartz container were collected to obtain a phosphorus disulfide pentasulfide composition 2. Each evaluation was performed on the obtained phosphorus pentasulfide composition 2. The results obtained are shown in Table 1.

<Example 3>
As a raw material composition of diphosphorus pentasulfide, diphosphorus pentasulfide manufactured by LIAONING RUIXING CHEMICAL GROUP (product name: SUPERIOR GRADE Powder and Flakes 1) was used.
Then, the raw material composition of diphosphorus pentasulfide was placed in a quartz container and set in a vacuum heating device (manufactured by Furukawa Machinery Co., Ltd.). Then, it was heated under vacuum at -0.094 MPa for 2 hours at 300 ° C. Then, the components accumulated at the bottom of the quartz container were collected to obtain a phosphorus pentasulfide composition 3. Each evaluation was performed on the obtained phosphorus pentasulfide composition 3. The results obtained are shown in Table 1.

<Example 4>
As a raw material composition of diphosphorus pentasulfide, phosphorus disulfide pentasulfide (product name: SUPERIOR GRADE Powder and Flake 2) manufactured by LIAONING RUIXING CHEMICAL GROUP was used.
Then, the raw material composition of diphosphorus pentasulfide was placed in a quartz container and set in a vacuum heating device (manufactured by Furukawa Machinery Co., Ltd.). Then, it was heated under vacuum at -0.094 MPa for 2 hours at 300 ° C. Then, the components accumulated at the bottom of the quartz container were collected to obtain phosphorus pentasulfide composition 4. Each evaluation was performed on the obtained phosphorus pentasulfide composition 4. The results obtained are shown in Table 1.

<Comparative Example 1>
As the phosphorus pentasulfide composition 5, phosphorus pentasulfide (product name: SUPERION GRADE Powder) manufactured by LIAONING RUIXING CHEMICAL GROUP was used as it was. Each evaluation was performed on the phosphorus pentasulfide composition 5. The results obtained are shown in Table 1.

<Comparative example 2>
As the diphosphorus pentasulfide composition 6, diphosphorus pentasulfide (product name: SUPERIOR GRADE Flake) manufactured by LIAONING RUIXING CHEMICAL GROUP was used as it was. Each evaluation was performed on the phosphorus pentasulfide composition 6. The results obtained are shown in Table 1.

<Comparative example 3>
As the diphosphorus pentasulfide composition 7, diphosphorus pentasulfide manufactured by LIAONING RUIXING CHEMICAL GROUP (product name: SUPERIOR GRADE Powder and Flakes 1) was used as it was. Each evaluation was performed on the phosphorus pentasulfide composition 7. The results obtained are shown in Table 1.

<Comparative example 4>
As the phosphorus pentasulfide composition 8, phosphorus pentasulfide (product name: SUPERION GRADE Powder and Flakes 2) manufactured by LIAONING RUIXING CHEMICAL GROUP was used as it was. Each evaluation was performed on the phosphorus pentasulfide composition 8. The results obtained are shown in Table 1.

  Here, the raw material compositions of diphosphorus pentasulfide manufactured by LIAONING RUIXING CHEMICAL GROUP, which were used in Examples and Comparative Examples, are sold as high-purity grades.

The sulfide-based inorganic solid electrolyte material obtained by using the phosphorus pentasulfide composition of Example as a raw material is a sulfide-based inorganic solid electrolyte material obtained by using the phosphorus pentasulfide composition of Comparative Example as a raw material. Was superior to lithium ion conductivity.
Here, X-ray diffraction spectra of the diphosphorus pentasulfide compositions in Examples and Comparative Examples are shown in FIGS. 2 and 3, 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 phosphorus pentasulfide composition for a sulfide-based inorganic solid electrolyte material,
Calculated from the peak showing the binding state of oxygen and phosphorus with respect to the quantitative value P1 for each P2p state calculated from the peak showing the binding state of sulfur and phosphorus in the P2p spectrum measured by X-ray photoelectron spectroscopy (XPS) A phosphorus pentasulfide composition in which the ratio (P2 / P1) of the quantitative value P2 for each P2p state is 0.25 or less. The diphosphorus pentasulfide composition according to claim 1,
A diphosphorus pentasulfide composition having a quantitative value P2 for each P2p state of 5.0 atomic% or less. The diphosphorus pentasulfide composition according to claim 1 or 2,
A phosphorus pentasulfide composition having a P2p state-specific quantitative value P1 of 15.0 atomic% or more. The diphosphorus pentasulfide composition according to any one of claims 1 to 3,
A phosphorus pentasulfide composition in which the content of phosphorus pentasulfide in the phosphorus pentasulfide composition is 95% by mass or more. The diphosphorus pentasulfide composition according to any one of claims 1 to 4,
A powdered diphosphorus pentasulfide composition.   A raw material composition for a sulfide-based inorganic solid electrolyte material, comprising 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, comprising the 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 comprising a positive electrode including a positive electrode active material layer, an electrolyte layer, and a negative electrode including a negative electrode active material layer,
At least one of the said positive electrode active material layer, the said electrolyte layer, and the said negative electrode active material layer is a lithium ion battery containing the sulfide type inorganic solid electrolyte material of Claim 8.

Images